+

WO2024218124A1 - Composition comprising an antimicrobial agent and an alkoxylated amine - Google Patents

Composition comprising an antimicrobial agent and an alkoxylated amine Download PDF

Info

Publication number
WO2024218124A1
WO2024218124A1 PCT/EP2024/060367 EP2024060367W WO2024218124A1 WO 2024218124 A1 WO2024218124 A1 WO 2024218124A1 EP 2024060367 W EP2024060367 W EP 2024060367W WO 2024218124 A1 WO2024218124 A1 WO 2024218124A1
Authority
WO
WIPO (PCT)
Prior art keywords
antimicrobial agent
weight
acid
composition
alkyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/EP2024/060367
Other languages
French (fr)
Inventor
Hauke Rohwer
Juergen Wiethan
Eva Maria BETTHAUSEN
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of WO2024218124A1 publication Critical patent/WO2024218124A1/en
Anticipated expiration legal-status Critical
Pending legal-status Critical Current

Links

Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P1/00—Disinfectants; Antimicrobial compounds or mixtures thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/30—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests characterised by the surfactants
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N31/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic oxygen or sulfur compounds
    • A01N31/08—Oxygen or sulfur directly attached to an aromatic ring system
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N31/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic oxygen or sulfur compounds
    • A01N31/08—Oxygen or sulfur directly attached to an aromatic ring system
    • A01N31/16—Oxygen or sulfur directly attached to an aromatic ring system with two or more oxygen or sulfur atoms directly attached to the same aromatic ring system
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
    • A01N33/16—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds containing nitrogen-to-oxygen bonds
    • A01N33/18—Nitro compounds
    • A01N33/20—Nitro compounds containing oxygen or sulfur attached to the carbon skeleton containing the nitro group
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/10—Aromatic or araliphatic carboxylic acids, or thio analogues thereof; Derivatives thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/36—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids
    • A01N37/38—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids having at least one oxygen or sulfur atom attached to an aromatic ring system
    • A01N37/40—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids having at least one oxygen or sulfur atom attached to an aromatic ring system having at least one carboxylic group or a thio analogue, or a derivative thereof, and one oxygen or sulfur atom attached to the same aromatic ring system
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/12—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, neither directly attached to a ring nor the nitrogen atom being a member of a heterocyclic ring

Definitions

  • composition comprising an antimicrobial agent and an alkoxylated amine
  • the present invention relates to a composition
  • a composition comprising an antimicrobial agent (a) as defined below and a specific alkoxylated amine (b) as defined below, to the use of an alkoxylated amine (b) as defined below for enhancing the antimicrobial, in particular the preserving, activity of the antimicrobial agent (a) and to a method for enhancing the antimicrobial, in particular the preserving, activity of the antimicrobial agent (a) comprising using the antimicrobial agent (a) in combination with said alkoxylated amine (b).
  • Antimicrobial agents like those listed below as component (a), are well established preservatives or biocides in a vast range of application areas.
  • a number of products and materials is susceptible to microbial attack or degradation, which attack not only reduces the economic value of such products or materials, but may even pose a health hazard for the user.
  • Microbial degradation in aqueous systems can become manifest in many forms, such as loss of viscosity, emulsion breaking, change of pH, color change, unpleasant odor, fouling, gas formation, slime formation, to name just a few and easily identifiable indicators. Some of these manifestation also occur in non-aqueous systems, e.g. fouling in fuels, heating oils, crude oils and the like.
  • Antimicrobial agents are either incorporated into susceptible products or materials to preserve them, or are used as such or in suitable formulations to treat infected products or materials.
  • Examples for products, materials and formulations containing antimicrobial agents are homecare compositions and articles, compositions and articles for cleaning or disinfecting on an industrial scale, personal care compositions and articles, process water, cooling water (e.g. in industrial plants, cooling towers), water in fish or shrimp ponds, water in drinking troughs, metal working fluids; water based raw materials, polymer solutions, polymer dispersions, polymer emulsions, inorganic slurries, organic slurries, surfactant compositions; compositions for treating animal hide, leather, textiles, lumber, or paper or the precursor materials thereof during papermaking processes; crop protection compositions; pharmaceutical compositions; paints, glues, adhesives, sealants, dyes, pigments and dispersions thereof, inks and the like.
  • the antimicrobial effect of some antimicrobials is moreover thwarted by some standard detergents, such as detergents with alkyl chains of at least 8 carbon atoms and in particular ethoxylated alkohols with at least 8 carbon atoms in the alkyl chain or alkyl benzene sulfonates with at least 10 carbon atoms in the alkyl chain. It would be desirable to reduce this thwarting effect.
  • the object of the present invention is to improve the effect of certain antimicrobials.
  • a more specific object is to provide a composition with an improved preservative and/or biocidal effect.
  • An additional object for detergent-containing compositions is to reduce the thwarting effect which some standard detergents have on the antimicrobial effect of certain antimicrobials.
  • the inventors of the present invention found that certain alkoxylated amines as defined below improve the preservative and/or biocidal effect of certain antimicrobials.
  • said alkoxylated amines have the advantage that they have a detergent-boosting effect, which allows to reduce the amount of other detergents which have the potential to reduce the antimicrobial effect of certain antimicrobials, such as 2-phenoxyethanol.
  • the present invention therefore relates to a composition
  • a composition comprising
  • At least one antimicrobial agent selected from the group consisting of 2-phenoxy- ethanol, phenoxyisopropanol, 4,4’-dichloro 2’-hydroxydiphenylether, 2-bromo-2- nitropropane-1 ,3-diol (bronopol), glutaraldehyde, 2,4-dichlorobenzylalcohol, 1 ,3,5-tris-(2-hydroxyethyl)-1 ,3,5-hexahydrotriazine, formic acid and salts thereof, benzoic acid and salts thereof, sorbic acid and salts thereof, lactic acid and salts thereof, isothiazolinones selected from the group consisting of 1 ,2-benzisothia- zol-3(2H)-one (BIT), 2-methyl-2H-isothiazol-3-one (MIT), 2-octyl-2H-isothiazol-3- one (OIT), 5-chloro-2-methyl-2H-isothiazol
  • R 1 is -CH 2 CH 2 O-A n -B m -H; -CH 2 CH 2 O-B m -A n -H or -CH 2 CH 2 O-E m+n -H; where A is -CH 2 CH 2 O-;
  • B is -CH(R a )-CH 2 -O- or -CH 2 -CH(R a )-O-;
  • E is randomly distributed A and B;
  • R a is Ci-C -alkyl; m is 0 to 30; and n is 0 to 15; where the sum of m + n is 5 to 40; and R 2 and R 3 have independently one of the meanings of R 1 or are Ci-C -alkyl.
  • the invention relates moreover to the use of an alkoxylated amine (I) as defined above for enhancing the antimicrobial, in particular the preserving, activity of the antimicrobial agent as defined above as component (a).
  • the invention relates also to a method for enhancing the antimicrobial, in particular the preserving, activity of the antimicrobial agent as defined above as component (a), comprising using the antimicrobial agent (a) in combination with said alkoxylated amine (I).
  • the invention relates further to a kit of parts comprising at least two parts, where the first part comprises at least one antimicrobial agent as defined above as component (a); the second part comprises at least one alkoxylated amine (I) as defined above and optionally at least one organic solvent; and an optional third part comprises at least one organic solvent.
  • an antimicrobial agent or short antimicrobial is an agent that combats or controls microbes.
  • microbicide and “biocide” are used as synonyms for antimicrobials.
  • Microbes in the terms of the present invention are undesired harmful microorganisms and comprise bacteria, fungi (including yeasts and molds), microscopic algae, protozoans, spores thereof and, despite the fact that they are generally not considered as living beings, also viruses and prions.
  • "Harmful” means that the microorganism have an unwanted presence or a detrimental effect on humans, their activities or the products they use or produce, or on animals, materials, plants or the environment.
  • An antimicrobial effect encompasses a preservative as well as a biocidal effect.
  • Preservative or preserving effect in terms of the present invention means that the material or product as such comprising an antimicrobial agent is protected against deterioration by microbial attack. As a consequence, the thusly protected material or product has for example a longer storage stability.
  • an antimicrobial is used in a laundry detergent composition as a preservative to keep the composition storage-stable by avoiding or reducing the proliferation or growth of microbes present therein and thus avoiding or reducing the deterioration of the properties of the composition, such as the formation of malodours, a change in viscosity or pH, a phase separation etc.
  • Biocidal effect in terms of the present invention means that the composition comprising an antimicrobial agent exerts its antimicrobial effect on a product or material treated with and different from this composition.
  • this composition exerts a biocidal effect in terms of the present invention if microorganisms on or in laundry treated therewith are killed or hampered in their proliferation or growth by the application of said composition.
  • Another example of a biocidal application is a disinfectant or sanitizer composition which exerts its biocidal effect on materials or products treated therewith.
  • the biocidal effect has to be fast, since microbes on or in the treated materials or products have to be eliminated or reduced within seconds or minutes, whereas the preservative effect is a long-term effect, since it has to prevail throughout the shelf-life of the product, which can be years.
  • Many antimicrobials have both a preservative and a biocidal effect, the prevalence depending mainly on the concentration of the antimicrobial in the composition.
  • Phenoxyisopropanol is 1-phenoxy-propan-2-ol. Commercially available phenoxyisopropanol may however also contain minor amounts (i.e. up to 5% by weight) of the isomeric 2-phenoxy-propan-2-ol; such mixtures also fall under the term “phenoxyisopropanol” as used in context of the present invention. Phenoxyisopropanol contains a stereo- genic center and can thus be present in form of the essentially pure S enantiomer, the essentially pure R enantiomer and mixtures of the two enantiomers, including racemic mixtures. The present invention encompasses both the use of the essentially pure enantiomers and of mixtures of the two enantiomers, including racemic mixtures. Generally, however, the racemate is used, since this is the commercially most common form thereof.
  • the organic moieties mentioned below are collective terms for individual listings of the individual group members.
  • the prefix C n -C m indicates in each case the possible number of carbon atoms in the group.
  • alkyl as used herein is used in the proper sense and refers to saturated straight-chain (linear) or branched non-cyclic hydrocarbon radicals having the indicated number of carbon atoms.
  • Ci-C4-Alkyl denotes thus an alkyl radical with 1 to 4 carbon atoms. Examples are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and tert-butyl.
  • Ci-Cs-Alkyl denotes an alkyl radical with 1 to 5 carbon atoms.
  • Ci-C4-alkyl examples are, in addition to those mentioned above for Ci-C4-alkyl, n-pentyl, 1 -methyl butyl, 2-methyl- butyl, 3-methylbutyl, 2,2-dimethylpropyl, 1 -ethylpropyl, 1 ,1 -dimethylpropyl, 1 ,2-dime- thylpropyl and other structural isomers thereof.
  • Ci-Ce-Alkyl denotes an alkyl radical with 1 to 6 carbon atoms.
  • Ci-Cs-al- kyl examples are, in addition to those mentioned above for Ci-Cs-al- kyl, n-hexyl, 1 -methylpentyl, 2-methyl pentyl, 3-methylpentyl, 4-methylpentyl, 1 ,1-dime- thylbutyl, 1 ,2-dimethylbutyl, 1 ,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3- dimethylbutyl, 1 -ethylbutyl, 2-ethylbutyl, 1 , 1 ,2-trimethylpropyl, 1 ,2,2-trimethylpropyl, 1- ethyl-1-methylpropyl, 1-ethyl-2-methylpropyl and other structural isomers thereof.
  • Ci- Cs-Alkyl denotes an alkyl radical with 1 to 8 carbon atoms. Examples are, in addition to those mentioned above for Ci-Ce-alkyl, n-heptyl, n-octyl, 2-ethylhexyl and (other) structural isomers thereof. Ci-C -Alkyl denotes an alkyl radical with 1 to 10 carbon atoms. Examples are, in addition to those mentioned above for Ci-Cs-alkyl, n-nonyl, n-decyl, 2- propylheptyl and (other) structural isomers thereof. Ci-C -Alkyl denotes an alkyl radical with 1 to 16 carbon atoms.
  • Ci-C -alkyl examples are, in addition to those mentioned above for Ci-C -alkyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl and structural isomers thereof.
  • Ci-Cis-Alkyl denotes an alky radical with 1 to 18 carbon atoms. Examples are, in addition to those mentioned for Ci-C -alkyl, n-heptadecyl, n- octadecyl and structural isomers thereof.
  • Ci-C4-Hydroxyalkyl denotes a linear or branched Ci-C4-alkyl radical, as defined above, wherein one hydrogen atom is replaced by an OH group.
  • Ci-Cs-Hydroxyalkyl denotes a linear or branched Ci-Cs-alkyl radical, as defined above, wherein one hydrogen atom is replaced by an OH group.
  • Examples are hydroxymethyl, 1-hydroxyethyl, 2-hydroxy- ethyl, 1-hydroxy-n-propyl, 2-hydroxy-n-propyl, 3-hydroxy-n-propyl, 1 -hydroxy- 1 -methylethyl, 2-hydroxy-1-methyl-ethyl, 1-hydroxy-n-butyl, 2-hydroxy-n-butyl, 3-hydroxy-n-bu- tyl, 4-hydroxy-n-butyl and the like.
  • ppm means weight-ppm and corresponds to 1 g of component per 1,000,000 g of the reference. Alternatively expressed, 1 ppm corresponds to 0.0001% by weight.
  • Embodiments (E.x) of the invention Embodiments (E.x) of the invention
  • At least one antimicrobial agent selected from the group consisting of 2-phenoxy- ethanol, phenoxyisopropanol, 4,4’-dichloro 2’-hydroxydiphenylether, 2-bromo-2- nitropropane-1,3-diol, glutaraldehyde, 2,4-dichlorobenzylalcohol, 1 ,3,5-tris-(2-hy- droxyethyl)-1 ,3,5-hexahydrotriazine, formic acid and salts thereof, benzoic acid and salts thereof, sorbic acid and salts thereof, lactic acid and salts thereof, iso- thiazolinones selected from the group consisting of 1 ,2-benzisothiazol-3(2H)-one (BIT), 2-methyl-2H-isothiazol-3-one (MIT), 2-octyl-2H-isothiazol-3-one (OIT), 5- chloro-2-methyl-2H-isothiazol
  • DBNPA 2,2-dibromo-2-cyanoacetamide
  • Diamine N-(3-ami- nopropyl)-N-dodecylpropane-1 ,3-diamine
  • THPS tetrakis(hydroxymethyl)- phosphonium sulphate(2:1)
  • DTBMA 2,2-dithiobis[N-methylbenzamide]
  • R 1 is -CH 2 CH 2 O-A n -B m -H; -CH 2 CH 2 O-B m -A n -H or -CH 2 CH 2 O-E m+n -H; where A is -CH 2 CH 2 O-;
  • B is -CH(R a )-CH 2 -O- or -CH 2 -CH(R a )-O-;
  • E is randomly distributed A and B;
  • R a is Ci-C -alkyl; m is 0 to 30; and n is 0 to 15; where the sum of m + n is 5 to 40; and R 2 and R 3 have independently one of the definitions given for R 1 or are C1-C18- alkyl.
  • composition according to embodiment E.1 where the antimicrobial agent is selected from the group consisting of 2-phenoxyethanol, phenoxyisopropanol, 4,4’-dichloro 2’-hydroxydiphenylether, 2-bromo-2-nitropropane-1 ,3-diol, glutaraldehyde, benzoic acid and salts thereof and isothiazolinones selected from the group consisting of 1 ,2-benzisothiazol-3(2H)-one (BIT), 2-methyl-2H-isothiazol-3- one (MIT), 2-octyl-2H-isothiazol-3-one (OIT), 5-chloro-2-methyl-2H-isothiazol-3- one (CM IT) and 2-butyl-benzo[d]isothiazol-3-one (BBIT); and preferably from the group consisting of 2-phenoxyethanol, phenoxyisopropanol, 4,4’-dichloro 2’-hy- dr
  • the antimicrobial agent is selected from the group consisting of 2-phenoxyethanol, 4,4’-dichloro 2’-hy- droxydiphenylether, benzoic acid and salts thereof and 1 ,2-benzisothiazol- 3(2H)one (BIT).
  • composition according to embodiment E.2, where the antimicrobial agent is selected from the group consisting of 2-phenoxyethanol, 2-bromo-2-nitropropane- 1 ,3-diol, glutaraldehyde and 1 ,2-benzisothiazol-3(2H)one (BIT).
  • composition according to embodiment E.21 where the antimicrobial agent and the alkoxylated amine are present in an overall weight ratio of from 2:1 to 1 :450.
  • E.23 The composition according to any of the preceding embodiments, where the antimicrobial agent is 2-phenoxyethanol, and 2-phenoxyethanol and the alkoxylated amine are present in an overall weight ratio of from 3:1 to 1 :3.
  • the antimicrobial agent is selected from the group consisting of 2-bromo-2-nitropropane- 1 ,3-diol, glutaraldehyde and 1 ,2-benzisothiazol-3(2H)one (BIT); and the antimicrobial agent and the alkoxylated amine are present in an overall weight ratio of from 1 :1 to 1 :10000.
  • composition according to embodiment E.31 where the antimicrobial agent and the alkoxylated amine are present in an overall weight ratio of from 1 :1 to 1 :450.
  • the antimicrobial agent is selected from the group consisting of 2-phenoxyethanol, 2- bromo-2-nitropropane-1 ,3-diol, glutaraldehyde and 1 ,2-benzisothiazol-3(2H)one (BIT); in the
  • the antimicrobial agent is selected from the group consisting of 2-phenoxyethanol, 2-bromo-2-nitropropane- 1 ,3-diol, glutaraldehyde and 1 ,2-benzisothiazol-3(2H)one (BIT); in the alkoxyl
  • E.36 The composition according to any of embodiments E.34 or E.35, where the antimicrobial agent is 2-phenoxyethanol; in the alkoxylated amine of the formula (I) R 1 , R 2 and R 3 are independently -CH2CH2O-A n -B m -H, where R a is methyl, m is 10 to 30 and n is 3 to 12; or m is 10 to 20 and n is 0; and the antimicrobial agent and the alkoxylated amine are present in an overall weight ratio of from 3:1 to 1 :5.
  • the antimicrobial agent is selected from the group consisting of 2-bromo-2-nitropropane- 1 ,3-diol, glutaraldehyde and 1 ,2-benzisothiazol-3(2H)one (BIT); in the alkoxylated amine of the formula (
  • composition according to any of embodiments E.42 to E.44, the antimicrobial agent and the alkoxylated amine are present in an overall weight ratio of from 1 :1 to 1 :450.
  • R 4 is hydrogen or Ci-Cs-alkyl
  • R 5 is Ci-Cs-alkyl
  • R 6 is Ci-Cs-alkyl or Ci-Cs-hydroxyalkyl
  • R 6 is Ci-Cs-alkyl or Ci-Cs-hydroxyalkyl
  • R 7 is Ci-Cio-alkyl
  • R 9 and R 10 are independently Ci-C4-alkyl or form together an oxo group
  • R 11 is Ci-C4-alkyl or Ci-C4-hydroxyalkyl
  • Ci-Ce-alkylmonoethers of diethylene glycol or dipropylene glycol Ci-Ce-alkylmonoethers of diethylene glycol or dipropylene glycol; and (c.8) the lactone of formula (C-8), where R 8 is methyl.
  • composition according to embodiment E.48, where the organic solvent of component (c) is selected from the group consisting of
  • E.55. The composition according to any of the preceding embodiments, which is selected from the group consisting of antimicrobial concentrates, homecare compositions, compositions for cleaning or disinfecting on an industrial scale, personal care compositions, process water, cooling water, water in fish or shrimp ponds, water in drinking troughs, metal working fluids; water based raw materials, polymer solutions, polymer dispersions, polymer emulsions, inorganic slurries, organic slurries, surfactant compositions; compositions for treating animal hide; compositions for treating leather; compositions for treating textiles during the manufacturing process thereof; compositions for treating lumber; compositions for treating paper or the precursor material during papermaking processes; crop protection compositions; pharmaceutical compositions; paints, glues, adhesives, sealants, dyes, pigments and dispersions thereof, inks, and wet wipes.
  • Kit of parts comprising at least two parts, where the first part comprises at least one antimicrobial agent as defined in any of embodiments E.1 to E.6; the second part comprises an alkoxylated amine as defined in any of embodiments E.1 and E.6 to E.15 and optionally at least one organic solvent; and an optional third part comprises at least one organic solvent; where the first part does not comprise an alkoxylated amine as defined in any of embodiments E.1 and E.6 to E.15; where the second part does not comprise any antimicrobial agent as defined in any of embodiments E.1 to E.5; where the optional third part does not comprise any antimicrobial agent as defined in any of embodiments E.1 to E.5 nor an alkoxylated amine as defined in any of embodiments E.1 and E.6 to E.15; and where the first and second parts contain the at least one antimicrobial agent as defined in any of embodiments E.1 to E.5 and the alkoxylated amine as defined in any of embodiments E.1 to
  • E.58 The use according to embodiment E.57 of an alkoxylated amine as defined in any of embodiments E.1 and E.6 to E.15 for enhancing the antimicrobial, in particular the preserving, activity of 2-phenoxyethanol.
  • the antimicrobial agent is inter alia selected from formic acid and salts thereof, benzoic acid and salts thereof, sorbic acid and salts thereof, lactic acid and salts thereof.
  • Suitable salts of these acids are alkali metal salts, such as the lithium, sodium or potassium salts; earth alkaline metal salts, such as the magnesium and calcium salts, and ammonium salts, such as the salts containing an ammonium cation of the formula [NR a R b R c R d ] + , where R a , R b , R c and R d , independently of each other, are selected from the group consisting of hydrogen, Ci-C4-alkyl and Ci-C4-alkoxy.
  • alkali metal salts, and in particular the sodium or potassium salts are used.
  • the antimicrobial agent is preferably selected from the group consisting of 2-phenoxy- ethanol, phenoxyisopropanol, 4,4’-dichloro 2’-hydroxydiphenylether (diclosan), 2- bromo-2-nitropropane-1 ,3-diol (bronopol), glutaraldehyde, benzoic acid and salts thereof and isothiazolinones selected from the group consisting of 1 ,2-benzisothiazol- 3(2H)-one (BIT), 2-methyl-2H-isothiazol-3-one (MIT), 2-octyl-2H-isothiazol-3-one (OIT), 5-chloro-2-methyl-2H-isothiazol-3-one (CM IT) and 2-butyl-benzo[d]isothiazol-3-one (BBIT); and more preferably from the group consisting of 2-phenoxyethanol, phenoxyisopropanol, 4,4’-dichloro 2’-hydroxydiphenyl
  • the antimicrobial agent is selected from the group consisting of 2-phenoxyethanol, 2-bromo-2-nitropropane-1 ,3-diol (bronopol), glutaraldehyde and 1 ,2-benzisothiazol-3(2H)-one (BIT).
  • the antimicrobial agent is 2-phenoxyethanol.
  • the antimicrobial agents of component (a) are known in the art and are commercially available or can be prepared by known methods.
  • the alkoxylated amines (I) are also known in the art and are either commercially available, e.g. Plurafac® LF 1430 from BASF, or can be prepared by standard methods of organic chemistry.
  • Plurafac® LF 1430 from BASF
  • triethanolamine N(CH2CH2OH)s is typically reacted with the necessary amounts of propylene oxide (PO) and/or ethylene oxide (EO).
  • alkoxylated amines (I) in which R 1 , R 2 and R 3 are -CF ⁇ CFW-An-Bm-H or - CH 2 CH 2 O-Bm-An-H and in which neither m nor n are 0, i.e.
  • triethanolamine is reacted with a mixture of EO and PO containing EO and PO in an amount corresponding to the desired m and n.
  • triethanolamine is reacted with the necessary amount of PO only.
  • triethanolamine is reacted with the necessary amount of EO only.
  • Alkoxylated amines in which one or both of R 2 and R 3 are C1-C1 s-alkyl can be obtained analogously by reacting a Ci-Ci8-alkyl-diethanolamine (if only one R 2 and R 3 is C1-C1 s-alkyl) with PO and/or EO as described above, or by reacting a di-(Ci-Cis-alkyl)-ethanolamine (if both of R 2 and R 3 are C1-C1 s-alkyl) with PO and/or EO as described above.
  • corresponding alkylene oxides are used instead of PO, such as butylene oxide, pentylene oxide etc.
  • m and n are generally average values, since the degrees of alkoxylation are in general statistical averages which, for a specific product, may be an integer or a fraction.
  • R 1 may contain more than 14 B units or less than 14 B units and/or more than 5 A units or less than 5 A units, the average number m of repeat units B being however 14 and the average number n of repeat units A being 5.
  • R 2 and R 3 have independently one of the meanings of R 1 .
  • one of R 2 and R 3 has one of the meanings of R 1 (and the other is Ci-C -alkyl).
  • R 2 and R 3 have independently one of the meanings of R 1 .
  • units B R a is methyl, B thus being preferably derived from PO.
  • m is 10 to 30 (on average) and n is 3 to 12 (on average); or m is 10 to 25 (on average) and n is 0. More preferably, m is 13 to 30 (on average) and n is 4 to 10 (on average); or m is 14 to 16 (on average) and n is 0. In a specific embodiment, m is 14 to 27 (on average) and n is 5 to 10 (on average); or m is 15 (on average) and n is 0. In a specific embodiment, m is 14 (on average) and n is 5 (on average); or m is 15 (on average) and n is 0.
  • R 1 is -CH2CH2O-A n -B m -H.
  • n, m and R a in B have the above preferred meanings.
  • R 1 , R 2 and R 3 are -CH2CH2O-A n -B m -H. Even more preferably, R 1 , R 2 and R 3 are -CH2CH2O-A n -B m -H, where R a in B is methyl, m is 10 to 30 (on average) and n is 3 to 12 (on average); or m is 10 to 25 (on average) and n is 0.
  • R 1 , R 2 and R 3 are -CH2CH2O-A n -B m -H, where R a in B is methyl, m is 13 to 30 (on average) and n is 4 to 10 (on average); or m is 14 to 16 (on average) and n is 0.
  • R 1 , R 2 and R 3 are -CH2CH2O-A n -B m -H, where R a in B is methyl, m is 14 to 27 (on average) and n is 5 to 10 (on average); or m is 15 (on average) and n is 0.
  • R 1 , R 2 and R 3 are -CH2CH2O-A n -B m -H, where R a in B is methyl, m is 10 to 20 (on average) and n is 3 to 8 (on average); or m is 10 to 25 (on average) and n is 0. More specifically, R 1 , R 2 and R 3 are -CH2CH2O-A n -B m -H, where R a in B is methyl, m is 13 to 15 (on average) and n is 4 to 6 (on average); or m is 14 to 16 (on average) and n is 0.
  • R 1 , R 2 and R 3 are -CH2CH2O-A n -B m -H, where R a in B is methyl, m is 14 (on average) and n is 5 (on average); or m is 15 (on average) and n is 0.
  • the antimicrobial agent and the alkoxylated amine are preferably present in an overall weight ratio of from 100:1 to 1 :10000 (e.g. 5:1 to 1 :10000), more preferably from 50:1 to 1 :2000 (e.g. 5:1 to 1 :2000), even more preferably from 50:1 to 1 :1000 (e.g. 5:1 to 1 :1000), particularly preferably from 50:1 to 1 :500, in particular from 20:1 to 1 :500, more particularly from 10:1 to 1 :500, even more particularly from 5:1 to 1 :500, specifically from 5:1 to 1 :450, very specifically from 2:1 to 1 :450.
  • the antimicrobial agent is 2-phenoxyethanol
  • 2-phe- noxyethanol and the alkoxylated amine are present in an overall weight ratio of from 3:1 to 1 :5, preferably from 3:1 to 1 :3, more preferably from 2.5:1 to 1 :2.5, even more preferably from 2:1 to 1 :2.5, in particular from 1.5:1 to 1 :2.5, more particularly from 1.5:1 to 1 :2, specifically from 1.3:1 to 1 :2 and very specifically from 1 :1 to 1 :2.
  • the antimicrobial agent is selected from the group consisting of 2-bromo-2-nitropropane-1 ,3-diol, glutaraldehyde and 1 ,2-benzisothiazol- 3(2H)one (BIT), and said antimicrobial agent and the alkoxylated amine are present in an overall weight ratio of from 1 : 1 to 1 :500, preferably from 1 : 1 to 1 :450, and more preferably from 1 : 100 to 1 :450.
  • BIT 2-bromo-2-nitropropane-1 ,3-diol, glutaraldehyde and 1 ,2-benzisothiazol- 3(2H)one
  • the antimicrobial agent is selected from the group consisting of 2-phenoxyethanol, 2-bromo-2-nitropropane-1 ,3-diol, glutaraldehyde and 1 ,2-benzisothiazol-3(2H)one (BIT); in the alkoxylated amine of the formula (I) R 1 , R 2 and R 3 are independently -CF ⁇ CFW-An-Bm-H, where R a is methyl, m is 10 to 30 and n is 3 to 12; or m is 10 to 20 and n is 0; and the antimicrobial agent and the alkoxylated amine are present in an overall weight ratio of from 3:1 to 1 :500; where specifically in the alkoxylated amine of the formula (I) R 1 , R 2 and R 3 are independently -CH2CH2O-A n - Bm-H, where R a is methyl, m is 14 to 27 and n is 5 to 10; or m is 15 and
  • the antimicrobial agent is 2-phenoxyethanol; in the alkoxylated amine of the formula (I) R 1 , R 2 and R 3 are independently -CH2CH2O-A n -B m -H, where R a is methyl, m is 10 to 30 and n is 3 to 12; or m is 10 to 20 and n is 0; and the antimicrobial agent and the alkoxylated amine are present in an overall weight ratio of from 3:1 to 1 :5, preferably from 3:1 to 1 :3, more preferably from 2.5:1 to 1 :2.5, even more preferably from 2:1 to 1 :2.5, in particular from 1.5:1 to 1 :2.5, specifically from 1.5:1 to 1 :2, more specifically from 1.3:1 to 1 :2 and very specifically from 1 :1 to 1 :2.
  • the antimicrobial agent is 2-phenoxyethanol; in the alkoxylated amine of the formula (I) R 1 , R 2 and R 3 are independently -CH2CH2O-A n -B m -H, where R a is methyl, m is 13 to 15 and n is 4 to 6; or m is 14 to 16 and n is 0; and the antimicrobial agent and the alkoxylated amine are present in an overall weight ratio of from 2:1 to 1 :5, preferably from 2:1 to 1 :3, more preferably from 1.5:1 to 1 :2.5, and even more preferably from 1 :1 to 1 :2.
  • the antimicrobial agent is 2-phenoxyethanol; in the alkoxylated amine of the formula (I) R 1 , R 2 and R 3 are independently -CH2CH2O-A n -B m -H, where R a is methyl, m is 14 and n is 5; or m is 15 and n is 0; and the antimicrobial agent and the alkoxylated amine are present in an overall weight ratio of from 2:1 to 1 :5, preferably from 2:1 to 1 :3, more preferably from 1.5:1 to 1 :2.5, and even more preferably from 1 :1 to 1 :2.
  • the antimicrobial agent is selected from the group consisting of 2-bromo-2-nitropropane-1 ,3-diol, glutaraldehyde and 1 ,2-benzisothiazol- 3(2H)one (BIT); in the alkoxylated amine of the formula (I) R 1 , R 2 and R 3 are independently -CH 2 CH 2 O-An-Bm-H, where R a is methyl, m is 10 to 20 and n is 3 to 8; and said antimicrobial agent and the alkoxylated amine are present in an overall weight ratio of from 1 :1 to 1 :500, preferably from 1 :1 to 1 :450, and more preferably from 1 :100 to 1 :450.
  • BIT 2-bromo-2-nitropropane-1 ,3-diol, glutaraldehyde and 1 ,2-benzisothiazol- 3(2H)one
  • the antimicrobial agent is selected from the group consisting of 2- bromo-2-nitropropane-1 ,3-diol, glutaraldehyde and 1 ,2-benzisothiazol-3(2H)one (BIT); in the alkoxylated amine of the formula (I) R 1 , R 2 and R 3 are independently -CH2CH2O- An-Bm-H, where R a is methyl, m is 13 to 15 and n is 4 to 6; and said antimicrobial agent and the alkoxylated amine are present in an overall weight ratio of from 1 :1 to 1 :500, preferably from 1 :1 to 1 :450, and more preferably from 1 :100 to 1 :450.
  • BIT 2- bromo-2-nitropropane-1 ,3-diol, glutaraldehyde and 1 ,2-benzisothiazol-3(2H)one
  • the antimicrobial agent is selected from the group consisting of 2-bromo-2- nitropropane-1 ,3-diol, glutaraldehyde and 1 ,2-benzisothiazol-3(2H)one (BIT); in the alkoxylated amine of the formula (I) R 1 , R 2 and R 3 are independently -CF ⁇ CFW-An-Bm- H, where R a is methyl, m is 14 and n is 5; and said antimicrobial agent and the alkoxylated amine are present in an overall weight ratio of from 1 :1 to 1 :500, preferably from 1 :1 to 1 :450, and more preferably from 1 :100 to 1 :450.
  • BIT 2-bromo-2- nitropropane-1 ,3-diol, glutaraldehyde and 1 ,2-benzisothiazol-3(2H)one
  • the composition further comprises at least one organic solvent.
  • the organic solvent is preferably selected from the group consisting of Ci-Cs-alkanols, C2-Cs-alkanediols, C1- Cs-alkylmonoethers of C2-Cs-alkanediols, polyetherpolyols, Ci-Cs-alkylmonoethers of polyetherpolyols, 5-, 6- or 7-membered lactones which may be substituted by one or more C1-C12-alkyl groups; 5-, 6- or 7-membered cyclic carbonates which may be substituted by one or more Ci-Ci2-alkyl groups; aliphatic esters, carboxamides, dioxolanes which may be substituted by one or more Ci-C4-alkyl and/or Ci-C4-hydroxyalkyl groups, aliphatic, alicyclic or heterocyclic amine-
  • organic solvents in this context are not restricted to “typical” solvents, i.e. to organic compounds with solvating properties which are liquid at 25°C, but encompass compounds with solvating properties having a higher melting point of at most 50°C, and also compounds which exert their solvating properties only when mixed with water, such as the above-mentioned aliphatic, alicyclic or heterocyclic amine-N-oxides, which would more correctly be termed solubilizers.
  • Ci-Cs-alkanols are compounds R-OH, where R is linear or branched Ci-Cs-alkyl. Examples are methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, isobutanol, tert-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 1-octanol, 2-ethylhexanol and (other) structural isomers of the four last-mentioned 1 -alkanols.
  • C2-Cs-alkanediols are compounds HO-A-OH, where A is linear or branched C2-Cs-al- kanediyl (or C2-Cs-alkylene), where the two OH groups are not geminally bound (i.e. are not bound to the same carbon atom).
  • Examples are ethylene glycol (1 ,2-ethane- diol), propylene glycol (1 ,2-propanediol), 1 ,3-propanediol, 1 ,2-butanediol, 1 ,4-butane- diol, 1 ,2-pentanediol, 1 ,5-pentanediol, 1 ,2-hexanediol, 1 ,6-hexanediol, 1 ,2-heptanediol, 1 ,2-octanediol and the like.
  • Ci-Cs-Alkylmonoethers of C2-Cs-alkanediols are compounds RO-A-OH, where A is as defined for the alkanediols above and R is Ci-Cs-alkyl.
  • Examples are ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol monoisopropyl ether, ethylene glycol mono-n-butyl ether (butyl glycol), ethylene glycol mono-sec-butyl ether, ethylene glycol mono-isobutyl ether, ethylene glycol mono-tert-butyl ether, ethylene glycol monopentyl ether, ethylene glycol monohexyl ether, ethylene glycol monoheptyl ether, ethylene glycol monooctyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glyco
  • Polyetherpolyols are formally the etherification products of alkanediols and thus compounds HO-A-[O-A] n -OH, where each A is independently an alkylene group, generally a C2-Cs-alkylene group, such as 1 ,2-ethylene, 1 ,2-propylene or 1 ,3-propylene, and n is from 1 to 100.
  • Examples are polyethylene glycol, generally with a molecular weight of from 106 to ca. 4500 (the term polyethylene glycol thus including diethylene glycol, triethylene glycol and other ethylene glycol oligomers), and polypropyleneglycol, generally with a molecular weight of from 134 to ca. 6000 (the term polypropylene glycol thus including dipropylene glycol, tripropylene glycol and other propylene glycol oligomers).
  • Ci-Cs-Alkylmonoethers of polyetherpolyols are compounds RO-A-[O-A] n -OH, where A and n are as defined for the polyetherpolyols above and R is Ci-Cs-alkyl.
  • Examples are polyethylene glycol monomethyl ether, polyethylene glycol monoethyl ether, polyethylene glycol mono-n-propyl ether, polyethylene glycol mono-n-butyl ether, and the like.
  • Examples for 5-, 6- or 7-membered lactones which may be substituted by one or more Ci-Ci2-alkyl groups are y-butyrolactone, y-valerolactone, y-octalactone, y-nonalactone, 5-valerolactone, 5-decanolactone, 5-dodecanolactone and s-caprolactone which may carry one or more Ci-Ci2-alkyl substituents.
  • Examples for 5-, 6- or 7-membered cyclic carbonates which may be substituted by one or more Ci -Ci 2-alkyl groups are ethylene carbonate, propylene carbonate and butylene carbonate which may carry one or more Ci-Ci2-alkyl substituents.
  • Suitable aliphatic esters are ethyl acetate, propyl acetate, butyl acetate, methylpropionate, ethyl propionate and further esters described below in context with solvent (C-2).
  • the ring is morpholin-4-yl, i.e.
  • carboxamide solvents are N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethyla- cetamide, N,N-dimethyloctanamide, N,N-dimethylnonanamide, N,N-dimethylde- canamide, N,N-dimethyllactamide, octanyolmorpholine and further carboxamides described below in context with solvent (C-1).
  • dioxolanes which may be substituted by one or more Ci-C4-alkyl and/or Ci-C4-hydroxyalkyl groups are given below in context with solvent (C-9).
  • Suitable aliphatic, alicyclic or heterocyclic amine-N-oxides are N,N-dime- thyl-N-ethylamine N-oxide, N,N,N-triethylamine N-oxide, N,N-dimethyl-N-cyclohexyla- mine N-oxide, N,N-dimethyl-N-ethanolamine N-oxide (DMEAO) and N-methylmorpho- line N-oxide.
  • the solvent is selected from the group consisting of Ci-Cs-alkanols, C2-Cs-alkanediols, Ci-Cs-alkylmonoethers of C2-Cs-alkanediols, 5-, 6- or 7-membered lactones which may carry one or more C1-C12-alkyl groups, and mixtures thereof.
  • Ci-Cs-alkanols preference is given to Ci-C4-alkanols, in particular to C2-C3- alkanols (i.e. to ethanol, n-propanol, isopropanol or a mixture thereof), and specifically to n-propanol.
  • C2-Cs-alkanediols preference is given to C2-C4-alkanediols, in particular to C2-C3-alkanediols, such as ethylene glycol, 1 ,2-propanediol and 1 ,3-pro- panediol, and specifically to 1 ,2-propanediol (propylene glycol).
  • Ci-Cs-alkyl- monoethers of C2-Cs-alkanediols preference is given to Ci-Ce-alkylmonoethers of C2- C4-alkanediols and in particular to Ci-C4-alkylmonoethers of a C2-C3-alkanediol, such as the Ci-C4-alkylmonoethers of ethylene glycol or propylene glycol, specific examples being ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether (also termed butylglyol), propylene glycol mono-n-propyl ether, propylene glycol mono-n-bu- tyl ether and mixtures thereof.
  • Ci-C4-alkylmonoethers of ethylene glycol or propylene glycol specific examples being ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether (also termed but
  • the solvent is a C2-Cs-alkanediol, more preferably a C2-C4-alkanediol, in particular a C2-C3-alkanediol, such as ethylene glycol, 1 ,2-propanediol and 1 ,3-pro- panediol, and specifically 1 ,2-propanediol (propylene glycol).
  • the solvent is a Ci-Cs-alkanol, more preferably a Ci- C4-alkanol, and in particular a C2-C3-alkanol (i.e. ethanol, n-propanol, isopropanol or a mixture thereof), specifically ethanol.
  • composition additionally comprises
  • R 4 is hydrogen or Ci-Cs-alkyl
  • R 5 is Ci-Cs-alkyl
  • R 6 is Ci-Cs-alkyl or Ci-Cs-hydroxyalkyl
  • R 6 is Ci-Cs-alkyl or Ci-Cs-hydroxyalkyl
  • R 7 is Ci-Cio-alkyl
  • Ci-Cs-alkylmonoethers of C2-Cs-alkanediols diethylene glycol, dipropylene glycol, a polyethylene glycol with up to 10 repeat units or a polypropylene glycol with up to 10 repeat units;
  • R 9 and R 10 are independently Ci-C4-alkyl or form together an oxo group
  • R 11 is Ci-C4-alkyl or Ci-C4-hydroxyalkyl
  • carboxamides of the formula (C-1) are N-methylacetamide, N,N-dime- thylacetamide, N-ethylacetamide, N,N-diethylacetamide, N-ethyl-N-methylacetamide, N-propylacetamide, N,N-dipropylacetamide, N-methyl-N-propylacetamide, N-ethyl-N- propylacetamide, N-isopropylacetamide, N,N-diisopropylacetamide, N-methyl-N-iso- propylacetamide, N-ethyl-N-isopropylacetamide, N-n-butylacetamide, N,N-di-n-butyla- cetamide, N-n-butyl-N-methylacetamide, N-n-butyl-N-ethylacetamide, N-n-butyl-N-propylacetamide, N-n-butyl-N-
  • Examples for carboxylic acids of the formula (C-2) are methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, n-butyl acetate, n-hexyl acetate, 2-ethylhexyl acetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, n-butyl propionate, n-hexyl propionate, 2-ethylhexyl propionate, methyl lactate, ethyl lactate, propyl lactate, isopropyl lactate, n-butyl lactate, n-hexyl lactate, 2-ethylhexyl lactate and the like.
  • Cs-Cs-Alkanols are compounds R-OH wherein R is a linear or branched Cs-Cs-al- kyl group, as defined above. Examples are n-propanol, isopropanol, n-butanol, sec-bu- tanol, isobutanol, tert-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 1-octanol, 2-ethylhex- anol and (other) structural isomers of the four last-mentioned 1-alkanols.
  • Cs-Cs-Alkanediols are compounds HO-A-OH, where A is linear or branched C3- Cs-alkanediyl (or Cs-Cs-alkylene), where the two OH groups are not geminally bound (i.e. are not bound to the same carbon atom).
  • Examples are propylene glycol (1 ,2-pro- panediol), 1 ,3-propanediol, 1 ,2-butanediol, 1 ,4-butanediol, 1 ,2-pentanediol, 1 ,5-pen- tanediol, 1 ,2-hexanediol, 1 ,6-hexanediol, 1 ,2-heptanediol, 1 ,2-octanediol and the like.
  • Ci-Cs-Alkylmonoethers of C2-C8-alkanediols are compounds RO-A-OH, where A is 1 ,2-ethylene (-CH2CH2-) or is as defined for the Cs-Cs-alkanediols above, and R is Ci-Cs-alkyl.
  • Examples are ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol monoisopropyl ether, ethylene glycol mono-n-butyl ether (butyl glycol), ethylene glycol mono-sec-butyl ether, ethylene glycol mono-isobutyl ether, ethylene glycol mono-tert-butyl ether, ethylene glycol monopentyl ether, ethylene glycol monohexyl ether, ethylene glycol monoheptyl ether, ethylene glycol monooctyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol monoisopropyl ether, propylene glycol mono-n-butyl ether, propylene glycol mono-sec- butyl ether, propylene glycol mono-isobut
  • Polyethylene glycols with up to 10 repeat units are oligomers or polymers of the formula HO-A-[O-A] n -OH, where A is a 1 ,2-ethylene group (-CH2-CH2-), and n is from 2 to 9.
  • Polypropylene glycols with up to 10 repeat units (falling under (c.6) are oligomers or polymers of the formula HO-A-[O-A] n -OH, where A is a 1 ,2-propylene group (-CH(CHs)- CH2- or -CH2-CH(CH3)-, and n is from 2 to 9.
  • Ci-Cs-Alkylmonoethers of diethylene glycol are compounds RO- CH2CH2-O-CH2CH2-OH, where R is Ci-Cs-alkyl.
  • Examples are diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol monoisopropyl ether, diethylene glycol mono-n-butyl ether (also termed butyldiglycol), diethylene glycol mono-sec-butyl ether, diethylene glycol monoisobutyl ether, diethylene glycol mono-tert-butyl ether, diethylene glycol monopentyl ether, diethylene glycol monohexyl ether, diethylene glycol monoheptyl ether, diethylene glycol monooctyl ether and structural isomers thereof.
  • Ci-Cs-Alkylmonoethers of dipropylene glycol (falling under (c.7)) are compounds RO- CH(R a )CH(R b )-O- CH(R c )CH(R d )-OH, where R is Ci-C 8 -alkyl, one of R a and R b is H and the other is methyl, and one of R c and R d is H and the other is methyl.
  • Examples are dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol monoisopropyl ether, dipropylene glycol mono-n-butyl ether, dipropylene glycol mono-sec-butyl ether, dipropylene glycol monoisobutyl ether, dipropylene glycol mono-tert-butyl ether, dipropylene glycol monopentyl ether, dipropylene glycol monohexyl ether, dipropylene glycol monoheptyl ether, dipropylene glycol monooctyl ether and structural isomers thereof.
  • Examples of mono- di- or triesters of glycerol with Ci-C4-carboxylic acids are glycerol monoacetate, glycerol diacetate and glycerol triacetate.
  • R 6 is Ci-Cs-hydroxyalkyl, more preferably Ci-C4-hydroxyalkyl, even more preferably Ci-C2-hydroxyalkyl, specifically 1 -hydroxy- ethyl.
  • R 6 is Ci-C4-alkyl or Ci-C4-hy- droxyalkyl, more preferably Ci-C2-alkyl or Ci-C2-hydroxyalkyl, specifically methyl or 2- hydroxyethyl.
  • R 4 is preferably hydrogen or Ci-C4-alkyl, more preferably hydrogen or Ci-C2-alkyl, even more preferably Ci-C2-alkyl (i.e. methyl or ethyl), specifically methyl.
  • R 5 is preferably Ci-C4-alkyl, more preferably Ci-C2-alkyl (i.e. methyl or ethyl), specifically methyl.
  • solvent (c.1) of formula (C-1) is N,N-dimethyllactamide.
  • R 6 is Ci-Cs-hydroxyalkyl, more preferably Ci-C4-hydroxyalkyl, even more preferably Ci-C2-hydroxyalkyl, specifically 1 -hydroxy- ethyl.
  • R 6 is Ci-C4-alkyl or Ci-C4-hy- droxyalkyl, more preferably Ci-C2-alkyl or Ci-C2-hydroxyalkyl, specifically methyl or 2- hydroxyethyl.
  • R 7 is preferably C4-Cio-alkyl, more preferably Ce-C -alkyl, in particular Cs-alkyl, specifically 2-ethylhexyl.
  • solvent (c.2) of formula (C-2) is 2-ethylhexyllactate.
  • the solvent (c.3) is preferably selected from C3-C4-alkanols, specifically from n-propa- nol and n-butanol.
  • Solvent (c.4) is preferably selected from C4-Ce-alkanediols, in particular from Cs-al- kanediols, specifically from 1 ,2-pentanediol and neopentylglycol.
  • Solvent (c.5) is preferably selected from Ci-Ce-alkylmonoethers of C2-C3-alkanediols, more preferably C2-C5-alkylmonoethers of C2-C3-alkanediols, in particular C3-C4-alkyl- monoethers of C2-C3-alkanediols, specifically from 1-butoxy-propan-2-ol, (propyleneglycol n-butyl ether) 1-butoxy-ethan-2-ol (butyl glycol; ethyleneglycol n-butyl ether) or 1- propoxy-propan-2-ol (propyleneglycol n-propyl ether).
  • Solvent (c.6) is preferably selected from diethylene glycol, dipropylene glycol, a polyethylene glycol (PEG) with a number-average molecular weight of up to 200 or a polypropylene glycol (PPG) with a number-average molecular weight M n of up to 200, more preferably from dipropylene glycol or a polyethylene glycol with a number-average molecular weight of up to 200, and is specifically dipropylene glycol.
  • the number-average molecular weight is as determined by gel permeation chromatography using PEG standards.
  • Solvent (c.7) is preferably selected from Ci-Ce-alkylmonoethers of diethylene glycol or dipropylene glycol, specifically from diethyleneglycolmono-n-butyl ether, diethylenegly- colmono-n-hexyl ether (hexyldiglycol) or dipropyleneglycolmonomethyl ether.
  • R 8 is preferably linear Ci-C4-alkyl, specifically methyl.
  • Solvent (c.9) is preferably selected from propylene carbonate (4-methyl-1 ,3-dioxolan-2- one; R 9 and R 10 form together an oxo group; R 11 is methyl) or isopropylidenglycerol (2,2-dimethyl-4-(hydroxymethyl)-1 ,3-dioxolane; R 9 and R 10 are methyl; R 11 is hydroxymethyl).
  • Solvent (c.10) is preferably selected from glycerol monoacetate, glycerol diacetate and glycerol triacetate and is specifically glycerol triacetate (triacetine).
  • the organic solvent (c) is preferably selected from the group consisting of
  • the organic solvent selected from the group consisting of N,N-dimethyllac- tamide, 1-butoxy-propan-2-ol, diethyleneglycolmono-n-butyl ether (also termed butyldiglycol), y-valerolactone and mixtures thereof.
  • solvent (c) is particularly beneficial if the antimicrobial agent is 2-phe- noxyethanol.
  • the solvents can however of course also be used when other antimicrobials are used.
  • solvent (c) does not preclude the presence of other organic solvents, such as those listed above.
  • the antimicrobial agent and the organic solvent of component (c) are preferably present in an overall weight ratio of from 10:1 to 1 :10, more preferably from 5:1 to 1 :5, even more preferably from 3:1 to 1 :3, in particular from 2:1 to 1 :2, specifically from 2:1 to 1 :1.
  • the composition comprises water. In another preferred embodiment, the composition comprises both water and an organic solvent.
  • the composition of the invention can be a concentrate comprising the antimicrobial (a), the alkoxylated amine (I) and optionally a carrier, such as a diluent, e.g. an organic solvent and/or water; or can be an intermediate composition, i.e. a composition which is not yet the ready-to-use composition for the end user, but already comprises a part of the other components (i.e. components different from of the antimicrobial (a), the alkoxylated amine (I) and the optional carrier) of the final ready-to-use composition; or can be a ready-to-use-composition, i.e. a composition which is used as such and does not need any further dilution or addition of further substances.
  • a carrier such as a diluent, e.g. an organic solvent and/or water
  • an intermediate composition i.e. a composition which is not yet the ready-to-use composition for the end user, but already comprises a part of the other components (i
  • Antimicrobials find use in a vast field of application.
  • any water-containing system or material devoid of intrinsic protection is prone to microbial attack/infestation.
  • homecare compositions such as laundry compositions, e.g. detergents or fabric softeners; dishwashing compositions; cleaning compositions etc.
  • compositions for cleaning or disinfecting on an industrial scale in contrast to home care carried out on a distinctly smaller scale
  • personal care compositions including cosmetics
  • process water cooling water
  • compositions for treating animal hide compositions for treating leather
  • compositions for treating textiles during the manufacturing process thereof compositions for treating lumber; compositions for treating paper or the precursor material during papermaking processes; crop protection compositions; pharmaceutical compositions; paints, glues, adhesives, sealants, dyes, pigments and dispersions thereof, inks, wet wipes (for personal care, for homecare etc.) and the like.
  • composition of the invention is thus preferably selected from the group consisting of antimicrobial concentrates, homecare compositions, compositions for cleaning or disinfecting on an industrial scale, personal care compositions, process water, cooling water, water in fish or shrimp ponds, water in drinking troughs, metal working fluids; water based raw materials, polymer solutions, polymer dispersions, polymer emulsions, inorganic slurries, organic slurries, surfactant compositions; compositions for treating animal hide; compositions for treating leather; compositions for treating textiles during the manufacturing process thereof; compositions for treating lumber; compositions for treating paper or the precursor material during papermaking processes; crop protection compositions; pharmaceutical compositions; paints, glues, adhesives, sealants, dyes, pigments and dispersions thereof, inks, and wet wipes.
  • l&l compositions for cleaning or disinfecting on an industrial scale overlap largely, only that l&l compositions are adapted to the use on a larger scale and are thus often more aggressive (e.g. by being more concentrated and/or by having a distinctly higher or lower pH than the respective homecare composition) and/or are less “pleasant”, e.g. in the sense of odor or aspect or touch.
  • CIP clean-in-place
  • dishwashing compositions in liquid or gel form
  • laundry compositions in liquid or gel form
  • surface cleaning compositions also termed hard surface cleaners; for example glass, floor, counter, bath(room), toilet bowl, sink, kitchen, appliance and furniture cleaning compositions; all-purpose cleaners; sanitary cleaners
  • non-cosmetic deodorants e.g.
  • disinfectants for example spray air disinfectants, and spray, liquid and paste/gel surface disinfectants
  • surface protecting and/or polishing compositions rug shampoos, descaling agents, and compositions for wet wipes (e.g. for cleaning the floor, furniture, bath room surfaces etc.).
  • Personal care compositions are used for cleaning, washing, disinfecting, nurturing, grooming, protecting or embellishing the human body (and thus also include cosmetics).
  • cosmetics examples are creams, lotions, ointments, other o/w or w/o emulsions, liquid or gellike soaps, shampoos, make-up and other decorative cosmetics, and compositions for wet wipes (e.g. for cleaning the nappy area).
  • More specific examples are skin-washing and cleansing preparations in the form of soaps, syndets, washing gels, soapless detergents or washing pastes, bath preparations, e.g. foam baths, milks, oils, shower preparations; skin-care preparations, e.g.
  • cosmetic preparations e.g. facial make-up in the form of day creams or powder creams, face powder (loose or pressed), rouge or cream make-up, eye-care preparations, e.g. eyeshadow preparations, mascara, eyeliner, eye creams or eye-fix creams; lip-care preparations, e.g. lipsticks, lip gloss, lip contour pencils, nail- care preparations, such as nail varnish, nail varnish removers, nail hardeners or cuticle removers; foot-care preparations, e.g.
  • foot baths foot powders, foot creams or foot balsams, special deodorants and antiperspirants or callus-removing preparations
  • light- protective preparations such as sun milks, lotions, creams or oils, sunblocks or tropicals, pre-tanning preparations or after-sun preparations
  • skin-tanning preparations e.g. self-tanning creams
  • depigmenting preparations e.g. preparations for bleaching the skin or skin-lightening preparations
  • insect-repellents e.g.
  • insect-repellent oils, lotions, sprays or sticks deodorants, such as deodorant sprays, deodorant aerosols, pump-action sprays, deodorant gels, sticks or roll-ons, also water-free deodorant aerosols or sticks; antiperspirants, e.g. antiperspirant sticks, creams or roll-ons; preparations for cleansing and caring for blemished skin, e.g. synthetic detergents (solid or liquid), peeling or scrub preparations or peeling masks; hair-removal preparations in chemical form (depilation), e.g. liquid hair-removing preparations, cream- or paste-form hair-removing preparations, hair-removing preparations in gel form or aerosol foams; shaving preparations, e.g.
  • fragrance preparations e.g. fragrances (eau de Cologne, eau de toilette, eau de perfume, perfume de toilette, perfume), perfume oils or perfume creams
  • cosmetic hairtreatment preparations e.g. hair-washing preparations in the form of shampoos and conditioners, hair-care preparations, e.g. pre-treatment preparations, hair tonics, styling creams, styling gels, pomades, hair rinses, treatment packs, intensive hair treatments, hair-structuring preparations, e.g.
  • hair-waving preparations for permanent waves hot wave, mild wave, cold wave
  • hair-straightening preparations liquid hairsetting preparations, hair foams, hairsprays
  • bleaching preparations e.g. hydrogen peroxide solutions, lightening shampoos, bleaching creams, bleaching powders, bleaching pastes or oils, temporary, semi-permanent or permanent hair colorants, preparations containing selfoxidising dyes, or natural hair colorants, such as henna or camomile
  • oral care preparations such as (tooth) pastes, gels, mouth washes and sprays
  • disinfectants for mouth or skin disinfectants for mouth or skin.
  • Process water is for example process water used in food, feed, pharmaceutical or cosmetic industry (cooling and process water), or process water used in paper production, wood treatment, cooling water towers, air washers, air conditioners, printing fluids or oil production.
  • Crop protection compositions which are often also termed plant protection compositions, are compositions which are effective against various harmful microorganisms, harmful invertebrate pests or undesired plants relevant for agriculture, e.g. harmful fungi, harmful invertebrate pests, such as harmful insects, arachnids, nematodes or molluscs, and weeds, which cause damage to agricultural plants, plant propagation materials, such as seeds, or harvested crops.
  • Examples for crop protection compositions are fungicidal, insecticidal, acaricidal, nematicidal, moluscicidal or herbicidal compositions. The term encompasses also plant growth regulating compositions.
  • Plant growth regulators are plant protection products used to influence plant growth and are used, for example, for increasing the stability of cereals by shortening the stalk length, thus reducing or preventing lodging, for improving the rooting of cuttings, reducing plant height in horticulture, preventing the germination of potatoes and the like.
  • the term encompasses moreover compositions used in material protection for combating various harmful microorganisms and invertebrate pests, such as compositions for the treatment of lumber or the surroundings of lumber material against termites or compositions for the treatment of mosquito nets against harmful insects, such as Anopheles mosquitoes, and the like.
  • the composition is an antimicrobial concentrate.
  • the antimicrobial concentrate comprises:
  • concentrate is used in this context also for compositions in which components (a) and (b) do not constitute the major part (and thus do not form a concentrate in the proper sense). Nevertheless, it signals that components different from (a), (b) and the optional diluents (d) and (e), if at all present, do not predominate. Moreover, the term signals that the composition can consist of components (a) and (b) only. Preferably however, at least a diluent (d) or (e) or mixtures thereof are present to assure an easier handling.
  • the antimicrobial agent is 2-phenoxyethanol, phenoxyisopropanol, formic acid or a salt thereof, benzoic acid or a salt thereof, sorbic acid or a salt thereof, lactic acid or a salt thereof or N-(3-aminopropyl)-N-dodecylpropane-1,3-diamine (Diamine), this is preferably contained in an amount of 0.1 to 99.9% by weight, relative to the total weight of the composition.
  • Suitable and preferred components (a) and (b) and suitable and preferred weight ratios thereof are those mentioned above.
  • Further additives (c) are for example agents which stabilize the concentrate, such as emulsifiers and/or hydrotropic agents, activity enhancers different from component (b) and pH modifiers.
  • emulsifiers usual in such systems can be used.
  • a few non-limiting examples are carboxylic acids and their salts, alkyl phosphates or phosphoric acid esters, ethoxylated and/or propoxylated fatty acids, ethoxylated and/or propoxylated polyethyleneglycols, ethoxylated and/or propoxylated fatty alcohols, fatty acid monoglycerides, fatty acid saccharose esters, fatty acid sorbitol esters, fatty acid sorbitan esters, fatty acid glucose esters, ethoxylated and/or propoxylated derivatives of the listed fatty acid polyol esters, fatty sulfates and sulfonates, ethoxylated amines, ethoxylated amides, polysiloxane/polyalkyl/polyether copolymers and derivatives, poly(oxyethylene)- poly(oxypropylene)-blockpolymers,
  • Hydrotropic agents are compounds which solubilize hydrophobic compounds in aqueous solution by means other than micellar solubilization. Similar to surfactants, hydrotropes often (but not necessarily) consist of a hydrophilic part and a hydrophobic part, but in contrast to surfactants the hydrophobic part is generally too small to cause spontaneous self-aggregation. Examples are aromatic sulfonic acid salts, such as the alkali metal, earth alkaline metal or ammonium salts of p-toluenesulfonic acid (e.g. sodium, potassium, calcium or ammonium p-tosylate), of xylene sulfonic acids (e.g.
  • the sodium, potassium, calcium or ammonium salts of o-, m- or p-xylene sulfonates) or of cumene sulfonic acids generally of p-cumene sulfonic acid (e.g. the sodium, potassium, calcium or ammonium salts of p-cumenesulfonate); adenosine triphosphate (ATP); and urea.
  • p-cumene sulfonic acid e.g. the sodium, potassium, calcium or ammonium salts of p-cumenesulfonate
  • ATP adenosine triphosphate
  • Examples for activity enhancers different from component (b) are ethylhexylglycerine (3-(2-ethylhexyloxy)propan-1 ,2-diol) and polyethyleneimines (PEI). Further details are given below in context with homecare compositions.
  • pH modifiers are acids, bases and also buffers.
  • the acids can be inorganic or organic. Suitable inorganic acids are for example sulfuric acid, hydrochloric acid and phosphoric acid, where sulfuric acid is generally preferred.
  • Suitable organic acids are for example aliphatic, saturated non-substituted Ci-Ce- mono-, di- and tri-carboxylic acids such as formic acid, acetic acid, propanoic acid, oxalic acid, succinic acid and glutaric acid; aliphatic, saturated Ci-Ce-mono-, di- and tricarboxylic acids carrying one or more OH groups, such as lactic acid, tartric acid and citric acid; aliphatic, unsaturated Ci-Ce-mono-, di- and tri-carboxylic acids such as sorbic acid; aromatic carboxylic acids, such as benzoic acid, salicylic acid and mandelic acid, and sulfonic acids, such as methanesulfonic acid or toluenesulfonic acid.
  • Suitable bases are in particular inorganic bases, such as the carbonates mentioned below in context with the sequestrant, e.g. sodium or potassium carbonate; further alkali metal and earth alkaline meal hydroxides, such as NaOH or KOH.
  • Suitable buffering agents are the typical systems, such as hydrogenphosphate/dihy- drogenphosphate buffer, carbonate/hydrogencarbonate buffer, acetic acid/acetate buffer or Tris buffer. Moreover, most of the above acids which are weak and the anion of which is not a strong salt also have buffering capacity.
  • Suitable organic solvents (c) are those mentioned above.
  • Preferred organic solvents are thus Ci-Cs-alkanols, C2-C8-alkanediols, Ci-Cs-alkylmonoethers of C2-Cs-alkanedi- ols, polyetherpolyols, Ci-Cs-alkylmonoethers of polyetherpolyols, 5-, 6- or 7-membered lactones which may be substituted by one or more C1-C12-alkyl groups; 5-, 6- or 7- membered cyclic carbonates which may be substituted by one or more Ci-Ci2-alkyl groups; aliphatic esters, carboxamides, dioxolanes as defined above, aliphatic or alicyclic amine-N-oxides and mixtures of the afore-mentioned solvents.
  • the solvent (c) is selected from Ci-Cs-alkanols, C2-Cs-alkanediols, Ci-Cs-alkylmonoethers of C2-Cs-alkanediols, 5-, 6- or 7-membered lactones which may carry one or more C1-C12-alkyl groups and mixtures thereof.
  • Ci-Cs-alkanols preference is given to Ci-C4-alkanols, in particular to C2-C3-alkanols (i.e. to ethanol, n-propanol, isopropanol or a mixture thereof), and specifically to n-propanol.
  • C2-Cs-alkanediols preference is given to C2- C4-alkanediols, in particular to C2-C3-alkanediols, such as ethylene glycol, 1 ,2-propane- diol and 1 ,3-propanediol, and specifically to 1 ,2-propanediol (propylene glycol).
  • Ci-Cs-alkylmonoethers of C2-Cs-alkanediols preference is given to Ci-Ce-alkylmo- noethers of C2-C4-alkanediols and in particular to Ci-C4-alkylmonoethers of a C2-C3-al- kanediol, such as the Ci-C4-alkylmonoethers of ethylene glycol or propylene glycol, specific examples being ethylene glycol mono-n-propyl ether, ethylene glycol mono-n- butyl ether (also termed butylglyol), propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether and mixtures thereof.
  • Ci-C4-alkylmonoethers of ethylene glycol or propylene glycol specific examples being ethylene glycol mono-n-propyl ether, ethylene glycol mono-n- butyl ether (also termed
  • the solvent is a C2-Cs-alkanediol, more preferably a C2-C4-alkanediol, in particular a C2-C3-alkanediol, such as ethylene glycol, 1 ,2-propanediol and 1 ,3-pro- panediol, and specifically 1 ,2-propanediol (propylene glycol).
  • the solvent is a Ci-Cs-alkanol, more preferably a Ci- C4-alkanol, and in particular a C2-C3-alkanol (i.e. ethanol, n-propanol, isopropanol or a mixture thereof), specifically n-propanol.
  • the solvent comprises at least one of the solvents (c.1) to (c.10) as defined above, and, if desired, also another organic solvent. More particularly, the solvent comprises N,N-dimethyllactamide, 1-butoxy-propan-2-ol, diethy- leneglycolmono-n-butyl ether, y-valerolactone or a mixture of two or more of these solvents and, if desired, also a C2-C3-alkanol (i.e.
  • ethanol n-propanol, isopropanol or a mixture thereof
  • a C2-C3-alkanediol such as ethylene glycol, 1 ,2-propanediol and 1 ,3-propanediol, and specifically 1 ,2-propanediol (propylene glycol).
  • the antimicrobial concentrate comprises:
  • the antimicrobial concentrate comprises:
  • Examples for homecare and l&l compositions are listed above. Among these, preference is given to dishwashing compositions, laundry compositions, surface cleaning compositions, and rug shampoos.
  • composition of the invention is selected from the group consisting of dishwashing compositions, laundry compositions, surface cleaning compositions, and rug shampoos.
  • Such compositions preferably comprise:
  • Suitable and preferred components (a) and (b) and suitable and preferred weight ratios thereof are those mentioned above.
  • Suitable organic solvents (c) are those mentioned above.
  • Preferred organic solvents are thus Ci-Cs-alkanols, C2-Cs-alkanediols, Ci-Cs-alkylmonoethers of C2-Cs-alkanedi- ols, polyetherpolyols, Ci-Cs-alkylmonoethers of polyetherpolyols, 5-, 6- or 7-membered lactones which may be substituted by one or more C1-C12-alkyl groups; 5-, 6- or 7- membered cyclic carbonates which may be substituted by one or more Ci-Ci2-alkyl groups; aliphatic esters, carboxamides, aliphatic or alicyclic amine-N-oxides and mixtures of the afore-mentioned solvents.
  • the solvent (c) is selected from Ci-Cs-alkanols, C2-C8- alkanediols, Ci-Cs-alkylmonoethers of C2-Cs-alkanediols, 5-, 6- or 7-membered lactones which may carry one or more Ci -Ci 2-alkyl groups and mixtures thereof.
  • Ci-Cs-alkanols preference is given to Ci-C4-alkanols, in particular to C2-C3-alkanols (i.e. to ethanol, n-propanol, isopropanol or a mixture thereof), and specifically to n-pro- panol.
  • C2-Cs-alkanediols preference is given to C2-C4-alkanediols, in particular to C2-C3-alkanediols, such as ethylene glycol, 1 ,2-propanediol and 1 ,3-propane- diol, and specifically to 1 ,2-propanediol (propylene glycol).
  • Ci-Cs-alkylmo- noethers of C2-Cs-alkanediols preference is given to Ci-Ce-alkylmonoethers of C2-C4- alkanediols and in particular to Ci-C4-alkylmonoethers of a C2-C3-alkanediol, such as the Ci-C4-alkylmonoethers of ethylene glycol or propylene glycol, specific examples being ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether (also termed butylglyol), propylene glycol mono-n-propyl ether, propylene glycol mono-n-bu- tyl ether and mixtures thereof.
  • the solvent is a C2-Cs-alkanediol, more preferably a C2-C4-alkanediol, in particular a C2-C3-alkanediol, such as ethylene glycol, 1 ,2-propanediol and 1 ,3-pro- panediol, and specifically 1 ,2-propanediol (propylene glycol).
  • the solvent is a Ci-Cs-alkanol, more preferably a C1- C4-alkanol, and in particular a C2-C3-alkanol (i.e. ethanol, n-propanol, isopropanol or a mixture thereof), specifically n-propanol.
  • the solvent comprises at least one of the solvents (c.1) to (c.10) as defined above, and, if desired, also onother organic solvent. More particularly, the solvent comprises N,N-dimethyllactamide, 1-butoxy-propan-2-ol, diethy- leneglycolmono-n-butyl ether, y-valerolactone or a mixture of these solvents and, if desired, also a C2-C3-alkanol (i.e.
  • ethanol n-propanol, isopropanol or a mixture thereof
  • a C2-C3-alkanediol such as ethylene glycol, 1 ,2-propanediol and 1 ,3-propane- diol, and specifically 1 ,2-propanediol (propylene glycol).
  • Surfactants (or surface-active compounds) of component (d) can be anionic, cationic, non-ionic or amphoteric (zwitterionic).
  • Anionic surfactants are, for example, of the sulfate, sulfonate or carboxylate type or mixed forms thereof.
  • Examples are alkylbenzenesulfonates, alkyl sulfates, alkyl ether sulfates, olefin sulfonates, fatty acid salts, alkyl and alkenyl ether carboxylates or to an alpha-sulfonic fatty acid salt or an ester thereof.
  • alkylbenzenesulfonates having from 10 to 20 carbon atoms in the alkyl radical (e.g. sodium dodecylbenzene sulfonate), alkyl sulfates having from 8 to 18 carbon atoms in the alkyl radical (e.g. sodium lauryl sulfate), alkyl ether sulfates having from 8 to 18 carbon atoms in the alkyl radical (e.g. sodium laureth sulfate; SLES), and fatty acid salts derived from oils or fats, e.g.
  • the counter-cation is preferably an alkali metal cation, especially sodium or potassium, specifically sodium.
  • Preferred carboxylates are alkali metal sarcosinates of formula R-CON(R’)CH2COO'M + wherein R’ is Cg-Ci7-alkyl or Cg-Ci7-alkenyl, R’ is Ci-C4-alkyl and M + is an alkali metal cation, especially Na + .
  • Cationic surfactants are, for example, ammonium salts such as Cs-Cie-dialkyldime- thylammonium halides, dialkoxydimethylammonium halides or imidazolinium salts with a long-chain alkyl radical.
  • Non-ionic surfactants are, for example, a primary or secondary alcohol ethoxylate, especially a C8-C20 aliphatic alcohol ethoxylated with an average of from 1 to 20 mol of ethylene oxide per alcohol group. Preference is given to primary and secondary C10-C15 aliphatic alcohols ethoxylated with an average of from 1 to 10 mol of ethylene oxide per alcohol group.
  • Non-ethoxylated non-ionic surfactants for example alkylpolyglycosides, glycerol monoethers and polyhydroxyamides (glucamide), may likewise be used.
  • Amphoteric surfactants are, for example, derivatives of secondary or tertiary amines, for example Ce-C -alkyl betaines (e.g. cocoamidopropyl betaine; disodium cocoam- phodiacetate (DSCADA)) or Ce-Cis-alkyl sulfobetaines, or amine oxides such as alkyldimethylamine oxides.
  • Ce-C -alkyl betaines e.g. cocoamidopropyl betaine; disodium cocoam- phodiacetate (DSCADA)
  • Ce-Cis-alkyl sulfobetaines e.g., amine oxides such as alkyldimethylamine oxides.
  • Examples for enzymes of component (e) are those typically used in laundry, dishwashing or cleaning compositions.
  • Enzyme herein means catalytically active proteins which are characterized by an amino acid sequence. Variants of an enzyme may be described by a certain sequence identity of an amino acid sequence of the variant when compared to a respective starting sequence.
  • sequence identities in a first step a pairwise global sequence alignment has to be produced, meaning that two sequences have to be aligned over their complete length typically by using the algorithm of Needleman and Wunsch (J. Mol. Biol. (1979) 48, p. 443-453).
  • the enzymes are preferably selected from hydrolases, such as proteases, esterases, glucosidases, lipases, DNAses, amylases, cellulases, mannanases, other glycosylhydrolases and mixtures of the aforementioned enzymes. All these hydrolases contribute to dissolution and removal of soil from protein-, grease- or starch-containing stains/resi- dues. For bleaching, it is also possible to use oxidoreductases. Particularly suitable are active enzymatic ingredients obtained from bacterial strains or fungi, such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus and Humicola insolens.
  • hydrolases such as proteases, esterases, glucosidases, lipases, DNAses, amylases, cellulases, mannanases, other glycosylhydrolases and mixtures of the aforementioned enzymes. All these hydrolases
  • Preferred hydrolases are selected from the group of enzymes acting on ester bonds (esterases) (E.C. 3.1), glycosylases (E.C. 3.2), and peptidases (E.C. 3.4).
  • Enzymes acting on ester bonds (E.C. 3.1) are for example lipases and DNAses.
  • Glycosylases (E.C. 3.2) are for example amylases, cellulases, and mannanases.
  • Peptidases are for example proteases.
  • Suitable hydrolases are, for example, a-glucosidases (EC number 3.2.1.20), proteases (e.g. Ovozyme® (from Novozymes); EC number 3.2.1.20), amylases [e.g. Purastar® (from Genencor), Termamyl® (from Novozymes), Stainzyme® (from Novozymes), Du- ramyl® (from Novozymes)], mannanases [e.g. Purabrite® (from Genencor), Mannastar® (from Genencor), Mannaway® (from Novozymes)] and cellulases [e.g.
  • a-glucosidases EC number 3.2.1.20
  • proteases e.g. Ovozyme® (from Novozymes); EC number 3.2.1.20
  • amylases e.g. Purastar® (from Genencor), Termamyl® (from Novozymes), Stainzy
  • the suitable amylases include especially a-amylases (EC number 3.2.1.1), iso-amylases, pullulanases and pectinases.
  • the cellulases used are preferably cellobiohydrolases, endoglucanases and p-glucosidases, which are also referred to as cellobiases, or mixtures thereof. Since different cellulase types differ by their CMCase and Avicelase activities, it is possible to establish the desired activities by means of controlled mixtures of the cellulases.
  • Suitable lipases are for example Lipex and Lipolase.
  • lipolytically active enzymes are the known cutinases.
  • Peroxidases or oxidases have also been found to be suitable in some cases.
  • the enzymes comprise at least one protease (EC 3.4).
  • at least one protease is selected from serine proteases (EC 3.4.21), more preferably from subtilisins (EC 3.4.21.62).
  • At least one subtilisin may have SEQ ID NO:22 as described in EP 1921147 (which may be called BLAP WT herein), or is a variant thereof which is at least 80% identical SEQ ID NO:22 as described in EP 1921147 and has proteolytic activity.
  • a subtilisin is at least 80% identical to SEQ ID NO:22 as described in EP 1921147 and is characterized by having amino acid glutamic acid (E), or aspartic acid (D), or asparagine (N), or glutamine (Q), or alanine (A), or glycine (G), or serine (S) at position 101 (according to BPN’ numbering), preferably R101 E.
  • At least one subtilisin is at least 80% identical to SEQ ID NO:22 as described in EP 1921147 having the mutations (according to BPN’ numbering) S3T + V4I + V205I. In one embodiment, at least one subtilisin is at least 80% identical to SEQ ID NO:22 as described in EP 1921147 having the mutations (according to BPN’ numbering) S3T + V4I + R101 E + V205I. In one embodiment, at least one subtilisin is at least 80% identical to SEQ ID NO:22 as described in EP 1921147 having the mutation (according to BPN’ numbering) S3T + V4I + V199M + V205I + L217D.
  • At least one subtilisin has an amino acid sequence being at least 80% identical with SEQ ID NO:22 as described in EP 1921147 having the mutations S3T + V4I + S9R + A15T + V68A + D99S + R101S + A103S + 1104V + N218D (according to the BPN’ numbering), at least one subtilisin has an amino acid sequence at least 80% identical to SEQ ID NO:22 as described in EP 1921147 and having the mutation R101 E together with one or more substitutions selected from the group consisting of S156D, L262E, Q137H, S3T, R45E,D,Q, P55N, T58W,Y,L, Q59D,M,N,T, G61 D,R, S87E, G97S, A98D,E,R, S106A.W, N117E, H120V,D,K,N, S125M, P129D, E136Q, S144W, S161T, S163A
  • the enzymes comprise at least one amylase, preferably at least one alpha-amylase (EC 3.2.1.1). Preferably, the enzymes comprise at least one alpha-amylase selected from hybrid amylases. In one embodiment, the enzymes comprise at least one hybrid amylase at least 95% identical to SEQ ID NO: 23 of WO 2014/183920. In one embodiment, the enzymes comprise at least one hybrid amylase 95% identical to SEQ ID NQ:30 of WO 2014/183921.
  • detergent formulations comprise at least one lipase, preferably at least one triacylglycerol lipase (EC 3.1.1.3).
  • the enzymes comprise at least one Thermomyces lanuginosus triacylglycerol lipase.
  • said lipase at least 80% identical to amino acids 1-269 of SEQ ID NO:2 of US5869438.
  • said lipase comprises at least the amino acid substitutions T231 R and N233R.
  • the enzymes comprise at least one lipase comprising T231 R and N233R and one or more of the following amino acid exchanges when compared to amino acids 1-269 of SEQ ID NO:2 of US5869438: Q4V, V60S, A150G, L227G, P256K.
  • the enzymes comprise at least one lipase at least 95% identical to the full length polypeptide sequence of amino acids 1-269 of SEQ ID NO:1 of WO 2015/01009, preferably comprising at least the amino acid substitutions N 11 K/A18K/G23K/K24A/V77I/D130A/V154I/V187T/T189Q or N 11 K/A18K/G23K/K24A/L75R/V77I/D130A/V154I /187T/T189Q.
  • the enzymes comprise at least one cellulase, preferably at least one beta-1 ,4-glucanase (EC 3.2.1.4), also called endoglucanase herein.
  • the enzymes comprise at least one Humicola insolens DSM 1800 endoglucanase at least 80% identical to the amino acid sequence disclosed in Fig. 14A-E of WO 91/17244, preferably to the sequence according to amino acids 20-434.
  • said endoglucanase having one or more substitutions at positions selected from 182, 223, and 231 , most preferably selected from P182S, A223V, and A231V.
  • the enzymes comprise at least one endoglucanase at least 80% identical to a polypeptide according to SEQ ID NO: 2 of WO 95/02675. In one embodiment, the enzymes comprise at least one Bacillus sp. endoglucanase which is at least 80% identical to the amino acid sequence of position 1 to position 773 of SEQ ID NO: 2 of WO 2004/053039. In one embodiment, the enzymes comprise at least one Thielavia terrestris endoglucanase which is at least 80% identical to the amino acid sequence of position 1 to position 299 of SEQ ID NO:4 of WO 2004/053039.
  • the enzymes comprise at least one mannanase, preferably at least one beta-mannanase (EC 3.2.1.78). In one embodiment, the enzymes comprise at least one beta-mannanase selected from GH5 family mannanase. In one embodiment, the enzymes comprise at least one beta-mannanase at least 90% identical to SEQ ID NO:12 of WO 2018/184767. In one embodiment, the enzymes comprise at least one beta-mannanase at least 90% identical to SEQ ID NO: 16 of WO 2018/184767. In one embodiment, the enzymes comprise at least one beta-mannanase at least 90% identical to SEQ ID NQ:20 of WO 2018/184767.
  • the enzymes comprise at least one mannanase 95% identical to a polypeptide sequence of SEQ ID NQ:20 of WO 2018/184767 having at least one substitution selected from A101V, E405G, and Y459F.
  • the enzymes comprise at least one beta-mannanase originating from Trichoderma organisms, such as those disclosed in WO 93/24622.
  • at least one beta-mannanase is 80% identical to SEQ ID NO:1 of WO 2008/009673.
  • the beta-mannanase according to SEQ ID NO:1 of WO 2008/009673 comprises at least one substitution selected from S3R, S66P, N113Y, V181H, L207F, A215T and F274L.
  • detergent formulations comprise at least one DNAse.
  • the enzymes comprise at least one DNAse at least 80% identical to SEQ ID NO: 1-24 and SEQ ID NO: 27-28 of WO 2019/081724 and WO 2019/081721.
  • the enzymes comprise at least one DNAse comprising one or both motifs selected from SEQ ID NO:25 and SEQ ID NO:26 of WO 2019/081724.
  • the enzymes comprise at least one DNAse comprising one or more motifs selected from SEQ ID NO:73, SEQ ID NO:74 and SEQ ID NO:75 of WO 2017/060493.
  • composition is a dishwashing composition
  • this comprises preferably at least one protease and/or amylase. More preferably, it comprises an enzyme mixture.
  • enzyme mixtures which comprise or consist of the following enzymes: protease and amylase, protease and lipase (or lipolytically active enzymes), protease and cellulase, protease and mannanase, amylase, cellulase and lipase (or lipolytically active enzymes), protease, amylase and lipase (or lipolytically active enzymes), protease, lipase (or lipolytically active enzymes) and cellulase, protease, lipase (or lipolytically active enzymes) and mannanase, protease, amylase, lipase (or lipolytically active enzymes) and mannanase.
  • Liquid automated dishwashing formulations usually comprise at least one subtilisin protease as disclosed herein in amounts of about 0.10% to 0.25% by weight, more preferably about 0.12% to 0.21 % by weight, all relative to the total weight of the detergent formulation.
  • Liquid automated dishwashing formulations usually comprise at least one alpha-amylase as disclosed herein in amounts of about 0.002% to 0.015%by weight, more preferably 0.004 to 0.01 % by weight, all relative to the total weight of the detergent formulation.
  • Liquid manual dishwashing formulations usually comprise at least one subtilisin protease as disclosed herein in amounts of about 0.005% to 0.15% by weight, more preferably about 0.01 % to 0.1 % by weight, all relative to the total weight of the detergent formulation.
  • Liquid manual dishwashing formulations usually comprise at least one alpha-amylase as disclosed herein in amounts of about 0.001% to 0.015% by weight, more preferably 0.002% to 0.015% by weight, all relative to the total weight of the detergent formulation.
  • Liquid manual dishwashing formulations usually comprise at least one triacylglycerol lipase as disclosed herein in amounts of about 0.001% to 0.005% by weight, more preferably 0.001 % to 0.002% by weight, all relative to the total weight of the detergent formulation.
  • Liquid manual dishwashing formulations usually comprise at least one endoglucanase as disclosed herein in amounts of about 0.001% to 0.01 % by weight, more preferably 0.002% to 0.009% by weight, all relative to the total weight of the detergent formulation.
  • Liquid manual dishwashing formulations usually comprise at least one beta-man- nanase as disclosed herein in amounts of about 0.0005% to 0.005% by weight, more preferably 0.0005% to 0.002% by weight, all relative to the total weight of the detergent formulation.
  • composition is a laundry composition
  • this comprises preferably at least one of amylases, lipases, proteases and cellulases. More preferably, it comprises an enzyme mixture.
  • a few exemplary mixtures are: protease and amylase, protease and cellulase, cellulase and amylase, amylase, cellulase and lipase (or lipolytically active enzymes), protease, amylase and lipase (or lipolytically active enzymes), protease, lipase (or lipolytically active enzymes) and cellulase, protease, lipase (or lipolytically active enzymes) and mannanase, protease, amylase, lipase (or lipolytically active enzymes) and mannanase.
  • Liquid laundry formulations usually comprise at least one subtilisin protease as disclosed herein in amounts of about 0.005% to 0.15% by weight, more preferably about 0.01 % to 0.1 % by weight, all relative to the total weight of the detergent formulation.
  • Liquid laundry formulations usually comprise at least one alpha-amylase as disclosed herein in amounts of about 0.001 % to 0.015% by weight, more preferably 0.002% to 0.015% by weight, all relative to the total weight of the detergent formulation.
  • Liquid laundry formulations usually comprise at least one triacylglycerol lipase as disclosed herein in amounts of about 0.001% to 0.005% by weight, more preferably 0.001% to 0.002% by weight, all relative to the total weight of the detergent formulation.
  • Liquid laundry formulations usually comprise at least one endoglucanase as disclosed herein in amounts of about 0.001 % to 0.01% by weight, more preferably 0.002% to 0.009% by weight, all relative to the total weight of the detergent formulation.
  • Liquid laundry formulations usually comprise at least one beta-mannanase as disclosed herein in amounts of about 0.0005% to 0.005% by weight, more preferably 0.0005% to 0.002% by weight, all relative to the total weight of the detergent formulation.
  • the enzymes may be adsorbed onto carriers in order to protect them from premature decomposition.
  • composition comprises one or more enzymes, it may also comprise enzyme stabilizers (for more details see component (h)). Enzymes or enzyme packages suitable for such compositions are commercially available. Examples are the Lavergy® brands from BASF.
  • Sequestrants (f) also termed builders, structural substances, framework substances, complexing agents, chelators, chelating agents or softeners, bind alkaline earth metals and other water-soluble metal salts without precipitating. They help to break up soil, disperse soil components, help to detach soil and in some cases themselves have a washing effect. Many of the sequenstrants listed below are multi-functional, meaning that the substances have additional functions, such as a dispersing activity or anti-grey- ing properties.
  • Suitable sequestrants may be either organic or inorganic in nature. Examples are aluminosilicates, carbonates, phosphates and polyphosphates, polycarboxylic acids, polycarboxylates, hydroxycarboxylic acids, phosphonic acids, e.g. hydroxyalkylphosphonic acids, phosphonates, aminopolycarboxylic acids and salts thereof, and polymeric compounds containing carboxylic acid groups and salts thereof.
  • Suitable inorganic sequestrants are, for example, crystalline or amorphous aluminosilicates with ion-exchanging properties, such as zeolites.
  • Crystalline silicates suitable as sequestrants are, for example, disilicates or sheet silicates, e.g. 5-Na2Si20s or B- Na2Si2C>5 (SKS 6 or SKS 7).
  • Suitable inorganic sequestrant substances based on carbonate are carbonates and hydrogencarbonates. These can be used in the form of their alkali metal, alkaline earth metal or ammonium salts.
  • Customary phosphates used as inorganic sequestrants are alkali metal orthophosphates and/or polyphosphates, for example pentasodium triphosphate.
  • Suitable organic sequestrants are, for example, C4-C3o-di-, -tri- and -tetracarboxylic acids, for example succinic acid, propanetricarboxylic acid, butanetetracarboxylic acid, cyclopentanetetracarboxylic acid, and alkyl- and alkenylsuccinic acids with C2-C2o-alkyl or -alkenyl radicals.
  • Suitable organic sequestrants are also hydroxycarboxylic acids and polyhydroxycarboxylic acids (sugar acids).
  • C4-C20-hydroxycarboxylic acids for example malic acid, tartaric acid, glutonic acid, mucic acid, lactic acid, glutaric acid, citric acid, tartronic acid, glucoheptonic acid, lactobionic acid, and sucrose- mono-, -di- and -tricarboxylic acid.
  • citric acid and salts thereof preference is given to citric acid and salts thereof.
  • Suitable organic sequestrants are also phosphonic acids, for example hydroxyalkylphosphonic acids or aminophosphonic acids, and the salts thereof.
  • Suitable organic sequestrants are moreover polyas- paratic acids.
  • Polyaspartic acid include salts of polyaspartic acids. Salt forming cations may be monovalent or multivalent, examples being sodium, potassium, magnesium, calcium, ammonium, and the ammonium salt of mono-, di- and triethanolamine.
  • Such polymers may be co-polymers, in particular of (a) L- or D-aspartic acid (preferably L- aspartic acid), (b) a carboxylic acid and (c) a diamone or an amino alcohol.
  • Such copolymers generally comprise 70-95 mol% of (a), 5-30 mol% of (b) and 2-20 mol% of (c).
  • the molar ratio of the carboxyl-containing compound (b) to the diamine or amino alcohol (c) is preferably between 5:1 and 1 :1.5 or between 3:1 and 1 :1.2, and more preferably between 3:1 and 1 :1 or 2:1 and 1 :1.
  • Suitable organic sequestrants are additionally aminopolycarboxylic acids, such as nitrilotriacetic acid (NTA), nitrilomonoacetic dipropionic acid, nitrilotripropionic acid, p-alaninediacetic acid (p-ADA), ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid, 1 ,3-propylenediaminetet- raacetic acid, 1 ,2-propylenediaminetetraacetic acid, N-(alkyl)ethylenediaminetriacetic acid, N-(hydroxyalkyl)ethylenediaminetriacetic acid, ethylenediaminetriacetic acid, cy- clohexylene-1 ,2-diaminetetraacetic acid, iminodisuccinic acid, ethylenediaminedisuccinic acid, serinediacetic acid, isoserinediacetic acid, L-asparagin
  • Suitable organic sequestrants are additionally polymeric compounds containing carboxylic acid groups, such as acrylic acid homopolymers.
  • carboxylic acid groups such as acrylic acid homopolymers.
  • the term "acrylic acid homopolymer” also comprises polymers in which some or all of the carboxylic acid groups are present in neutralized form.
  • Suitable polymeric compounds containing carboxylic acid groups are also oligomaleic acids.
  • Suitable polymeric compounds containing carboxylic acid groups are also terpolymers of unsaturated C4-Cs-dicarboxylic acids.
  • Suitable unsaturated C4-Cs-dicarboxylic acids in this context are, for example, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, methylenemalonic acid and citraconic acid.
  • Suitable polymeric compounds containing carboxylic acid groups are also homopolymers of the monoethylenically unsaturated Cs-Cs-monocarboxylic acids, for example acrylic acid, methacrylic acid, crotonic acid, 2-ethylacrylic acid, 2-phenylacrylic acid, cinnamic acid, vinylacetic acid and sorbic acid, copolymers of dicarboxylic acids, for example of maleic acid and acrylic acid; terpolymers of maleic acid, acrylic acid and a vinyl ester of a Ci-Cs-carboxylic acid; and copolymers of maleic acid with C2-Cs-olefins.
  • Defoamer and/or foam stabilizer (g) are for example soaps, paraffins and silicone oils.
  • Further additives (h) are for example hydrotropic agents, acids, bases, buffering agents, enzyme stabilizers, bleaching agents, corrosion inhibitors, dyes, fragrances, thickeners, activity enhancers different from component (b) and inorganic salts.
  • Hydrotropic agents are compounds which solubilizes hydrophobic compounds in aqueous solution by means other than micellar solubilization. Similar to surfactants, hydrotropes often (but not necessarily) consist of a hydrophilic part and a hydrophobic part, but in contrast to surfactants the hydrophobic part is generally too small to cause spontaneous self-aggregation. Examples are aromatic sulfonic acid salts, such as the alkali metal, earth alkaline metal or ammonium salts of p-toluenesulfonic acid (e.g. sodium, potassium, calcium or ammonium p-tosylate), of xylene sulfonic acids (e.g.
  • the sodium, potassium, calcium or ammonium salts of o-, m- or p-xylene sulfonates) or of cumene sulfonic acids generally of p-cumene sulfonic acid (e.g. the sodium, potassium, calcium or ammonium salts of p-cumenesulfonate); adenosine triphosphate (ATP); and urea.
  • p-cumene sulfonic acid e.g. the sodium, potassium, calcium or ammonium salts of p-cumenesulfonate
  • ATP adenosine triphosphate
  • the acids can be inorganic or organic. Suitable inorganic acids are for example sulfuric acid, hydrochloric acd and phosphoric acid, where sulfuric acid is generally preferred. Suitable organic acids are for example aliphatic, saturated non-substituted Ci-Ce- mono-, di- and tri-carboxylic acids such as formic acid, acetic acid, propanoic acid, oxalic acid, succinic acid and glutaric acid; aliphatic, saturated Ci-Ce-mono-, di- and tricarboxylic acids carrying one or more OH groups, such as lactic acid, tartric acid and citric acid; aliphatic, unsaturated Ci-Ce-mono-, di- and tri-carboxylic acids such as sorbic acid; aromatic carboxylic acids, such as benzoic acid, salicylic acid and mandelic acid; and sulfonic acids, such as methanesulfonic acid or toluenesulfonic acid.
  • Suitable bases are in particular inorganic bases, such as the carbonates mentioned in context with the sequestrant, e.g. sodium or potassium carbonate; further alkali metal and earth alkaline meal hydroxides, such as NaOH or KOH.
  • Suitable buffering agents are the typical systems, such as hydrogenphosphate/dihy- drogenphosphate buffer, carbonate/hydrogencarbonate buffer, acetic acid/acetate buffer or Tris buffer. Moreover, most of the above acids which are weak and the anion of which is not a strong salt also have buffering capacity.
  • composition comprises one or more enzymes
  • it may also comprise enzyme stabilizers, for example calcium propionate, sodium formate, boric acid or salts thereof, boronic acids and salts thereof, polyols, peptide aldehydes, and/or antioxidants.
  • enzyme stabilizers for example calcium propionate, sodium formate, boric acid or salts thereof, boronic acids and salts thereof, polyols, peptide aldehydes, and/or antioxidants.
  • Suitable boronic acids are for examples aromatic and heteroaromatic boronic acids, such as benzene boronic acid (BBA; also termed phenylboronic acid (PBA)), 4- formylphenylboronic acid (4-FPBA), 2-FPBA, 3-FPBA, 4-carboxyphenylboronic acid (4- CPBA), 4-(hydroxymethyl)-phenylboronic acid (4-HMPBA), p-tolylboronic acid (p-TBA), (2-acetamidophenyl)-boronic acid, 2-bromophenylboronic acid, 3-bromophenylboronic acid, 4-bromophenylboronic acid, 2-chlorophenylboronic acid, 3-chlorophenylboronic acid, 4-chlorophenylboronic acid, 2,4-dichlorophenylboronic acid, 3,5-dichlorophenyl- boronic acid, 4-fluorophenylboronic acid, 3-chloro-4-fluoropheny
  • Suitable are p-methyl-phenylethylboronic acid, diphenyl boronic acid anhydride and octyl boronic acid. Suitable are also mixtures of two or more different boronic acids. Suitable salts of the above-mentioned boronic acids are for example the alkali metal salts, such as the sodium or potassium salts, the earth alkaline metal salts, such as the magnesium and calcium salts, and ammonium salts.
  • Suitable polyols are for example polyols containing from 2 to 6 hydroxyl groups, such as ethylene glycol, propylene glycol, 1 ,2-propanediol, 1 ,2-butanediol, 1 ,2-pentanediol, hexyleneglycol, glycerol, sorbitol, mannitol, erythriol, glucose, fructose, and lactose.
  • Peptide aldehydes are oligopeptides with reduced C-terminus (i.e. in which the C(O)OH group is reduced to an aldehyde [CH(O)] group)
  • amino acid(s) optionally comprising an N-terminal protection group, or is a protease inhibitor of the protein type such as RASI, BASI, WASI (bifunctional alpha-amylase/ subtilisin inhibitors of rice, barley and wheat) or CI2 or SSI.
  • a suitable bleaching agent is hydrogen peroxide.
  • some enzymes have bleaching properties.
  • Dyes can be added to obtain a specific aesthetic appearance, but also be used as shading dyes for reducing or avoiding (auto-)oxidation of components of the composition, especially of unsaturated organic compounds, triggered by UV or visible light (e.g. if the container in which the composition is kept allows transmission of UV or visible light) and/or transition metal ion catalysis (if present). If used as shading dyes, these impart generally a violet or blue color. Shading dyes are particularly useful in laundry compositions, such as laundry detergents or textile softening compositions, where they can help avoiding yellowing of the textiles.
  • shading dyes are direct dyes (also known as substantive dyes; water soluble dyes with an affinity for fibres and which are taken up directly; generally azo dyes), e.g. violet 7, direct violet 9, direct violet 11 , direct violet 26, direct violet 31 , direct violet 35, direct violet 40, direct violet 41 , direct violet 51 , and direct violet 99; moreover direct violet 66; acid dyes, such as azine dyes, e.g. acid blue 98, acid violet 50, and acid blue 59, more preferably acid violet 50 and acid blue 98; or non-azine dyes, e.g.
  • hydrophobic dyes dyes which do not contain any charged water solubilising group; generally selected from the groups of disperse and solvent dyes, in particular blue and violet anthraquinone and mono-azo dyes, e.g. solvent violet 13, disperse violet 27 disperse violet 26, disperse violet 28, disperse violet 63 and disperse violet 77; basic dyes (organic dyes which carry a net positive charge and deposit onto cotton), e.g.
  • triarylmethane basic dyes methane basic dye, anthraquinone basic dyes, basic blue 16, basic blue 65, basic blue 66, basic blue 67, basic blue 71 , basic blue 159, basic violet 19, basic violet 35, basic violet 38, basic violet 48; basic blue 3, basic blue 75, basic blue 95, basic blue 122, basic blue 124, basic blue 141 ; reactive dyes (dyes which contain an organic group capable of reacting with cellulose and linking the dye to cellulose with a covalent bond, and deposit onto cotton), e.g. reactive blue 19, reactive blue 163, reactive blue 182 and reactive blue, reactive blue 96; and dye conjugates (formed by binding direct, acid or basic dyes to polymers or particles via physical forces).
  • Fragrances can be of natural or synthetic origin; their nature is in general not critical.
  • natural aromatic substances are, for instance, extracts from blossom (lilies, lavender, roses, jasmine, neroli, ylang-ylang), from stems and leaves (geranium, patchouli, petitgrain), from fruit (aniseed, coriander, carraway, juniper), from fruit peel (bergamot, lemons, oranges), from roots (mace, angelica, celery, cardamom, costus, iris, calmus), from wood (pinewood, sandalwood, guaiacum wood, cedarwood, rosewood), from herbs and grasses (tarragon, lemon grass, sage, thyme), from needles and twigs (spruce, pine, Scots pine, mountain pine), from resins and balsams (galbanum, elemi, benzoin, myrrh, olibanum, opoponax).
  • Aromatic substance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethylmethylphenyl glycinate, allylcyclohexyl propionate, styrallyl propionate and ben-'zyl salicylate.
  • the ethers include, for example, benzyl ethyl ether;
  • the aldehydes include, for example, the linear alkanals having from 8 to 18 hydrocarbon atoms, citral, citronellal, citronellyl oxyacetaldehyde, cyclamen aldehyde, hy- droxycitronellal, lilial and bourgeonal;
  • the ketones include, for example, the ionones, isomethylionone and methyl cedryl ketone;
  • the alcohols include, for example, anethol, citronellol, eugenol, isoeugenol, geraniol, linalool, phenyl ethyl alcohol and terpinol; and
  • the hydrocarbons include mainly the terpenes and balsams.
  • Ethereal oils of relatively low volatility which are chiefly used as aroma components, are also suitable as perfume oils, e.g. sage oil, chamomile oil, clove oil, melissa oil, oil of cinnamon leaves, lime blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil, labolanum oil and lavandin oil.
  • alpha-hexylcinnamaldehyde 2-phenoxyethyl isobutyrate (Pheni- rat 1 ), dihydromyrcenol (2,6-dimethyl-7-octen-2-ol), methyl dihydrojasmonate (preferably having a cis-isomer content of more than 60 wt.%) (Hedione 9 , Hedione HC 9 ), 4,6,6,7,8,8-hexamethyl-1 ,3, 4, 6, 7, 8- hexahydrocyclopenta[g]benzopyran (Galaxolide 3 ), tetrahydrolinalool (3,7-dimethyloctan-3-ol), ethyl linalool, benzyl salicylate, 2-methyl-3- (4-tertbutylphenyl)propanal (Lilial 2 ), cinnamyl alcohol, 4,7-methano-3a,4,5,6,7,7a
  • the fragrances may optionally be incorporated in encapsulated form.
  • the thickeners serve to impart the desired viscosity to the composition of the invention.
  • any known thickener rheology modifier
  • Suitable thickeners may either be of natural origin or of synthetic nature.
  • Thickeners of natural origin are mostly derived from polysaccharides. Examples are xanthan, gellan gum, carob flour, guar flour or gum, carrageenan, agar, tragacanth, gum arabic, alginates, modified starches such as hydroxyethyl starch, starch phosphate esters or starch acetates, dextrins, pectins and cellulose derivatives, such as carboxymethylcellulose, hydroxyethylcellulose, hydrophobically modified hydroxyethyl cellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, methylcellulose and the like.
  • bacterial cellulose meaning any type of cellulose produced via fermentation of a bacteria of the genus Acetobacter such as CELLULON® (CPKelco U.S.) and including materials referred to as microfibrillated cellulose or reticulated bacterial cellulose; and non-bacterial cellulose, e.g. cellulosic fibers extracted from vegetables, fruits or wood, e.g. AvicelO from FMC, Citri-Fi from Fiberstar or Betafib from Cosun.
  • CELLULON® CPKelco U.S.
  • non-bacterial cellulose e.g. cellulosic fibers extracted from vegetables, fruits or wood, e.g. AvicelO from FMC, Citri-Fi from Fiberstar or Betafib from Cosun.
  • Thickeners of natural origin are also inorganic thickeners, such as polysilicic acids and clay minerals, for example sheet silicates, and also the silicates mentioned for the builders. More specific examples are listed in the following table. Most are derived from smectite clays and silica derivatives.
  • synthetic thickeners are polyacrylic and polymethacrylic compounds, such as (partly) crosslinked homopolymers of acrylic acid, for example homopolymers of acrylic acid which have been crosslinked with an allyl ether of sucrose or pentaerythritol, or with propylene (carbomers), for example the Carbopol® brands from BF Goodrich (e.g. Carbopol® 676, 940, 941 , 934 and the like) or the Polygel® brands from 3V Sigma (e.g.
  • Polygel® DA copolymers of ethylenically unsaturated mono- or dicarboxylic acids, for example terpolymers of acrylic acid, methacrylic acid or maleic acid with methyl acrylate or ethyl acrylate and a (meth)acrylate which derives from long- chain ethoxylated alcohols, for example the Acusol® brands from Rohm & Haas (e.g.
  • Acusol® 820 or 1206A copolymers of two or more monomers which are selected from acrylic acid, methacrylic acid and the Ci-C4-alkyl esters thereof, for example copolymers of methacrylic acid, butyl acrylate and methyl methacrylate or of butyl acrylate and methyl methacrylate, for example the Aculyn® and Acusol® brands from Rohm & Haas (e.g.
  • Aculyn® 22, 28 or 33 and Acusol® 810, 823 and 830), or crosslinked high molecular weight acrylic acid copolymers for example copolymers of C -Cso-alkyl acrylates with one or more comonomers selected from acrylic acid, methacrylic acid and the Ci-C4-alkyl esters thereof, said copolymers having been crosslinked with an allyl ether of sucrose or pentaerythritol (e.g. Carbopol® ETD 2623, Carbopol® 1382 or Carbopol® AQUA 30 from Rohm & Haas).
  • an allyl ether of sucrose or pentaerythritol e.g. Carbopol® ETD 2623, Carbopol® 1382 or Carbopol® AQUA 30 from Rohm & Haas.
  • Suitable thickeners are moreover phospholipids, such as alkylated phosphatidyl choline, phosphobetaines or alkyl phosphate quaternary compounds.
  • Examples of synthetic thickeners are also reaction products of maleic acid polymers with ethoxylated long-chain alcohols, for example the Surfonic L series from Texaco Chemical Co. or Gantrez AN-119 from ISP; polyethylene glycols, polyamides, polyimines and polycarboxylic acids.
  • Examples of synthetic thickeners are moreover dibenzylidene polyol acetal derivatives (DBPA derivative). These may comprise a dibenzylidene sorbitol acetal derivative (DBS).
  • Said DBS derivative may be selected from the group consisting of: 1 ,3:2, 4- dibenzylidene sorbitol; 1 ,3:2,4-di(p-methylbenzylidene) sorbitol; 1 ,3:2,4-di(p-chloroben- zylidene) sorbitol; 1 ,3:2,4-di(2,4-dimethyldibenzylidene) sorbitol; 1 ,3:2,4-di (p-ethyl-ben- zylidene) sorbitol; 1 ,3:2,4-di(3,4-dimethyldibenzylidene) sorbitol; and mixtures thereof.
  • Suitable thickeners are moreover di-amido gellants, e.g. selected from those having a molecular weight from about 150g/mol to about 1,500g/mol, or even from about 500g/mol to about 900 g/mol.
  • Such di-amido gellants may comprise at least two nitrogen atoms, wherein at least two of said nitrogen atoms form amido functional substitution groups.
  • R a and R b may comprise a pH-tunable group, wherein the pH- tunable amido-gellant may have a pKa of from about 1 to about 30, or even from about 2 to about 10.
  • the pH tunable group may comprise a pyridine.
  • L may comprise a carbon chain comprising between 2 and 20 carbon atoms.
  • L may comprise a pH-tunable group.
  • the pH-tunable group may be a secondary amine.
  • Examples of synthetic thickeners are also non-polymeric crystalline, hydroxyl functional structurants .
  • Said compound may comprise a crystallizable glyceride which can be pre-emulsified to aid dispersion into the final liquid detergent formulation.
  • the crystallizable glycerides may comprise hydrogenated castor oil or "HCO" or derivatives thereof, provided that it is capable of crystallizing in the liquid formulation.
  • Suitable activity enhancers different from component (b) are in particular PEI.
  • PEI are polymers of ethylenediamine and can be characterized by repeating groups of the empirical formula -[CH2-CH2-NH] n - wherein n ranges from approximately from 10 to 100,000, e.g. from 10 to 15000.
  • PEI can be linear or branched (branched forms are not correctly reflected in the above formula; nevertheless the formula should also symbolize branched forms), where branching can result in dendrimers, star-like polymers, hyperbranched polymers and other branched forms.
  • Branched polyethylenimines can be characterized by their degree of branching (DB).
  • DB may be determined, for example, by 13 C-NMR spectrometry and is defined as follows:
  • DB D +T/D+T+L
  • D stands for the fraction of tertiary amino groups
  • L linear
  • T terminal
  • DB ranges from 0.1 to 0.95, more preferably from 0.25 to 0.90, in particular from 0.30 to 0.80, and specifically from 0.5-0.8.
  • the PEIs used in the present compositions have weight average molecular weight M w of from 500 to 1 ,000,000 g/mol, more preferably from 600 to 75,000 g/mol, and in particular from 800 to 25000 g/mol, as determined by gel permeation chromatography (GPC with PEG or PMMA standard; specifically with multi angle light scattering (MALS) detector of the intermediate respective polyalkylenimine, with 1.5% by weight aqueous formic acid as eluent and cross-linked poly-hydroxyethyl methacrylate as stationary phase).
  • GPC gel permeation chromatography
  • MALS multi angle light scattering
  • the PEIs used in the present compositions are grafted with ethylene oxide (EG) and/or propylene oxide (PO).
  • EG ethylene oxide
  • PO propylene oxide
  • the PEI is grafted with 5 to 100 mol of alkylene oxide per mol of PEI.
  • the PEI is typically contained in the homecare or l&l composition in an amount of from 0.001 to 10% by weight, preferably from 0.001 to 1% by weight, relative to the total weight of the composition.
  • Suitable PEIs are commercially available, e.g. under the Lupasol® and Sokolan® HP brands from BASF.
  • Suitable inorganic salts are for example sodium chloride and calcium chloride.
  • composition of the invention is a dishwashing composition.
  • Dishwashing compositions preferably comprise:
  • dishwashing compositions are in liquid or gel form and are suitable both for machine washing as well as for manual dishwashing.
  • manual dishwashing compositions have to be adapted so as not to present any hazard for the user.
  • the amount of optionally present acids and/or bases is such that the resulting pH does not harm the user’s skin.
  • Suitable and preferred components (a) to (h) are those listed above.
  • Dishwashing compositions may further comprise as component (h) anti-greying polymers and scale inhibitor or scale dispersing agents.
  • composition of the invention is a dishwashing composition comprising:
  • the antimicrobial agent (a) is 2-phenoxyethanol, and this is contained in an amount of from 0.1 to 5% by weight, e.g. 0.1 to 2% by weight, relative to the total weight of the composition; and the alkoxylated amine (b) is contained in an amount of from 0.1 to 7% by weight.
  • composition of the invention is a laundry composition.
  • Laundry compositions preferably comprise:
  • Such laundry compositions are in liquid or gel form and are suitable both for machine washing as well as for manual laundry washing.
  • manual laundry compositions have to be adapted so as not to present any hazard for the user.
  • the amount of optionally present acids and/or bases is such that the resulting pH does not harm the user’s skin.
  • Suitable and preferred components (a) to (h) are those listed above.
  • laundry compositions are laundry detergents, fabric softeners, rinsing compositions, bleacher compositions, and stain remover compositions.
  • Laundry detergents may further comprise as component (h) dye transfer inhibitors, anti-greying polymers, soil release polymers, anti-redeposition agents, anti-shrinking agents, anti-wrinkle agents, ironing aids, skin benefit agents, antistatic agents, processing aids, such as electrolyts, pearlisers, opacifiers, sunscreens, and/or antioxidants.
  • component (h) dye transfer inhibitors such as dye transfer inhibitors, anti-greying polymers, soil release polymers, anti-redeposition agents, anti-shrinking agents, anti-wrinkle agents, ironing aids, skin benefit agents, antistatic agents, processing aids, such as electrolyts, pearlisers, opacifiers, sunscreens, and/or antioxidants.
  • anti-greying and anti-redeposition agents are often used interchangeably. Suitable examples for such agents are the aforementioned PEIs in grafted (alkox- ylated) or ungrafted form, other alkyleneimine polymers, such as polypropyleneimine (PPI), also in grafted or ungrafted form, further ethoxylated hexamethylene diamine polymers which are quaternized and - optionally but preferably - sulfated, and graft polymer GP comprising as a graft base a polyether and as grafted side chains copolymers comprising at least one comonomer (CM) as described below.
  • PEIs alkox- ylated
  • PPI polypropyleneimine
  • graft polymer GP comprising as a graft base a polyether and as grafted side chains copolymers comprising at least one comonomer (CM) as described below.
  • CM comonomer
  • the ethoxylated hexamethylene diamine polymers preferably contain in average 10 to 50, more preferably 15 to 40 and even more preferably 20 to 30 EG (ethoxylate) groups per NH group, resulting in an average molecular weight Mw in the range from 2,000 to 10,000 g/mol, more preferably 3,000-8,000, most preferably 4,000-6,000.
  • the ethoxylated hexamethylene diamine is quaternized and also sulfated, preferably bearing 2 cationic ammonium groups and 2 anionic sulfate groups.
  • the side chains comprise at least one comonomer (CM) selected from
  • CH 2 CZ-CO-OR b (CM-lc) wherein R a is selected from Ci-C 2 i-alkyl, for example methyl, n-propyl, n-pentyl, n-hep- tyl, n-nonyl, iso-nonyl, n-undecyl, n-tridecyl, n-pentadecyl, n-heptadecyl, or n-non- adecyl, R b is selected from C 2 -C 2 o-alkyl, preferably with an even number of carbon atoms, for example ethyl, n- and iso propyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl or isodec
  • the polyethers bear at least 5 ether groups per mole and - if at all - only hydroxyl groups, for example one, two or three hydroxyl groups per molecule. Such hydroxyl groups may be primary or secondary hydroxyl groups, primary hydroxyl groups being preferred.
  • the polyethers are preferably polyethylene glycols, for example with an average molecular weight M n in the range of from 500 to 25,000 g/mol, preferably 1 ,000 to 15,000 g/mole and even more preferably 1 ,500 to 10,000 g/mol, e.g. 1 ,500 to 4,000 g/mol or 4,000 to 6,000 g/mol or 5,000 to 8,000 g/mol.
  • the polyethers are preferably polypropylene glycols, for example with an average molecular weight M n in the range of from 500 to 20,000 g/mol, preferably 2,000 to 10,000 g/mol and even more preferably 4,000 to 9,000 g/mol
  • the polyethers are copolymers of ethylene glycol and propylene glycol units, for example random copolymers and preferably block copolymers, for example di-block copolymers and tri-block copolymers.
  • copolymers of ethylene glycol and propylene glycol are block copolymers.
  • the polyethylene glycols, polypropylene glycols and EO-PO block copolymers can be non-capped or end-capped with Ci-C2o-alkyl or C3-C2o-2-hydroxyalkyl.
  • anti-greying agents are carboxymethyl cellulose (CMC), ether sulfonic acid salts of starch, ether sulfonic acid salts of cellulose, acidic sulfuric acid ester salts of cellulose, acidic sulfuric acid ester salts of starch, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose methyl hydroxyethyl cellulose, methyl carboxymethyl cellulose, ethyl hydroxyethyl cellulose and mixtures thereof.
  • CMC carboxymethyl cellulose
  • ether sulfonic acid salts of starch ether sulfonic acid salts of cellulose
  • acidic sulfuric acid ester salts of cellulose acidic sulfuric acid ester salts of starch
  • anti-greying agents are polyalkylene oxide polymers (ethylene oxide, propylene oxide and/or butylene oxide polymers) grafted with methyl acrylate, ethyl acrylate, methyl methacrylate and/or ethyl methacrylate.
  • Suitable softening agents are quaternary ammonium salts, especially quats or ester quats.
  • Quats are compounds [NR 1 R 2 R 3 R 4 ] + X; wherein R 1 , R 2 , R 3 and R 4 are alkyl groups, where at least one, generally two is/are long-chained alkyl and the others are generally methyl or ethyl, and X- is a counter anion, such as chloride.
  • DSDMAC disearyl dimethyl ammonium chloride, also termed DODMAC (dioctadecyl dimethyl ammonium chloride)
  • TDMAC disitallow di-methyl ammonium chloride
  • DHTDMAC dehydrogenated tallow alkyl dimethyl ammonium chloride
  • DDAC- C10 dehydrogenated tallow alkyldimethylammonium chloride.
  • Esterquats are derived from alkanolamines in which at least one alkanol group is esterified with a fatty acid.
  • esterquats are derived from methyl-triethanol-ammmonium salts, where 1 , 2 or 3 of the OH groups are esterified with a fatty acid, and from dimethyl-diethanol-ammonium salts, where 1 or 2 OH groups are esterified with a fatty acid. Preference is given to esterquats.
  • composition of the invention is a laundry composition comprising:
  • the antimicrobial agent (a) is 2-phenoxyethanol, and this is contained in an amount of from 0.1 to 5% by weight, e.g. 0.1 to 2% by weight, relative to the total weight of the composition; and the alkoxylated amine (b) is contained in an amount of from 0.1 to 7% by weight.
  • composition of the invention is a surface cleaning composition.
  • Surface cleaning compositions preferably comprise:
  • Such surface cleaning compositions are in liquid or gel form and are suitable for manual use.
  • surface cleaning compositions for household use have to be adapted so as not to present any hazard for the user.
  • the amount of optionally present acids and/or bases is such that the resulting pH does not harm the user’s skin.
  • Suitable and preferred components (a) to (h) are those listed above.
  • Surface cleaning compositions may further comprise as component (h) anti-greying polymers and scale inhibitor or scale dispersing agents.
  • composition of the invention is a surface cleaning compositioncomprising:
  • composition of the invention is a surface cleaning composition comprising:
  • the antimicrobial agent (a) is 2-phenoxyethanol, and this is contained in an amount of from 0.1 to 5% by weight, e.g. 0.1 to 2% by weight, relative to the total weight of the composition; and the alkoxylated amine (b) is contained in an amount of from 0.1 to 7% by weight.
  • the homecare or l&l composition is a refill concentrate.
  • Refill concentrates contain all ingredients of the final ready-to-use product, but for water which is either essentially absent (“essentially” taking account of the fact that some of the ingredients may contain some residual water) or contained in amounts far below those of the final ready-to-use product.
  • the end user has just to fill the refill concentrate into a suitable container and add the indicated amount of water.
  • Such refill concentrates preferably comprise:
  • the antimicrobial agent (a) is 2-phenoxyethanol, and this is contained in an amount of from 0.1 to 10% by weight, relative to the total weight of the composition; and the alkoxylated amine (b) is contained in an amount of from 0.1 to 10% by weight.
  • Crop protection compositions needing preservation generally contain water.
  • compositions are e. g. solutions, emulsions, suspensions, pastes, capsules, and mixtures thereof.
  • composition types are suspensions (e.g. SC, OD, FS), emulsifiable concentrates (e.g. EC), emulsions (e.g. EW, EO, ES, ME), capsules (e.g. CS, ZC), pastes, as well as gel formulations for the treatment of plant propagation materials such as seeds (e.g. GF).
  • suspensions e.g. SC, OD, FS
  • emulsifiable concentrates e.g. EC
  • emulsions e.g. EW, EO, ES, ME
  • capsules e.g. CS, ZC
  • pastes e.g. GF
  • gel formulations for the treatment of plant propagation materials e.g. GF.
  • compositions are prepared in a known manner, such as described by Mollet and Grubemann, Formulation technology, Wiley VCH, Weinheim, 2001 ; or Knowles, New developments in crop protection product formulation, Agrow Reports DS243, T&F Informa, London, 2005.
  • auxiliaries are solvents, liquid carriers, surfactants, dispersants, emulsifiers, wetters, adjuvants, solubilizers, penetration enhancers, protective colloids, adhesion agents, thickeners, humectants, repellents, attractants, feeding stimulants, compatibilizers, anti-freezing agents, anti-foaming agents, colorants, tackifiers and binders.
  • Suitable solvents and liquid carriers are water and organic solvents, such as mineral oil fractions of medium to high boiling point, e.g. kerosene, diesel oil; oils of vegetable or animal origin; aliphatic, cyclic and aromatic hydrocarbons, e. g. toluene, paraffin, tetrahydronaphthalene, alkylated naphthalenes; alcohols, e.g. ethanol, propanol, butanol, benzylalcohol, cyclo-'hexanol; glycols; DMSO; ketones, e.g. cyclo-'hexanone; esters, e.g. lactates, carbonates, fatty acid esters, gamma-butyrolactone; fatty acids; phospho- nates; amines; amides, e.g. fatty acid dhmethylamides; and mixtures thereof.
  • mineral oil fractions of medium to high boiling point e.g.
  • Suitable surfactants are surface-active compounds, such as anionic, cationic, nonionic and amphoteric surfactants, block polymers, polyelectrolytes, and mixtures there _, of.
  • Such surfactants can be used as emusifier, dispersant, solubilizer, wetter, penetration enhancer, protective colloid, or adjuvant. Examples of surfactants are listed in McCutcheon's, Vol.1 : Emulsifiers & Detergents, McCutcheon's Directories, Glen Rock, USA, 2008 (International Ed. or North American Ed.).
  • Suitable anionic surfactants are alkali, alkaline earth or ammonium salts of sulf-'onates, sulfates, phosphates, carboxylates, and mixtures thereof.
  • sulf-'onates are alkylarylsulfonates, diphenylsulfonates, alpha-olefin sulfonates, lignine sulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of alkoxylated arylphenols, sulfonates of condensed naphthalenes, sulf-'onates of dodecyl- and tridecylbenzenes, sulfonates of naphthalenes and alkyhnaphtha-'lenes, sulfosuccinates or sulfosuccinamates.
  • Examples of sulfates are sulfates of fatty acids and oils, of ethoxylated alkylphenols, of alcohols, of ethoxylated alcohols, or of fatty acid esters.
  • Examples of phosphates are phosphate esters.
  • Examples of carboxylates are alkyl carboxylates, and carboxylated alcohol or alkylphenol ethoxylates.
  • Suitable nonionic surfactants are alkoxylates, N-subsituted fatty acid amides, amine oxides, esters, sugar-based surfactants, polymeric surfactants, and mixtures thereof.
  • alkoxylates are compounds such as alcohols, alkylphenols, amines, amides, arylphenols, fatty acids or fatty acid esters which have been alkoxylated with 1 to 50 equivalents.
  • Ethylene oxide and/or propylene oxide may be employed for the alkoxyla- tion, preferably ethylene oxide.
  • N-subsititued fatty acid amides are fatty acid glucamides or fatty acid alkanolamides.
  • esters are fatty acid esters, glycerol esters or monoglycerides.
  • sugar-based surfactants are sorbitans, ethoxylated sorbitans, sucrose and glucose esters or alkylpolyglucosides.
  • polymeric surfactants are home- or copolymers of vinylpyrrolidone, vinylalcohols, or vinylacetate.
  • Suitable cationic surfactants are quaternary surfactants, for example quaternary am-rnonium compounds with one or two hydrophobic groups, or salts of long-chain primary amines.
  • Suitable amphoteric surfactants are alkylbetains and imidazolines.
  • Suitable block polymers are block polymers of the A-B or A-B-A type comprising blocks of polyethylene oxide and polypropylene oxide, or of the A-B-C type comprising alkanol, polyethylene oxide and polypropylene oxide.
  • Suitable polyelectrolytes are polyacids or polybases. Examples of polyacids are alkali salts of polyacrylic acid or polyacid comb polymers.
  • polybases are polyvinylamines or polyethyleneamines.
  • Suitable adjuvants are compounds which have a neglectable or even no pesticidal activity themselves, and which improve the biological performance of the polymeric, ionic compound comprising imidazolium groups on the target. Examples are surfactants, mineral or vegetable oils, and other auxilaries. Further examples are listed by Knowles, Adjuvants and additives, Agrow Reports DS256, T&F Informa UK, 2006, chapter 5.
  • Suitable thickeners are polysaccharides (e.g. xanthan gum, carboxymethylcellu-'lose), anorganic clays (organically modified or unmodified), polycarboxylates, and silicates.
  • Suitable anti-freezing agents are ethylene glycol, propylene glycol, urea and glycerin.
  • Suitable anti-foaming agents are silicones, long chain alcohols, and salts of fatty acids.
  • Suitable colorants e.g. in red, blue, or green
  • Suitable colorants are pigments of low water solubility and water-soluble dyes. Examples are inorganic colorants (e.g. iron oxide, titan oxide, iron hexacyanoferrate) and organic colorants (e.g. alizarin-, azo- and phthalocyanine colorants).
  • Suitable tackifiers or binders are polyvinylpyrrolidons, polyvinylacetates, polyvinyl alcohols, polyacrylates, biological or synthetic waxes, and cellulose ethers.
  • the crop protection compositions contain of course at least one active agent suitable for combating harmul microorganisms, invertebrate pests or weeds, e.g. at least one fungicide, insecticide, acaricide, nematicide, moluscicide and/or herbicide; or for regulating the growth of plants.
  • active agent suitable for combating harmul microorganisms, invertebrate pests or weeds, e.g. at least one fungicide, insecticide, acaricide, nematicide, moluscicide and/or herbicide; or for regulating the growth of plants.
  • fungicidally active substances comprise:
  • acylalanines such as benalaxyl, metalaxyl, ofurace or oxadixyl
  • amine derivatives such as aldimorph, dodine, dodemorph, fenpropimorph, fenpropidin, guazatine, iminoctadine, spiroxamine or tridemorph;
  • anilinopyrimidines such as pyrimethanil, mepanipyrim or cyprodinil
  • antibiotics such as cycloheximide, griseofulvin, kasugamycin, natamycin, polyoxin and streptomycin;
  • azoles such as bitertanol, bromoconazole, cyproconazole, difenoconazole, dini- conazole, epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imazalil, ipconazole, metconazole, myclobutanil, penconazole, pro- piconazole, prochloraz, prothioconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triflumizole or triticonazole;
  • 2-methoxybenzophenones such as those disclosed in EP-A 897 904 by the general formula (I), e.g. metrafenone;
  • dicarboximides such as iprodione, myclozolin, procymidone or vinclozolin;
  • dithiocarbamates such as ferbam, nabam, maneb, mancozeb, metam, metiram, propineb, polycarbamate, thiram, ziram or zineb;
  • heterocyclic compounds such as anilazine, benomyl, boscalid, carbendazim, carboxin, oxycarboxin, cyazofamid, dazomet, dithianon, famoxadone, fenamidone, fenarimol, fuberidazole, flutolanil, furametpyr, isoprothiolane, mepronil, nuarimol, picobenzamid, probenazole, proquinazid, pyrifenox, pyroquilon, quinoxyfen, silthi- ofam, thiabendazole, thifluzamide, thiophanate-methyl, tiadinil, tricyclazole or tri- forine; • nitrophenyl derivatives, such as binapacryl, dinocap, dinobuton or nitrothal-isopro- pyi;
  • phenylpyrroles such as fenpiclonil or fludioxonil
  • unclassified fungicides such as acibenzolar-S-methyl, benthiavalicarb, carpropa- mid, chlorothalonil, cyflufenamid, cymoxanil, diclomezine, diclocymet, diethofencarb, edifenphos, ethaboxam, fenhexamid, fentin acetate, fenoxanil, ferimzone, fluazinam, fosetyl, fosetyl-aluminum, iprovalicarb, hexachlorobenzene, met- rafenone, pencycuron, propamocarb, phthalide, tolclofos-methyl, quintozene or zoxamide;
  • strobilurins such as those disclosed in WO 03/075663 by the general formula (I), for example azoxystrobin, dimoxystrobin, fluoxastrobin, kresoxim-methyl, metom- inostrobin, orysastrobin, picoxystrobin, pyraclostrobin and trifloxystrobin;
  • sulfenic acid derivatives such as captafol, captan, dichlofluanid, folpet or tol- ylfluanid;
  • amide fungicides such as cyflufenamid and (Z)-N-[D-(cyclopropylmethoxyimino)- 2,3-difluoro-6-(difluoromethoxy)benzyl]-2-phenylacetamide.
  • herbicides comprise:
  • 1,3,4-thiadiazoles such as buthidazole and cyprazole
  • amides such as allidochlor, benzoylprop-ethyl, bromobutide, chlorthiamid, dimepiperate, dimethenamid, diphenamid, etobenzanid, flamprop-methyl, fosa- mine, isoxaben, metazachlor, monalide, naptalam, pronamide or propanil;
  • aminophosphoric acids such as bilanafos, buminafos, glufosinate-ammonium, glyphosate or sulfosate;
  • aminotriazoles such as amitrole, or anilides, such as anilofos or mefenacet;
  • aryloxyalkanoic acid such as 2,4-D, 2,4-DB, clomeprop, dichlorprop, dichlorprop- P, fenoprop, fluroxypyr, MCPA, MCPB, mecoprop, mecoprop-P, napropamide, naproanilide or triclopyr;
  • benzoic acids such as chloramben or dicamba
  • bleachers such as clomazone, diflufenican, fluorochloridone, flupoxam, fluridone, pyrazolate or sulcotrione;
  • carbamates such as carbetamide, clorbufam, chlorpropham, desmedipham, phen- medipham or vernolate;
  • dichloropropionic acids such as dalapon
  • dihydrobenzofurans such as ethofumesate
  • dinitroanilines such as benefin, butralin, dinitramine, ethalfluralin, fluchloralin, isopropalin, nitralin, oryzalin, pendimethalin, prodiamine, profluralin, trifluralin;
  • dinitrophenols such as bromofenoxim, dinoseb, dinoseb acetate, dinoterb, DNOC or minoterb acetate;
  • diphenyl ethers such as acifluorfen-sodium, aclonifen, bifenox, chlornitrofen, dif- enoxuron, ethoxyfen, fluorodifen, fluoroglycofen-ethyl, fomesafen, furyloxyfen, lactofen, nitrofen, nitrofluorfen or oxyfluorfen;
  • dipyridyls such as cyperquat, difenzoquat metilsulfate, diquat or paraquat dichloride;
  • imidazoles such as isocarbamid
  • imidazolinones such as imazamethapyr, imazapyr, imazaquin, imazethabenzme- thyl, imazethapyr, imazapic or imazamox;
  • oxadiazoles such as methazole, oxadiargyl or oxadiazone
  • oxiranes such as tridiphane
  • phenols such as bromoxynil or ioxynil
  • phenoxyphenoxypropionic acid esters such as clodinafop, cyhalofop-butyl, diclo- fop-methyl, fenoxaprop-ethyl, fenoxaprop-P-ethyl, fenthiaprop-ethyl, fluazifop-butyl, fluazifop-P-butyl, haloxyfop-ethoxyethyl, haloxyfop-methyl, haloxyfop-P-methyl, isoxapyrifop, propaquizafop, quizalofop-ethyl, quizalofop-P-ethyl or quizalofop-P- tefuryl;
  • phenylpropionic acids such as chlorphenprop-methyl
  • ppi-active substances such as benzofenap, flumiclorac-pentyl, flumioxazin, flumipropyn, flupropacil, pyrazoxyfen, sulfentrazone or thidiazimin;
  • pyrazoles such as nipyraclofen
  • pyridazines such as chloridazon, maleic hydrazide, norflurazon or pyridate
  • pyridinecarboxylic acids such as clopyralid, dithiopyr, picloram or thiazopyr;
  • pyrimidyl ethers such as pyrithiobac acid, pyrithiobac-sodium, KIH-2023 or KIH- 6127;
  • sulfonamides such as flumetsulam or metosulam
  • triazolecarboxamides such as triazofenamide
  • uracils such as bromacil, lenacil or terbacil
  • plant protection active substances of the cyclohexenone type such as alloxydim, clethodim, cloproxydim, cycloxydim, sethoxydim and tralkoxydim.
  • Very particularly preferred herbicidal active substances of the cyclohexenone type are: tepraloxydim (cf. AGROW, No.
  • insecticides comprise:
  • organophosphates such as acephate, azinphos-methyl, chlorpyrifos, chlorfenvinphos, diazinon, dichlorvos, dimethylvinphos, dioxabenzofos, dicrotophos, dimethoate, disulfoton, ethion, EPN, fenitrothion, fenthion, isoxathion, malathion, methamidophos, methidathion, methyl parathion, mevinphos, monocrotophos, ox- ydemeton-methyl, paraoxon, parathion, phenthoate, phosalone, phosmet, phos- phamidon, phorate, phoxim, pirimiphos-methyl, profenofos, prothiofos, pirimiphos- ethyl, pyraclofos, pyridaphenthion, sulprophos, triazophos,
  • carbamates such as alanycarb, benfuracarb, bendiocarb, carbaryl, carbofuran, carbosulfan, fenoxycarb, furathiocarb, indoxacarb, methiocarb, methomyl, oxamyl, pirimicarb, propoxur, thiodicarb or triazamate; pyrethroids, such as bifenthrin, cyfluthrin, cycloprothrin, cypermethrin, deltame- thrin, esfenvalerate, etofenprox, fenpropathrin, fenvalerate, cyhalothrin, lambda- cyhalothrin, permethrin, silafluofen, tau-fluval inate, tefluthrin, tralomethrin, alpha- cypermethrin or zeta-cy
  • benzoylureas such as chlorfluazuron, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, teflubenzuron, triflumuron, buprofezin, diofenolan, hexythi- azox, etoxazole or clofentezine; b) ecdysone antagonists, such as halofenozide, methoxyfenozide or tebufenozide; c) juvenile hormone mimics, such as pyriproxyfen, methoprene or fenoxycarb; d) lipid biosynthesis inhibitors such as spirodiclofen; neonicotinoids, such as flonicamid, clothianidin, dinotefuran, imidacloprid, thia- methoxam, nitenpyram, nithiazine, acetami
  • N-phenylsemicarbazones such as those disclosed in EP-A 462 456 by the general formula (I), especially compounds of the general formula (A) in which R 2 and R 3 represent, independently of one another, hydrogen, halogen, CN, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 haloalkyl or Ci-C4 haloalkoxy and R 4 represents C1-C4 alkoxy, C1-C4 haloalkyl or C1-C4 haloalkoxy, e.g. compound IV, in which R 2 represents 3-CF3, R 3 represents 4-CN and R 4 represents 4-OCF3.
  • Examples for plant growth regulators comprise chlormequat chloride, mepiquat chloride, prohexadione-calcium, trinexapac ethyl or the group of the gibberellins. These include, e.g. the gibberellin GA1, GA3, GA4, GA5 and GA7, and the like, and the corresponding exo-16,17-dihydrogibberellins, and also the derivatives thereof, e.g. the esters with C1-C4 carboxylic acids.
  • Water-soluble concentrates comprise for example:
  • a wetting agent e.g. alcohol alkoxylates
  • Emulsions comprise for example:
  • emulsifiers e.g. calcium dodecylbenzenesulfonate and castor oil ethoxylate
  • Suspensions comprise for example:
  • dispersants and/or wetting agents e.g. sodium lignosulfonate and alcohol ethoxylate
  • a thickener e.g. xanthan gum
  • binder e.g. polyvinylalcohol
  • Gels (GW, GF) comprise for example:
  • a thickener e.g. carboxymethylcellulose
  • Microemulsions comprise for example:
  • an organic solvent blend e.g. fatty acid dimethylamide and cyclohexanone
  • surfactant blend e.g. alcohol ethoxylate and arylphenol ethoxylate
  • the above crop protection compositions may optionally comprise further auxiliaries, such as 0.1-1 wt% other bactericides, 0.1-1 wt% anti-foaming agents, and 0.1-1 wt% colorants.
  • Suitable pharmaceutical compositions may exist in a wide variety of forms, for example in the form of liquid preparations as a W/O, O/W, O/W/O, W/O/W or PIT emulsion and all kinds of microemulsions; in the form of a non-emulsified, water-based liquid, in the form of a gel, in the form of an oil, a cream, milk or lotion, in the form of a spray (spray with propellant gas or pump-action spray) or an aerosol, in the form of a foam, in the form of a paste, in the form of a wet wipe (such as for cleaning the nappy area).
  • a non-emulsified, water-based liquid in the form of a gel, in the form of an oil, a cream, milk or lotion, in the form of a spray (spray with propellant gas or pump-action spray) or an aerosol, in the form of a foam, in the form of a paste, in the form of a we
  • compositions may be, for example, creams, gels, lotions, alcoholic and aqueous/alcoholic solutions, emulsions, wax/fat compositions, or ointments.
  • Preserving personal care products from microbial degradation is imperative and simultaneously challenging, since most topical cosmetics and dermatological products contain significant amounts of water, thus providing a very hospitable environment for microbial growth. Many other ingredients in personal care products can also be a good source of nutrients to microbes. Moreover, shelf-life and pot life of personal care products are rather long as compared to, for example, food products. Generally, personal care products are neither sterilized and nor packed in hermetic conditions, and thus the presence of preservatives can hardly be dispensed with. On the other hand, the public regards preservatives in personal care products as problematic. The consumers expect the preservatives to be not only effective, but extremely mild during the whole shelf and pot life.
  • Antimicrobials which are not or at least less hazardous, like 2- phenoxyethanol, are often not very effective and need to be used in rather high concentrations to achieve an acceptable antimicrobial effect. In personal care applications, high concentrations are however not acceptable.
  • the present combination of antimicrobials (a) and alkoxylated amines (I) allows to reduce the amount of antimicrobial substantially, without compromising the desired antimicrobial effect.
  • the antimicrobial is preferably 2- phenoxyethanol.
  • Personal care compositions can be such for hygienic or cosmetic use. Examples for suitable personal care compositions are given above.
  • Suitable personal care compositions may exist in a wide variety of forms, for example in the form of liquid preparations as a W/O, O/W, O/W/O, W/O/W or PIT emulsion and all kinds of microemulsions; in the form of a non-emulsified, water-based liquid, in the form of a gel, in the form of an oil, a cream, milk or lotion, in the form of a spray (spray with propellant gas or pump-action spray) or an aerosol, in the form of a foam, in the form of a paste, in the form of a wet wipe (such as for cleaning the nappy area).
  • a non-emulsified, water-based liquid in the form of a gel, in the form of an oil, a cream, milk or lotion, in the form of a spray (spray with propellant gas or pump-action spray) or an aerosol, in the form of a foam, in the form of a paste, in the form of a
  • the personal care compositions may be, for example, creams, gels, lotions, alcoholic and aqueous/alcoholic solutions, emulsions, wax/fat compositions, or ointments.
  • ingredients typically present in such personal care compositions and their amounts vary according to the specific formulation.
  • ingredients are solvents, surfactants, emulsifiers, rheology modifiers (generally thickeners), conditioners, emollients, skin caring ingredients, lubricants, fillers, antioxidants, dermatologically active ingredients, fragrances and water.
  • the preparations generally contain at least one oil component, at least one emulsifier, water and optionally at least one further cosmetically acceptable adjuvants; for example, from 0.1 to 30% by weight, preferably from 0.1 to 15% by weight and especially from 0.5 to 10% by weight, based on the total weight of the composition, from 1 to 60% by weight, especially from 5 to 50% by weight and preferably from 10 to 35% by weight, based on the total weight of the composition, of at least one oil component, from 0 to 30% by weight, especially from 1 to 30% by weight und preferably from 4 to 20% by weight, based on the total weight of the composition, of at least one emulsifier, from 10 to 90% by weight, especially from 30 to 90% by weight, based on the total weight of the composition, of water, and from 0 to 88.9% by weight
  • Preparation intended mainly for cleaning such as soaps, shower gels and shampoos, contain at least one or more surfactants, often of the anionic type, optionally in combination with such of the zwitterionic type; and water. Furthermore, they generally contain at least one of following components: emulsifier, sequestrant, fragrance, pH modifier (generally an organic acid and/or an inorganic base), inorganic salt (mostly NaCI), dye,
  • cosmetic preparations for the hair especially with the purpose of antidandruff treatment, especially hair-washing preparations in the form of shampoos, hair conditioners, hair-care preparations, e.g. pre-treatment preparations, hair tonics, styling creams, styling gels, pomades, hair rinses, treatment packs, intensive hair treatments, hair-straightening preparations, liquid hair-setting preparations, hair foams and hairsprays.
  • hair-washing preparations in the form of shampoos Of special interest are moreover shower gels.
  • Shampoos as well as shower gels generally contain water and at least one anionic surfactant.
  • Suitable anionic surfactants are principally all those described above in context with homecare and l&l compositions which are cosmetically acceptable. In shampoos and in shower gels, it is useful to use surfactants which are good foam-formers.
  • Suitable anionic surfactants in this context are alkyl sulfates, alkyl ether sulphates, alkaryl sulfonates, alkanoyl isethionates, alkyl succinates, alkyl sulfosuccinates, alkyl ether sulfosuccinates, N-alkyl sarcosinates, alkyl phosphates, alkyl ether phosphates, and alkyl ether carboxylic acids and salts thereof, especially sodium, magnesium, ammonium and mono-, di- and triethanolamine salts.
  • the alkyl and acyl groups generally contain from 8 to 18, preferably from 10 to 16 carbon atoms and may be unsaturated.
  • alkyl ether sulfates, alkyl ether sulfosuccinates, alkyl ether phosphates and alkyl ether carboxylic acids and salts thereof may contain from 1 to 20 ethylene oxide or propylene oxide units per molecule.
  • Typical surfactants for use in shampoo compositions include sodium oleyl succinate, ammonium lauryl sulfosuccinate, sodium lauryl sulfate, sodium lauryl ether sulfate (sodium laureth sulfate), sodium lauryl ether sulfosuccinate, ammonium lauryl sulfate, ammonium lauryl ether sulfate, sodium dodecylbenzene sulfonate, triethanolamine dodecylbenzene sulfonate, sodium cocoyl isethionate, sodium lauryl isethionate, lauryl ether carboxylic acid and sodium N-lauryl sarcosinate.
  • the overall amount of anionic surfactant in the shampoo compositions of the invention generally ranges from 0.5 to 45% by weight, e.g. from 1.5 to 35% by weight, based on the total weight of the composition.
  • the shampoo or shower gel composition can moreover include non-ionic, amphoteric and/or cationic co-surfactants, which help impart aesthetic, haptic, combing, physical or cleansing properties to the composition.
  • Suitable non-ionic surfactants are those listed above, e.g. ethoxylated fatty alcohols, mono- or di-alkyl alkanolamides, such as coco mono- or di-ethanolamide and coco monoisopropanolamide; or alkyl polyglycosides (APGs) such as Oramix NS10 ex Seppic; Plantaren 1200 and Plantaren 2000 ex Henkel.
  • the overall amount of non-ionic surfactant in the shampoo or shower gel compositions of the invention generally ranges from 0.5 to 8% by weight, preferably from 2 to 5% by weight, based on the total weight of the composition.
  • Suitable amphoteric or zwitterionic surfactants are those listed above, e.g. alkyl amine oxides, alkyl betaines, alkyl amidopropyl betaines, alkyl sulfobetaines (sultaines), alkyl glycinates, alkyl carboxyglycinates, alkyl amphoacetates, alkyl amphopropionates, al- kylamphoglycinates, alkyl amidopropyl hydroxysultaines, acyl taurates and acyl glutamates, wherein the alkyl and acyl groups have from 8 to 19 carbon atoms.
  • amphoteric or zwitterionic surfactant in the shampoo or shower gel compositions of the invention generally ranges from 0.5 to 8% by weight, preferably from 1 to 4% by weight, based on the total weight of the composition.
  • Suitable cationic polymers are those listed above. Examples are copolymers of vinyl monomers having cationic amine or quaternary ammonium functionalities with water soluble spacer monomers such as (meth)acrylamide, alkyl and dialkyl (methacrylamides, alkyl (meth)acrylate, vinyl caprolactone and vinyl pyrrolidine.
  • the alkyl and dialkyl substituted monomers preferably have Ci-C?-alkyl groups, more preferably C1-C3- alkyl groups.
  • Other suitable spacers include vinyl esters, vinyl alcohol, maleic anhydride, propylene glycol and ethylene glycol.
  • the cationic amines can be primary, secondary or tertiary amines, depending upon the particular species and the pH of the composition. In general secondary and tertiary amines, especially tertiary, are preferred. Other examples are cationic polysaccharide polymers, such as cationic cellulose derivatives, cationic starch derivatives, and cationic guar gum derivatives.
  • the overall amount of cationic surfactant in the shampoo or shower gel compositions of the invention generally ranges from 0.05 to 1% by weight, more preferably from 0.08 to 0.5% by weight, based on the total weight of the composition.
  • the total amount of surfactant (including any co-surfactant and/or any emulsifier) in a shampoo or shower gel composition is generally from 1 to 50% by weight, preferably from 2 to 40% by weight, more preferably from 10 to 25% by weight, based on the total weight of the composition.
  • suspending agents such as polyacrylic acids, cross-linked polymers of acrylic acid, copolymers of acrylic acid with a hydrophobic monomer, copolymers of carboxylic acidcontaining monomers and acrylic esters, cross-linked copolymers of acrylic acid and acrylate esters, heteropolysaccharide gums and crystalline long chain acyl derivatives, the latter being preferably selected from ethylene glycol stearate, alkanolamides of fatty acids having from 16 to 22 carbon atoms and mixtures thereof; fragrances, dyes and pigments, pH adjusting agents, pearlescers or opacifiers, viscosity modifiers, and salts, such as as NaCI; in shampoos moreover natural hair nutrients or dermatologically active ingredients, such as botanicals, fruit extracts, caffeine, panthenol, sugar derivatives, amino acids, such as hydrolized keratine or glycine, vegetable or hydrogenated vegetable oils.
  • suspending agents such as polyacrylic acids, cross-linked polymers of acrylic acid, copoly
  • the antimicrobial agent in combination with the alkoxylated amine (I)
  • the antimicrobial agent and the alkoxylated amine (I) are of course contained in a preservative effective amount denotes. This is an amount that is sufficient to reduce the cell population of an unwanted microorganism under a predetermined threshold value to obtain shelf-stability over a certain period of time.
  • a "preservative-effective amount” can be e.g. defined as an amount sufficient to reduce the cell population by, for example, at least one, preferably at least two, in particular at least three log orders of the at least one of following microorganisms: Alcali- geneses faecalis, Aspergillus niger, Burkholderia cepacia, Candida albicans, Escherichia coli, Pseudomonas aeruginosa, Pseudomonas putida and Staphylococcus aureus, and in particular at least one of following microorganisms: Alcaligeneses faecalis, Burkholderia cepacia, Escherichia coli, Pseudomonas aeruginosa, Pseudomonas putida and Staphylococcus aureus.
  • a "preservative-effective amount” can be e.g. defined as an amount sufficient to reduce the cell population by, for example, at least one, preferably at least two, in particular at least three log orders of the at least one of following microorganisms: Aspergillus brasiliensis, Rhodotorula mucilaginosa and Yarrowia lipolytica.
  • composition of the invention has a pH of preferably from 2 to 11, more preferably from 4 to 10, and in particular from 4 to 9.
  • compound of formula (I) means alkoxylated amine of the above-depicted formula (I).
  • R 1 , R 2 and R 3 are independently -CH2CH2O-A n -B m -H, where R a is methyl, m is 10 to 30 and n is 3 to 12; or m is 10 to 20 and n is 0.
  • R 1 , R 2 and R 3 are independently -CH2CH2O-A n -B m -H, where R a is methyl, m is 13 to 28 and n is 4 to 11 ; or m is 14 to 16 and n is 0.
  • R 1 , R 2 and R 3 are independently -CH2CH2O-A n -B m -H, where R a is methyl, m is 14 to 27 and n is 5 to 10; or m is 15 and n is 0.
  • R 1 , R 2 and R 3 are independently -CH2CH2O-A n -B m -H, where R a is methyl, m is 14 and n is 5; or m is 15 and n is 0.
  • 2-phe- noxyethanol, 4,4’-dichloro 2’-hydroxydiphenylether (diclosan), 2-bromo-2-nitropropane- 1 ,3-diol, glutaraldehyde or 1 ,2-benzisothiazol-3(2H)-one (BIT) is used. More specifically, 2-phenoxyethanol, 2-bromo-2-nitropropane-1 ,3-diol, glutaraldehyde or 1 ,2-ben- ziothiazol-3(2H)-one (BIT) is used. Very specifically, 2-phenoxyethanol is used. In another more specific embodiment, phenoxyisopropanol is used.
  • each of these antimicrobial agents is combined in each of the above formulations with one or more of the alkoxylated (I) as defined above.
  • one of the following alkoxylated amines (I) is used as compound (I): an alkoxylated amine (I) wherein R 1 , R 2 and R 3 are independently -CH2CH2O-A n -B m -H, where R a is methyl, m is 10 to 30 and n is 3 to 12; or m is 10 to 20 and n is 0.
  • alkoxylated amines (I) is used as compound (I): an alkoxylated amine (I) wherein R 1 , R 2 and R 3 are independently -CH2CH2O-A n -B m -H, where R a is methyl, m is 13 to 28 and n is 4 to 11 ; or m is 14 to 16 and n is 0.
  • one of the following alkoxylated amines (I) is used as compound (I): an alkoxylated amine (I) wherein R 1 , R 2 and R 3 are independently - CH 2 CH 2 O-An-Bm-H, where R a is methyl, m is 14 to 27 and n is 5 to 10; or m is 15 and n is 0.
  • one of the following alkoxylated amines (I) is used as compound (I): an alkoxylated amine (I) wherein R 1 , R 2 and R 3 are independently -CF ⁇ CFW-An-Bm- H, where R a is methyl, m is 14 and n is 5; or m is 15 and n is 0.
  • the solvent is ethanol, n-propanol, isopropanol, ethylene gycol, propylene glycol, ethylene glycol mono-n-butylether, propylene glycol mono-n-butylether, y-butyrolactone, y- valerolactone, y-octalactone, y-nonalactone or s-caprolactone.
  • the solvent is or comprises N,N-dimethyllactamide, 1- butoxy-propan-2-ol, diethyleneglycolmono-n-butyl ether, y-valerolactone or a mixture thereof. If the solvent comprises N,N-dimethyllactamide, 1-butoxy-propan-2-ol, diethy- leneglycolmono-n-butyl ether, y-valerolactone or a mixture thereof, the solvent may further comprise one or more of ethanol, n-propanol, isopropanol, ethylene gycol, propylene glycol, ethylene glycol mono-n-butylether and propylene glycol mono-n-butylether.
  • the invention relates moreover to a kit of parts comprising at least two parts, where the first part comprises at least one antimicrobial agent as defined above; the second part comprises at least one alkoxylated amine (I) as defined above and optionally at least one organic solvent [of course different from the alkoxylated amine (I) and from said antimicrobial agent], preferably as defined above; and an optional third part comprises at least one organic solvent [of course different from the alkoxylated amine (I) and from said antimicrobial agent], preferably as defined above; where the first part does not comprise any alkoxylated amine (I); where the second part does not comprise any antimicrobial agent as defined above; where the optional third part does not comprise any antimicrobial agent as defined above nor any alkoxylated amine (I); and where the first and second parts contain the at least one antimicrobial agent as defined above and the at least one alkoxylated amine (I) in such amounts that when the first and the second part are mixed the resulting overall weight ratio is as defined above,
  • 100:1 to 1 :10000 preferably from 50:1 to 1:2000, more preferably from 50:1 to 1 :1000, even more preferably from 50:1 to 1 :500, in particular from 20:1 to 1 :500, more particularly from 10:1 to 1 :450, even more particularly from 5:1 to 1:450, and specifically from 2:1 to 1 :450.
  • the resulting overall weight ratio of antimicrobial agent and alkoxylated amine (I) is preferably from 3:1 to 1:5, more preferably from 3:1 to 1 :3, even more preferably from 2.5:1 to 1:2.5, in particular from 2:1 to 1:2.5, specifically from 1.3:1 to 1 :2 and very specifically from 1:1 to 1:2.
  • the resulting overall weight ratio of antimicrobial agent and alkoxylated amine (I) is preferably from 1 :1 to 1 :500, more preferably from 1:1 to 1 :450, and in particular from 1:100 to 1 :450.
  • components (a) and (b) are present as a physical mixture, in a kit of parts they are formulated separately, but provided in such a form that they nevertheless form a functional unity. They form thus a true combination through a purpose-directed application.
  • the functional unity is expressed for example in the fact that the parts contain the antimicrobial agent and the alkoxylated amine (I) in such amounts that when mixed, they result in the desired weight ratio.
  • Another way to express functional unity may be a use instruction explaining the combined use of the two or more parts of the kit.
  • Yet another way to express functional unity may be a physical connection.
  • the different parts of the kit may be bond to each other via an adhesive tape or strap or any other type of tie, or may be assembled in a common container, such as a box, package, basket etc. or packed together in a plastic foil.
  • the kit of parts is a kit of two parts, where the first part comprises at least one antimicrobial agent as above; and the second part comprises at least one alkoxylated amine (I) as defined above and at least one organic solvent [different from the alkoxylated amine (I) and from said antimicrobial agent], where the organic solvent has preferably one of the above preferred meanings.
  • the kit of parts is a kit of three parts, where the first part comprises at least one antimicrobial agent as defined above; the second part comprises at least one alkoxylated amine (I) as defined above; and the third part comprises at least one organic solvent [different from the alkoxylated amine (I) and from said antimicrobial agent], where the organic solvent has preferably one of the above preferred meanings.
  • the invention relates moreover to the use of an alkoxylated amine (I) as defined above for enhancing the antimicrobial, in particular the preserving, activity of the antimicrobial agent as defined above, and in particular for enhancing the antimicrobial, in particular the preserving, activity of the antimicrobial agent in an aqueous liquid homecare composition as defined above.
  • an alkoxylated amine (I) as defined above for enhancing the antimicrobial, in particular the preserving, activity of the antimicrobial agent as defined above, and in particular for enhancing the antimicrobial, in particular the preserving, activity of the antimicrobial agent in an aqueous liquid homecare composition as defined above.
  • the invention relates to the use of an alkoxylated amine (I) as defined above for enhancing the antimicrobial, in particular the preserving, activity of 2-phenoxy- ethanol, 2-bromo-2-nitropropane-1 ,3-diol (bronopol), glutaraldehyde or 1 ,2-benzisothia- zol-3(2H)one (BIT); specifically of 2-phenoxyethanol.
  • an alkoxylated amine (I) as defined above for enhancing the antimicrobial, in particular the preserving, activity of 2-phenoxy- ethanol, 2-bromo-2-nitropropane-1 ,3-diol (bronopol), glutaraldehyde or 1 ,2-benzisothia- zol-3(2H)one (BIT); specifically of 2-phenoxyethanol.
  • the invention relates to the use of an alkoxylated amine (I), wherein R 1 , R 2 and R 3 are independently -CH2CH2O-A n -B m -H, where R a is methyl, m is 10 to 30 and n is 3 to 12; or m is 10 to 20 and n is 0, for enhancing the antimicrobial, in particular the preserving, activity of 2-phenoxyethanol, 2-bromo-2-nitropropane-1 ,3-diol (bronopol), glutaraldehyde or 1 ,2-benzisothiazol-3(2H)one (BIT); specifically of 2-phe- noxyethanol.
  • R 1 , R 2 and R 3 are independently -CH2CH2O-A n -B m -H, where R a is methyl, m is 10 to 30 and n is 3 to 12; or m is 10 to 20 and n is 0, for enhancing the antimicrobial, in particular the preserving, activity of 2-phen
  • the invention relates to the use of an alkoxylated amine (I), wherein R 1 , R 2 and R 3 are independently -CH2CH2O-A n -B m -H, where R a is methyl, m is 13 to 28 and n is 4 to 11 ; or m is 14 to 16 and n is 0, for enhancing the antimicrobial, in particular the preserving, activity of 2-phenoxyethanol, 2-bromo-2-nitro- propane-1 ,3-diol (bronopol), glutaraldehyde or 1 ,2-benzisothiazol-3(2H)one (BIT); specifically of 2-phenoxyethanol.
  • R 1 , R 2 and R 3 are independently -CH2CH2O-A n -B m -H, where R a is methyl, m is 13 to 28 and n is 4 to 11 ; or m is 14 to 16 and n is 0, for enhancing the antimicrobial, in particular the preserving, activity of 2-phenoxyethanol,
  • the invention relates to the use of an alkoxylated amine (I), wherein R 1 , R 2 and R 3 are independently -CH2CH2O-A n -B m -H, where R a is methyl, m is 14 to 27 and n is 5 to 10; or m is 15 and n is 0, for enhancing the antimicrobial, in particular the preserving, activity of 2-phenoxyethanol, 2-bromo-2-nitro- propane-1 ,3-diol (bronopol), glutaraldehyde or 1 ,2-benzisothiazol-3(2H)one (BIT); specifically of 2-phenoxyethanol.
  • R 1 , R 2 and R 3 are independently -CH2CH2O-A n -B m -H, where R a is methyl, m is 14 to 27 and n is 5 to 10; or m is 15 and n is 0, for enhancing the antimicrobial, in particular the preserving, activity of 2-phenoxyethanol, 2-bromo-2-
  • the invention relates to the use of an alkoxylated amine (I), wherein R 1 , R 2 and R 3 are independently -CH2CH2O-A n -B m -H, where R a is methyl, m is 14 to 27 and n is 5 to 10; or m is 14 to 16 and n is 0, for enhancing the antimicrobial, in particular the preserving, activity of 2-phenoxyethanol.
  • R 1 , R 2 and R 3 are independently -CH2CH2O-A n -B m -H, where R a is methyl, m is 14 to 27 and n is 5 to 10; or m is 14 to 16 and n is 0, for enhancing the antimicrobial, in particular the preserving, activity of 2-phenoxyethanol.
  • the invention relates to the use of an alkoxylated amine (I), wherein R 1 , R 2 and R 3 are independently -CH2CH2O- An-Bm-H, where R a is methyl, m is 14 and n is 5; or m is 15 and n is 0, for enhancing the antimicrobial, in particular the preserving, activity of 2-phenoxyethanol.
  • R 1 , R 2 and R 3 are independently -CH2CH2O- An-Bm-H, where R a is methyl, m is 14 and n is 5; or m is 15 and n is 0, for enhancing the antimicrobial, in particular the preserving, activity of 2-phenoxyethanol.
  • the invention relates to the use of an alkoxylated amine (I), wherein R 1 , R 2 and R 3 are independently -CH2CH2O-A n -B m -H, where R a is methyl, m is 13 to 15 and n is 4 to 6; or m is 14 to 16 and n is 0, for enhancing the antimicrobial, in particular the preserving, activity of 2-phenoxyethanol, 2-bromo-2-nitropropane-1 ,3-diol (bronopol), glutaraldehyde or 1 ,2-benzisothiazol-3(2H)one (BIT).
  • R 1 , R 2 and R 3 are independently -CH2CH2O-A n -B m -H, where R a is methyl, m is 13 to 15 and n is 4 to 6; or m is 14 to 16 and n is 0, for enhancing the antimicrobial, in particular the preserving, activity of 2-phenoxyethanol, 2-bromo-2-nitroprop
  • the invention relates to the use of an alkoxylated amine (I), wherein R 1 , R 2 and R 3 are independently - CH 2 CH 2 O-An-Bm-H, where R a is methyl, m is 14 and n is 5, for enhancing the antimicrobial, in particular the preserving, activity of 2-bromo-2-nitropropane-1 ,3-diol (bronopol), glutaraldehyde or 1 ,2-benzisothiazol-3(2H)one (BIT).
  • bronopol 2-bromo-2-nitropropane-1 ,3-diol
  • BIT 1-benzisothiazol-3(2H)one
  • the antimicrobial activity is in particular directed against fungi and bacteria as they typically occur in the compositions to be preserved against attack/infestation by microbes or on substrates, surfaces or materials to be disinfected, some few examples for fungi being Aspergillus brasiliensis, Rhodotorula mucilaginosa or Yarrowia lipolytica, and some few examples for bacteria being Escherichia coli, Alcaligenes faecalis, Pseudomonas aeruginosa, Staphylococcus aureus, Burkholderia cepacia, Pseudomonas putida, to name just a few.
  • the invention is now illustrated by the following examples.
  • Plurafac® LF 1430 from BASF (abbreviated as PLF): Triethanolamine alkoxylated with 5 EO on average and 14 PO on average per OH group of triethanolamine; to be more precise a compound (I) wherein R 1 , R 2 and R 3 are -CH2CH2O-A n -B m -H, where R a is methyl, m is 14 and n is 5.
  • TEA-15 PO Triethanolamine alkoxylated with 15 PO on average per OH group of triethanolamine, to be more precise a compound (I) wherein R 1 , R 2 and R 3 are - CH 2 CH 2 O-An-Bm-H, where R a is methyl, m is 15 and n is 0.
  • TEA-20PO/5EO Triethanolamine alkoxylated with 5 EO on average and 20 PO on average per OH group of triethanolamine; to be more precise a compound (I) wherein R 1 , R 2 and R 3 are -CH2CH2O-A n -B m -H, where R a is methyl, m is 20 and n is 5.
  • TEA-20PO/7.5EO Triethanolamine alkoxylated with 7.5 EO on average and 20 PO on average per OH group of triethanolamine; to be more precise a compound (I) wherein R 1 , R 2 and R 3 are -CH2CH2O-A n -B m -H, where R a is methyl, m is 20 and n is 7.5.
  • TEA-27PO/10EO Triethanolamine alkoxylated with 10 EO on average and 27 PO on average per OH group of triethanolamine; to be more precise a compound (I) wherein R 1 , R 2 and R 3 are -CH2CH2O-A n -B m -H, where R a is methyl, m is 27 and n is 10
  • Butyldiglycol diethylene glycol-mono-n-butyl ether
  • Butoxy-2-propanol 1-butoxy-2-propanol; propylene glycol-mono-n-butyl ether
  • a phosphate buffer solution of pH 7.0 was used.
  • the samples were contaminated with a fungal mix consisting of:
  • Yarrowia lipolytica DSM 8218 The samples were inoculated with the fungal mix at day 0 to obtain 1 - 3 x10E+05 CFU/ml inoculation in the test sample consisting of the above-defined phosphate buffer solution and stored at 25°C for 7 days. CFU was determined at day 7.
  • a phosphate buffer solution of pH 7.0 was used.
  • the samples were contaminated with a fungal mix consisting of:
  • the samples were inoculated with the fungal mix at day 0 and day 7 to obtain 1 - 3 x10E+05 CFU/ml inoculation in the test sample consisting of the above-defined phosphate buffer solution and stored at 25°C for 21 days. CFU was determined before reinoculation at day 7, and at day 14 and day 21.
  • HSC hard surface cleaner
  • the samples were contaminated with a fungal mix consisting of: Aspergillus brasiliensis DSM 1988 Rhodotorula mucilaginosa DSM 13621 Yarrowia lipolytica DSM 8218
  • the samples were inoculated with the fungal mix at day 0 and 7 to obtain 1 - 3 x10E+05 CFU/ml inoculation in the test sample consisting of the above-defined hard surface cleaner HSC and stored at 25°C for 14 days. CFU was determined before re-inoculation at day 7, and on day 14.
  • a phosphate buffer solution of pH 7.0 was used. Where indicated in table 1.4 below, this contained additionally 1.5% by weight of the following surfactant:
  • the samples were contaminated with a fungal mix consisting of:
  • Yarrowia lipolytica DSM 8218 The samples were inoculated with the fungal mix at day 0 to obtain 1 - 3 x10E+05 CFU/ml inoculation in the test sample consisting of the above-defined phosphate buffer solution and stored at 25°C for 7 days. CFU was determined at day 7.
  • Any CFU value at d7 obtained with a surfactant-containing phosphate buffer solution sample containing 2-phenoxyethanol (PE) and Plurafac® LF 1430 (PLF) lower than the respective value of the comparative examples indicates a better performance of the inventive combination of 2-phenoxyethanol with the alkoxylated amine. All percentages are % by weight and are relative to the total weight of the respective composition (here the phosphate buffer solution sample).
  • a phosphate buffer solution of pH 7.0 was used.
  • the samples were contaminated with a fungal mix consisting of:
  • Yarrowia lipolytica DSM 8218 The samples were inoculated with the fungal mix at days 0 and 7 to obtain 1 - 5 x10E+05 CFU/ml inoculation in the test sample consisting of the above-defined phosphate buffer solution and stored at 25°C for 14 days. CFU was determined at day 7 before re-inoculation, and at day 14.
  • a phosphate buffer solution of pH 7.0 was used.
  • the samples were contaminated with a fungal mix consisting of:
  • the samples were inoculated with the fungal mix at days 0 and 7 to obtain 1 - 5 x10E+05 CFU/ml inoculation in the test sample consisting of the above-defined phosphate buffer solution and stored at 25°C for 14 days. CFU was determined at day 7 before re-inoculation, and at day 14.
  • a phosphate buffer solution of pH 7.0 was used.
  • the samples were contaminated with a fungal mix consisting of:
  • the samples were inoculated with the fungal mix at day 0 to obtain 1 - 5 x10E+05 CFU/ml inoculation in the test sample consisting of the above-defined phosphate buffer solution and stored at 25°C for 7 days. CFU was determined at day 7.
  • any CFU value at d7 obtained with a phosphate buffer solution sample of the invention containing BIT and Plurafac® LF 1430 (PLF) lower than the respective value of the “comparative 1” example (phosphate buffer solution + 25 ppm BIT) or “comparative 2” example (phosphate buffer solution + 1.0% PLF) indicates a better performance of the inventive combination of BIT with the alkoxylated amine. All percentages are % by weight and are relative to the total weight of the respective composition (here the phosphate buffer solution sample), ppm is also by weight and relative to the total weight of the respective composition (here the phosphate buffer solution sample).
  • a 50% polyethylene glycol 6000 (PEG 6000) solution of pH 7.0 was used.
  • the samples were inoculated with the fungal mix at days 0 and 15 to obtain 1 - 3 x10E+05 CFU/ml inoculation in the test sample consisting of the above-defined PEG solution and stored at 25°C for 7 days.
  • CFU was determined at days 0, 2, 7, 14, 15 and 29.
  • a 50% polyethylene glycol 6000 (PEG 6000) solution of pH 7.0 was used.
  • the samples were inoculated with the fungal mix at days 0 and 15 to obtain 1 - 3 x10E+05 CFU/ml inoculation in the test sample consisting of the above-defined PEG so- lution and stored at 25°C for 7 days.
  • CFU was determined at days 0, 2, 7, 14, 15 and 29.
  • solvent B, C or D further enhances and accelerates the preservative activity of the combination of PE + PLF.
  • a phosphate buffer solution of pH 7.0 was used.
  • the samples were contaminated with a bacterial mix consisting of:
  • a phosphate buffer solution of pH 7.0 was used.
  • the samples were contaminated with a bacterial mix consisting of:
  • the samples were inoculated with the bacterial mix at day 0 to obtain 10E+06 to 10E+07 CFU/ml inoculation in the test samples and stored at 25°C for 7 days. CFU was determined at day 7.
  • a phosphate buffer solution of pH 7.0 was used.
  • the samples were contaminated with a bacterial mix consisting of: Escherichia coli DSM 1576
  • the samples were inoculated with the bacterial mix at day 0 to obtain 10E+06 to 10E+07 CFU/ml inoculation in the test samples and stored at 25°C for 7 days. CFU was determined at day 7.

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • General Health & Medical Sciences (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Zoology (AREA)
  • Pest Control & Pesticides (AREA)
  • Environmental Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Dentistry (AREA)
  • Toxicology (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The present invention relates to a composition comprising an antimicrobial agent (a) as defined in the claims and the description and an alkoxylated amine (b) of the formula (I) NR1R2R3 where the variables are as defined in the claims and the description, to the use of said alkoxylated amine (b) for enhancing the antimicrobial, in particular the preserving, activity of the antimicrobial agent (a) and to a method for enhancing the antimicrobial, in particular the preserving, activity of the antimicrobial agent (a) comprising using the antimicrobial agent (a) in combination with said alkoxylated amine (b).

Description

Composition comprising an antimicrobial agent and an alkoxylated amine
The present invention relates to a composition comprising an antimicrobial agent (a) as defined below and a specific alkoxylated amine (b) as defined below, to the use of an alkoxylated amine (b) as defined below for enhancing the antimicrobial, in particular the preserving, activity of the antimicrobial agent (a) and to a method for enhancing the antimicrobial, in particular the preserving, activity of the antimicrobial agent (a) comprising using the antimicrobial agent (a) in combination with said alkoxylated amine (b).
TECHNICAL BACKGROUND
Antimicrobial agents, like those listed below as component (a), are well established preservatives or biocides in a vast range of application areas. A number of products and materials is susceptible to microbial attack or degradation, which attack not only reduces the economic value of such products or materials, but may even pose a health hazard for the user. Microbial degradation in aqueous systems can become manifest in many forms, such as loss of viscosity, emulsion breaking, change of pH, color change, unpleasant odor, fouling, gas formation, slime formation, to name just a few and easily identifiable indicators. Some of these manifestation also occur in non-aqueous systems, e.g. fouling in fuels, heating oils, crude oils and the like. Antimicrobial agents are either incorporated into susceptible products or materials to preserve them, or are used as such or in suitable formulations to treat infected products or materials.
Examples for products, materials and formulations containing antimicrobial agents are homecare compositions and articles, compositions and articles for cleaning or disinfecting on an industrial scale, personal care compositions and articles, process water, cooling water (e.g. in industrial plants, cooling towers), water in fish or shrimp ponds, water in drinking troughs, metal working fluids; water based raw materials, polymer solutions, polymer dispersions, polymer emulsions, inorganic slurries, organic slurries, surfactant compositions; compositions for treating animal hide, leather, textiles, lumber, or paper or the precursor materials thereof during papermaking processes; crop protection compositions; pharmaceutical compositions; paints, glues, adhesives, sealants, dyes, pigments and dispersions thereof, inks and the like.
However, some established antimicrobial agents have been found to cause health risks. For instance, formaldehyde-releasing antimicrobials have lost acceptance because formaldehyde is classified as carcinogenic, mutagenic and as having reproductive toxicity. Halogenated organic antimicrobials, too, have lost ground because they exhibit a certain level of toxic effects, especially when combined with certain other ingredients usually present in the compositions which they are to preserve. The remaining antimicrobials which are not or at least less hazardous, like 2- phenoxyethanol, are often not very effective and need to be used in rather high concentrations to achieve an acceptable antimicrobial effect. In many applications, high concentrations are however not acceptable; for instance because of formulation issues or malodour or because beyond a certain concentration these products become hazardous, too. Moreover, under certain circumstances even high concentrations fail to give the desired effect.
Therefore, at least in certain applications it is not yet possible to renounce completely more hazardous, but very effective antimicrobials. It is however desired to reduce their amount to a minimum.
Altogether it is desirable to reduce the amount of antimicrobials, since intrinsically all of them pose a certain, albeit small, health or environmental risk (otherwise they wouldn’t have an antimicrobial effect), but at the same time the desired antimicrobial effect should not be compromised.
Accordingly, there is a need to improve the effect of antimicrobials. Specifically, in case of non- or less hazardous, but less effective antimicrobials, it is desired to boost their effect so that they can be applied in low or at least reasonable concentrations. In the specific case of more hazardous, but efficacious antimicrobials, it is desired to boost their effect so that their concentrations can be minimized to an extent which makes their application acceptable.
In detergent-containing compositions, the antimicrobial effect of some antimicrobials, especially of those having a limited activity combined with a rather poor water solubility, such as 2-phenoxyethanol, phenoxyisopropanol or benzyl alcohol, is moreover thwarted by some standard detergents, such as detergents with alkyl chains of at least 8 carbon atoms and in particular ethoxylated alkohols with at least 8 carbon atoms in the alkyl chain or alkyl benzene sulfonates with at least 10 carbon atoms in the alkyl chain. It would be desirable to reduce this thwarting effect.
SUMMARY OF THE INVENTION
The object of the present invention is to improve the effect of certain antimicrobials. A more specific object is to provide a composition with an improved preservative and/or biocidal effect. An additional object for detergent-containing compositions is to reduce the thwarting effect which some standard detergents have on the antimicrobial effect of certain antimicrobials. The inventors of the present invention found that certain alkoxylated amines as defined below improve the preservative and/or biocidal effect of certain antimicrobials. In addition to this antimicrobial-boosting effect, said alkoxylated amines have the advantage that they have a detergent-boosting effect, which allows to reduce the amount of other detergents which have the potential to reduce the antimicrobial effect of certain antimicrobials, such as 2-phenoxyethanol.
The present invention therefore relates to a composition comprising
(a) at least one antimicrobial agent selected from the group consisting of 2-phenoxy- ethanol, phenoxyisopropanol, 4,4’-dichloro 2’-hydroxydiphenylether, 2-bromo-2- nitropropane-1 ,3-diol (bronopol), glutaraldehyde, 2,4-dichlorobenzylalcohol, 1 ,3,5-tris-(2-hydroxyethyl)-1 ,3,5-hexahydrotriazine, formic acid and salts thereof, benzoic acid and salts thereof, sorbic acid and salts thereof, lactic acid and salts thereof, isothiazolinones selected from the group consisting of 1 ,2-benzisothia- zol-3(2H)-one (BIT), 2-methyl-2H-isothiazol-3-one (MIT), 2-octyl-2H-isothiazol-3- one (OIT), 5-chloro-2-methyl-2H-isothiazol-3-one (CMIT), and 2-butyl- benzo[d]isothiazol-3-one (BBIT); 3-iodo-2-propynylbutylcarbamate (IPBC), benzyl alcohol, pyridine-2-thiol 1-oxide and salts thereof; 2,2-dibromo-2-cyanoacetamide (DBNPA), N-(3-aminopropyl)-N-dodecylpropane-1 ,3-diamine (Diamine), tetrakis(hydroxymethyl)phosphonium sulphate(2:1) (THPS), 2,2-dithiobis[N- methylbenzamide] (DTBMA), 2-bromo-2-(bromomethyl)pentanedinitril (DBDCB); and mixtures thereof; and
(b) an alkoxylated amine of the formula (I)
NR1R2R3 (I) where R1 is -CH2CH2O-An-Bm-H; -CH2CH2O-Bm-An-H or -CH2CH2O-Em+n-H; where A is -CH2CH2O-;
B is -CH(Ra)-CH2-O- or -CH2-CH(Ra)-O-;
E is randomly distributed A and B;
Ra is Ci-C -alkyl; m is 0 to 30; and n is 0 to 15; where the sum of m + n is 5 to 40; and R2 and R3 have independently one of the meanings of R1 or are Ci-C -alkyl.
The invention relates moreover to the use of an alkoxylated amine (I) as defined above for enhancing the antimicrobial, in particular the preserving, activity of the antimicrobial agent as defined above as component (a). The invention relates also to a method for enhancing the antimicrobial, in particular the preserving, activity of the antimicrobial agent as defined above as component (a), comprising using the antimicrobial agent (a) in combination with said alkoxylated amine (I).
The invention relates further to a kit of parts comprising at least two parts, where the first part comprises at least one antimicrobial agent as defined above as component (a); the second part comprises at least one alkoxylated amine (I) as defined above and optionally at least one organic solvent; and an optional third part comprises at least one organic solvent.
DETAILED DESCRIPTION OF THE INVENTION
Definitions
An antimicrobial agent or short antimicrobial is an agent that combats or controls microbes. Unless specified otherwise, in terms of the present invention, the expressions “microbicide” and “biocide” are used as synonyms for antimicrobials.
Microbes in the terms of the present invention are undesired harmful microorganisms and comprise bacteria, fungi (including yeasts and molds), microscopic algae, protozoans, spores thereof and, despite the fact that they are generally not considered as living beings, also viruses and prions. "Harmful " means that the microorganism have an unwanted presence or a detrimental effect on humans, their activities or the products they use or produce, or on animals, materials, plants or the environment.
An antimicrobial effect encompasses a preservative as well as a biocidal effect. Preservative or preserving effect in terms of the present invention means that the material or product as such comprising an antimicrobial agent is protected against deterioration by microbial attack. As a consequence, the thusly protected material or product has for example a longer storage stability. Just by way of example, an antimicrobial is used in a laundry detergent composition as a preservative to keep the composition storage-stable by avoiding or reducing the proliferation or growth of microbes present therein and thus avoiding or reducing the deterioration of the properties of the composition, such as the formation of malodours, a change in viscosity or pH, a phase separation etc. Biocidal effect in terms of the present invention means that the composition comprising an antimicrobial agent exerts its antimicrobial effect on a product or material treated with and different from this composition. To stay with the example of a laundry detergent composition containing an antimicrobial, this composition exerts a biocidal effect in terms of the present invention if microorganisms on or in laundry treated therewith are killed or hampered in their proliferation or growth by the application of said composition. Another example of a biocidal application is a disinfectant or sanitizer composition which exerts its biocidal effect on materials or products treated therewith. The biocidal effect has to be fast, since microbes on or in the treated materials or products have to be eliminated or reduced within seconds or minutes, whereas the preservative effect is a long-term effect, since it has to prevail throughout the shelf-life of the product, which can be years. Many antimicrobials have both a preservative and a biocidal effect, the prevalence depending mainly on the concentration of the antimicrobial in the composition.
Phenoxyisopropanol is 1-phenoxy-propan-2-ol. Commercially available phenoxyisopropanol may however also contain minor amounts (i.e. up to 5% by weight) of the isomeric 2-phenoxy-propan-2-ol; such mixtures also fall under the term “phenoxyisopropanol” as used in context of the present invention. Phenoxyisopropanol contains a stereo- genic center and can thus be present in form of the essentially pure S enantiomer, the essentially pure R enantiomer and mixtures of the two enantiomers, including racemic mixtures. The present invention encompasses both the use of the essentially pure enantiomers and of mixtures of the two enantiomers, including racemic mixtures. Generally, however, the racemate is used, since this is the commercially most common form thereof.
The organic moieties mentioned below are collective terms for individual listings of the individual group members. The prefix Cn-Cm indicates in each case the possible number of carbon atoms in the group.
The term "alkyl" as used herein is used in the proper sense and refers to saturated straight-chain (linear) or branched non-cyclic hydrocarbon radicals having the indicated number of carbon atoms. Ci-C4-Alkyl denotes thus an alkyl radical with 1 to 4 carbon atoms. Examples are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and tert-butyl. Ci-Cs-Alkyl denotes an alkyl radical with 1 to 5 carbon atoms. Examples are, in addition to those mentioned above for Ci-C4-alkyl, n-pentyl, 1 -methyl butyl, 2-methyl- butyl, 3-methylbutyl, 2,2-dimethylpropyl, 1 -ethylpropyl, 1 ,1 -dimethylpropyl, 1 ,2-dime- thylpropyl and other structural isomers thereof. Ci-Ce-Alkyl denotes an alkyl radical with 1 to 6 carbon atoms. Examples are, in addition to those mentioned above for Ci-Cs-al- kyl, n-hexyl, 1 -methylpentyl, 2-methyl pentyl, 3-methylpentyl, 4-methylpentyl, 1 ,1-dime- thylbutyl, 1 ,2-dimethylbutyl, 1 ,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3- dimethylbutyl, 1 -ethylbutyl, 2-ethylbutyl, 1 , 1 ,2-trimethylpropyl, 1 ,2,2-trimethylpropyl, 1- ethyl-1-methylpropyl, 1-ethyl-2-methylpropyl and other structural isomers thereof. Ci- Cs-Alkyl denotes an alkyl radical with 1 to 8 carbon atoms. Examples are, in addition to those mentioned above for Ci-Ce-alkyl, n-heptyl, n-octyl, 2-ethylhexyl and (other) structural isomers thereof. Ci-C -Alkyl denotes an alkyl radical with 1 to 10 carbon atoms. Examples are, in addition to those mentioned above for Ci-Cs-alkyl, n-nonyl, n-decyl, 2- propylheptyl and (other) structural isomers thereof. Ci-C -Alkyl denotes an alkyl radical with 1 to 16 carbon atoms. Examples are, in addition to those mentioned above for Ci-C -alkyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl and structural isomers thereof. Ci-Cis-Alkyl denotes an alky radical with 1 to 18 carbon atoms. Examples are, in addition to those mentioned for Ci-C -alkyl, n-heptadecyl, n- octadecyl and structural isomers thereof.
Ci-C4-Hydroxyalkyl denotes a linear or branched Ci-C4-alkyl radical, as defined above, wherein one hydrogen atom is replaced by an OH group. Ci-Cs-Hydroxyalkyl denotes a linear or branched Ci-Cs-alkyl radical, as defined above, wherein one hydrogen atom is replaced by an OH group. Examples are hydroxymethyl, 1-hydroxyethyl, 2-hydroxy- ethyl, 1-hydroxy-n-propyl, 2-hydroxy-n-propyl, 3-hydroxy-n-propyl, 1 -hydroxy- 1 -methylethyl, 2-hydroxy-1-methyl-ethyl, 1-hydroxy-n-butyl, 2-hydroxy-n-butyl, 3-hydroxy-n-bu- tyl, 4-hydroxy-n-butyl and the like.
Oxo is a group =0. If for example in the definition of (C-9) R9 and R10 form together an oxo group, the compound (C-9) is in this case a 1,2-dioxolan-2-one substituted in the 4- position by R11.
In terms of the present invention, Ci-C4-carboxylic acids are compounds R-C(=O)OH, where R is H or Ci-Cs-alkyl. Examples are formic acid, acetic acid, propionic acid, butyric acid and isobutyric acid.
Unless specified otherwise, in terms of the present invention “ppm” means weight-ppm and corresponds to 1 g of component per 1,000,000 g of the reference. Alternatively expressed, 1 ppm corresponds to 0.0001% by weight.
Embodiments (E.x) of the invention
General and preferred embodiments E.x are summarized in the following, non-exhaus- tive list. Further preferred embodiments become apparent from the paragraphs following this list.
E.1. A composition comprising
(a) at least one antimicrobial agent selected from the group consisting of 2-phenoxy- ethanol, phenoxyisopropanol, 4,4’-dichloro 2’-hydroxydiphenylether, 2-bromo-2- nitropropane-1,3-diol, glutaraldehyde, 2,4-dichlorobenzylalcohol, 1 ,3,5-tris-(2-hy- droxyethyl)-1 ,3,5-hexahydrotriazine, formic acid and salts thereof, benzoic acid and salts thereof, sorbic acid and salts thereof, lactic acid and salts thereof, iso- thiazolinones selected from the group consisting of 1 ,2-benzisothiazol-3(2H)-one (BIT), 2-methyl-2H-isothiazol-3-one (MIT), 2-octyl-2H-isothiazol-3-one (OIT), 5- chloro-2-methyl-2H-isothiazol-3-one (CM IT), and 2-butyl-benzo[d]isothiazol-3-one (BBIT); 3-iodo-2-propynylbutylcarbamate (IPBC), benzyl alcohol, pyridine-2-thiol
1-oxide and salts thereof; 2,2-dibromo-2-cyanoacetamide (DBNPA), N-(3-ami- nopropyl)-N-dodecylpropane-1 ,3-diamine (Diamine), tetrakis(hydroxymethyl)- phosphonium sulphate(2:1) (THPS), 2,2-dithiobis[N-methylbenzamide] (DTBMA),
2-bromo-2-(bromomethyl)pentanedinitril (DBDCB); and mixtures thereof; and
(b) an alkoxylated amine of the formula (I) NR1R2R3 (I) where
R1 is -CH2CH2O-An-Bm-H; -CH2CH2O-Bm-An-H or -CH2CH2O-Em+n-H; where A is -CH2CH2O-;
B is -CH(Ra)-CH2-O- or -CH2-CH(Ra)-O-;
E is randomly distributed A and B;
Ra is Ci-C -alkyl; m is 0 to 30; and n is 0 to 15; where the sum of m + n is 5 to 40; and R2 and R3 have independently one of the definitions given for R1 or are C1-C18- alkyl.
E.2. The composition according to embodiment E.1 , where the antimicrobial agent is selected from the group consisting of 2-phenoxyethanol, phenoxyisopropanol, 4,4’-dichloro 2’-hydroxydiphenylether, 2-bromo-2-nitropropane-1 ,3-diol, glutaraldehyde, benzoic acid and salts thereof and isothiazolinones selected from the group consisting of 1 ,2-benzisothiazol-3(2H)-one (BIT), 2-methyl-2H-isothiazol-3- one (MIT), 2-octyl-2H-isothiazol-3-one (OIT), 5-chloro-2-methyl-2H-isothiazol-3- one (CM IT) and 2-butyl-benzo[d]isothiazol-3-one (BBIT); and preferably from the group consisting of 2-phenoxyethanol, phenoxyisopropanol, 4,4’-dichloro 2’-hy- droxydiphenylether, 2-bromo-2-nitropropane-1 ,3-diol and 1 ,2-benzisothiazol- 3(2H)one (BIT).
E.3. The composition according to embodiment E.2, where the antimicrobial agent is selected from the group consisting of 2-phenoxyethanol, 4,4’-dichloro 2’-hy- droxydiphenylether, benzoic acid and salts thereof and 1 ,2-benzisothiazol- 3(2H)one (BIT).
E.4. The composition according to embodiment E.2, where the antimicrobial agent is selected from the group consisting of 2-phenoxyethanol, 2-bromo-2-nitropropane- 1 ,3-diol, glutaraldehyde and 1 ,2-benzisothiazol-3(2H)one (BIT).
E.5. The composition according to any of embodiments E.3 or E.4, where the antimicrobial agent is 2-phenoxyethanol.
E.6. The composition according to any of the preceding embodiments, where R2 and R3 have independently one of the meanings of R1. E.7. The composition according to any of the preceding embodiments, where Ra is methyl.
E.8. The composition according to any of the preceding embodiments, where m is 10 to 30 and n is 3 to 12; or m is 10 to 25 and n is 0.
E.9. The composition according to embodiment E.8, where m is 12 to 30 and n is 4 to 12; or m is 10 to 20 and n is 0.
E.10. The composition according to embodiment E.9, where m is 14 to 27 and n is 5 to 10; or m is 15 and n is 0.
E.11. The composition according to embodiment E.8, where m is 10 to 20 and n is 3 to 8; or m is 10 to 25 and n is 0.
E.12. The composition according to embodiment E.11 , where m is 13 to 15 and n is 4 to 6; or m is 14 to 16 and n is 0.
E.13. The composition according to embodiment E.12, where m is 14 and n is 5; or m is 15 and n is 0.
E.14. The composition according to any of the preceding embodiments, where R1 is - CH2CH2O-An-Bm-H.
E.15. The composition according to any of embodiments E.1 to E.5 and E.7 to E.14, where one of R2 and R3 has one of the meanings of R1 (and the other is C1-C18- alkyl).
E.16. The composition according to any of the preceding embodiments, where the antimicrobial agent and the alkoxylated amine are present in an overall weight ratio of from 100:1 to 1 :10000; in particular from 5:1 to 1 :10000.
E.17. The composition according to embodiment E.16, where the antimicrobial agent and the alkoxylated amine are present in an overall weight ratio of from 50:1 to 1 :2000; in particular from 5:1 to 1 :2000.
E.18. The composition according to embodiment E.17, where the antimicrobial agent and the alkoxylated amine are present in an overall weight ratio of from 50:1 to 1 :1000; in particular from 5:1 to 1 :1000.
E.19. The composition according to embodiment E.18, where the antimicrobial agent and the alkoxylated amine are present in an overall weight ratio of from 50:1 to 1 :500; in particular from 5:1 to 1 :500.
E.20. The composition according to embodiment E.19, where the antimicrobial agent and the alkoxylated amine are present in an overall weight ratio of from 20:1 to 1 :500; in particular from 5:1 to 1 :500.
E.21. The composition according to embodiment E.20, where the antimicrobial agent and the alkoxylated amine are present in an overall weight ratio of from 10:1 to 1 :450; in particular from 5:1 to 1 :450.
E.22. The composition according to embodiment E.21 , where the antimicrobial agent and the alkoxylated amine are present in an overall weight ratio of from 2:1 to 1 :450. E.23. The composition according to any of the preceding embodiments, where the antimicrobial agent is 2-phenoxyethanol, and 2-phenoxyethanol and the alkoxylated amine are present in an overall weight ratio of from 3:1 to 1 :3.
E.24. The composition according to embodiment E.23, where 2-phenoxyethanol and the alkoxylated amine are present in an overall weight ratio of from 2.5:1 to 1 :2.5.
E.25. The composition according to embodiment E.24, where 2-phenoxyethanol and the alkoxylated amine are present in an overall weight ratio of from 2:1 to 1 :2.5.
E.26. The composition according to embodiment E.25, where 2-phenoxyethanol and the alkoxylated amine are present in an overall weight ratio of from 1 .5:1 to 1 :2.5.
E.27. The composition according to embodiment E.26, where 2-phenoxyethanol and the alkoxylated amine are present in an overall weight ratio of from 1.5:1 to 1 :2, e.g. 1.3:1 to 1 :2 or 1 :1 to 1 :2.
E.28. The composition according to any of embodiments E.1 to E.22, where the antimicrobial agent is selected from the group consisting of 2-bromo-2-nitropropane- 1 ,3-diol, glutaraldehyde and 1 ,2-benzisothiazol-3(2H)one (BIT); and the antimicrobial agent and the alkoxylated amine are present in an overall weight ratio of from 1 :1 to 1 :10000.
E.29. The composition according to embodiment E.28, where the antimicrobial agent and the alkoxylated amine are present in an overall weight ratio of from 1 :1 to 1 :2000.
E.30. The composition according to embodiment E.29, where the antimicrobial agent and the alkoxylated amine are present in an overall weight ratio of from 1 :1 to 1 :1000.
E.31. The composition according to embodiment E.30, where the antimicrobial agent and the alkoxylated amine are present in an overall weight ratio of from 1 :1 to 1 :500.
E.32. The composition according to embodiment E.31 , where the antimicrobial agent and the alkoxylated amine are present in an overall weight ratio of from 1 :1 to 1 :450.
E.33. The composition according to embodiment E.32, where the antimicrobial agent and the alkoxylated amine are present in an overall weight ratio of from 1 :100 to 1 :450.
E.34. The composition according to any of the preceding embodiments, where the antimicrobial agent is selected from the group consisting of 2-phenoxyethanol, 2- bromo-2-nitropropane-1 ,3-diol, glutaraldehyde and 1 ,2-benzisothiazol-3(2H)one (BIT); in the alkoxylated amine of the formula (I) R1, R2 and R3 are independently -CH2CH2O-An-Bm-H, where Ra is methyl, m is 10 to 30 and n is 3 to 12; or m is 10 to 20 and n is 0; and the antimicrobial agent and the alkoxylated amine are present in an overall weight ratio of from 3:1 to 1 :500.
E.35. The composition according to embodiment E.34, where the antimicrobial agent is selected from the group consisting of 2-phenoxyethanol, 2-bromo-2-nitropropane- 1 ,3-diol, glutaraldehyde and 1 ,2-benzisothiazol-3(2H)one (BIT); in the alkoxylated amine of the formula (I) R1, R2 and R3 are independently -CF^CFW-An-Bm-H, where Ra is methyl, m is 14 to 27 and n is 5 to 10; or m is 15 and n is 0; and the antimicrobial agent and the alkoxylated amine are present in an overall weight ratio of from 2:1 to 1 :450.
E.36. The composition according to any of embodiments E.34 or E.35, where the antimicrobial agent is 2-phenoxyethanol; in the alkoxylated amine of the formula (I) R1, R2 and R3 are independently -CH2CH2O-An-Bm-H, where Ra is methyl, m is 10 to 30 and n is 3 to 12; or m is 10 to 20 and n is 0; and the antimicrobial agent and the alkoxylated amine are present in an overall weight ratio of from 3:1 to 1 :5.
E.37. The composition according to embodiment E.36, where m is 13 to 15 and n is 4 to 6; or m is 14 to 16 and n is 0.
E.38. The composition according to embodiment E.37, where m is 14 and n is 5; or m is 15 and n is 0.
E.39. The composition according to any of embodiments E.36 to E.38, where the antimicrobial agent and the alkoxylated amine are present in an overall weight ratio of from 3:1 to 1 :3.
E.40. The composition according to embodiment E.39, where the antimicrobial agent and the alkoxylated amine are present in an overall weight ratio of from 2.5:1 to 1 :2.5.
E.41. The composition according to embodiment E.40, where the antimicrobial agent and the alkoxylated amine are present in an overall weight ratio of from 2:1 to 1 :2.5, preferably from 1.5:1 to 1 :2.5; e.g. 1.5:1 to 1 :2 or 1.3:1 to 1 :2 or 1 :1 to 1 :2.
E.42. The composition according to any of embodiments E.34 or E.35, where the antimicrobial agent is selected from the group consisting of 2-bromo-2-nitropropane- 1 ,3-diol, glutaraldehyde and 1 ,2-benzisothiazol-3(2H)one (BIT); in the alkoxylated amine of the formula (I) R1, R2 and R3 are independently -CH2CH2O-An-Bm-H, where Ra is methyl, m is 10 to 20 and n is 3 to 8; and the antimicrobial agent and the alkoxylated amine are present in an overall weight ratio of from 1 :1 to 1 :500.
E.43. The composition according to embodiment E.42, where m is 13 to 15 and n is 4 to 6.
E.44. The composition according to embodiment E.43, where m is 14 and n is 5.
E.45. The composition according to any of embodiments E.42 to E.44, the antimicrobial agent and the alkoxylated amine are present in an overall weight ratio of from 1 :1 to 1 :450.
E.46. The composition according to embodiment E.45, where the antimicrobial agent and the alkoxylated amine are present in an overall weight ratio of from 1 :100 to 1 :450.
E.47. The composition according to any of the preceding embodiments, where the composition further comprises
(c) at least one organic solvent selected from the group consisting of (c.1) carboxamides of the formula (C-1)
Figure imgf000012_0001
where
R4 is hydrogen or Ci-Cs-alkyl;
R5 is Ci-Cs-alkyl; and
R6 is Ci-Cs-alkyl or Ci-Cs-hydroxyalkyl;
(c.2) carboxylic esters of the formula (C-2)
Figure imgf000012_0002
(C- 2) where
R6 is Ci-Cs-alkyl or Ci-Cs-hydroxyalkyl; and
R7 is Ci-Cio-alkyl;
(c.3) Cs-Cs-alkanols;
(c.4) Cs-Cs-alkanediols;
(c.5) Ci-Cs-alkylmonoethers of C2-Cs-alkanediols;
(c.6) diethylene glycol, dipropylene glycol, a polyethylene glycol with up to
10 repeat units or a polypropylene glycol with up to 10 repeat units;
(c.7) Ci-Cs-alkylmonoethers of diethylene glycol or dipropylene glycol;
(c.8) lactones of formula (C-8)
(C- 8)
Figure imgf000012_0003
where R8 is Ci-Cs-alkyl;
(c.9) dioxolanes of the formula (C-9) (C- 9)
Figure imgf000013_0001
where
R9 and R10 are independently Ci-C4-alkyl or form together an oxo group; and
R11 is Ci-C4-alkyl or Ci-C4-hydroxyalkyl; and
(c.10) mono-, di- or triesters of glycerol with Ci-C4-carboxylic acids.
E.48. The composition according to embodiment E.47, where the organic solvent of component (c) is selected from the group consisting of
(c.1) the carboxamide of the formula (C-1), where R4 and R5 are methyl, and R6 is 1 -hydroxyethyl;
(c.5) Cs-Cs-alkylmonoethers of C2-C3-alkanediols;
(c.7) Ci-Ce-alkylmonoethers of diethylene glycol or dipropylene glycol; and (c.8) the lactone of formula (C-8), where R8 is methyl.
E.49. The composition according to embodiment E.48, where the organic solvent of component (c) is selected from the group consisting of
(c.1) the carboxamide of the formula (C-1), where R4 and R5 are methyl, and R6 is 1 -hydroxyethyl;
(c.5) 1-butoxy-propan-2-ol;
(c.7) diethyleneglycolmono-n-butyl ether; and
(c.8) the lactone of formula (C-8), where R8 is methyl.
E.50. The composition according to any of embodiments E.47 to 49, where the antimicrobial agent and the organic solvent of component (c) are present in an overall weight ratio of from 10:1 to 1 :10.
E.51. The composition according to embodiment E.50, where the antimicrobial agent and the organic solvent of component (c) are present in an overall weight ratio of from 5:1 to 1:5.
E.52. The composition according to embodiment E.51, where the antimicrobial agent and the organic solvent of component (c) are present in an overall weight ratio of from 3:1 to 1:3.
E.53. The composition according to embodiment E.52, where the antimicrobial agent and the organic solvent of component (c) are present in an overall weight ratio of from 2:1 to 1:2.
E.54. The composition according to embodiment E.53, where the antimicrobial agent and the organic solvent of component (c) are present in an overall weight ratio of from 2:1 to 1:1. E.55. The composition according to any of the preceding embodiments, which is selected from the group consisting of antimicrobial concentrates, homecare compositions, compositions for cleaning or disinfecting on an industrial scale, personal care compositions, process water, cooling water, water in fish or shrimp ponds, water in drinking troughs, metal working fluids; water based raw materials, polymer solutions, polymer dispersions, polymer emulsions, inorganic slurries, organic slurries, surfactant compositions; compositions for treating animal hide; compositions for treating leather; compositions for treating textiles during the manufacturing process thereof; compositions for treating lumber; compositions for treating paper or the precursor material during papermaking processes; crop protection compositions; pharmaceutical compositions; paints, glues, adhesives, sealants, dyes, pigments and dispersions thereof, inks, and wet wipes.
E.56. Kit of parts comprising at least two parts, where the first part comprises at least one antimicrobial agent as defined in any of embodiments E.1 to E.6; the second part comprises an alkoxylated amine as defined in any of embodiments E.1 and E.6 to E.15 and optionally at least one organic solvent; and an optional third part comprises at least one organic solvent; where the first part does not comprise an alkoxylated amine as defined in any of embodiments E.1 and E.6 to E.15; where the second part does not comprise any antimicrobial agent as defined in any of embodiments E.1 to E.5; where the optional third part does not comprise any antimicrobial agent as defined in any of embodiments E.1 to E.5 nor an alkoxylated amine as defined in any of embodiments E.1 and E.6 to E.15; and where the first and second parts contain the at least one antimicrobial agent as defined in any of embodiments E.1 to E.5 and the alkoxylated amine as defined in any of embodiments E.1 and E.6 to E.15 in such amounts that when the first and the second part are mixed the resulting overall weight ratio is as defined in any of embodiments E.16 to E.22.
E.57. The use of an alkoxylated amine as defined in any of embodiments E.1 and E.6 to E.15 for enhancing the antimicrobial, in particular the preserving, activity of the antimicrobial agent as defined in any of embodiments E.1 to E.5.
E.58. The use according to embodiment E.57 of an alkoxylated amine as defined in any of embodiments E.1 and E.6 to E.15 for enhancing the antimicrobial, in particular the preserving, activity of 2-phenoxyethanol.
E.59. The use according to any of embodiments E.57 or E.58, for enhancing the antimicrobial, in particular the preserving, activity of the antimicrobial agent in an aqueous liquid homecare composition.
E.60. The use according to any of embodiments E.57 to E.59, where the antimicrobial agent as defined in any of embodiments E.1 to E.5 and the alkoxylated amine as defined in any of embodiments E.1 and E.6 to E.15 are used in a weight ratio which is as defined in any of embodiments E.16 to E.22.
E.61 . The use according to any of embodiments E.57 to E.59, where the antimicrobial agent, the alkoxylated amine and their weight ratio are as defined in any of embodiments E.34 to E.46
Unless specified otherwise, the below remarks to suitable and preferred antimicrobial agents, alkoxylated amines (I), weight ratios in which these are used and compositions in which these are used apply both to the compositions of the inventions as well as to the use and method of the invention.
The antimicrobial agent is inter alia selected from formic acid and salts thereof, benzoic acid and salts thereof, sorbic acid and salts thereof, lactic acid and salts thereof. Suitable salts of these acids are alkali metal salts, such as the lithium, sodium or potassium salts; earth alkaline metal salts, such as the magnesium and calcium salts, and ammonium salts, such as the salts containing an ammonium cation of the formula [NRaRbRcRd]+, where Ra, Rb, Rc and Rd, independently of each other, are selected from the group consisting of hydrogen, Ci-C4-alkyl and Ci-C4-alkoxy. Preferably, alkali metal salts, and in particular the sodium or potassium salts are used.
The antimicrobial agent is preferably selected from the group consisting of 2-phenoxy- ethanol, phenoxyisopropanol, 4,4’-dichloro 2’-hydroxydiphenylether (diclosan), 2- bromo-2-nitropropane-1 ,3-diol (bronopol), glutaraldehyde, benzoic acid and salts thereof and isothiazolinones selected from the group consisting of 1 ,2-benzisothiazol- 3(2H)-one (BIT), 2-methyl-2H-isothiazol-3-one (MIT), 2-octyl-2H-isothiazol-3-one (OIT), 5-chloro-2-methyl-2H-isothiazol-3-one (CM IT) and 2-butyl-benzo[d]isothiazol-3-one (BBIT); and more preferably from the group consisting of 2-phenoxyethanol, phenoxyisopropanol, 4,4’-dichloro 2’-hydroxydiphenylether, 2-bromo-2-nitropropane-1 ,3-diol, glutaraldehyde, benzoic acid and salts thereof and 1 ,2-benzisothiazol-3(2H)one (BIT), and more preferably from 2-phenoxyethanol, 4,4’-dichloro 2’-hydroxydiphenylether (diclosan), benzoic acid and salts thereof and 1 ,2-benzisothiazol-3(2H)one (BIT).
In an alternatively more preferred embodiment, the antimicrobial agent is selected from the group consisting of 2-phenoxyethanol, 2-bromo-2-nitropropane-1 ,3-diol (bronopol), glutaraldehyde and 1 ,2-benzisothiazol-3(2H)-one (BIT).
In a particular embodiment, the antimicrobial agent is 2-phenoxyethanol.
The antimicrobial agents of component (a) are known in the art and are commercially available or can be prepared by known methods. The alkoxylated amines (I) are also known in the art and are either commercially available, e.g. Plurafac® LF 1430 from BASF, or can be prepared by standard methods of organic chemistry. To obtain for example compounds (I) in which R2 and R3 have one of the meanings of R1 and Ra is methyl, triethanolamine N(CH2CH2OH)s is typically reacted with the necessary amounts of propylene oxide (PO) and/or ethylene oxide (EO). To obtain alkoxylated amines (I) in which R1, R2 and R3 are -CF^CFW-An-Bm-H or - CH2CH2O-Bm-An-H and in which neither m nor n are 0, i.e. in which both A and B repeat units are present and arranged blockwise, triethanolamine is first reacted with EO and then with PO to afford compounds (I) wherein R1, R2 and R3 are -CH2CH2O-An-Bm- H; or triethanolamine is first reacted with PO and then with EO to afford compounds (I) wherein R1, R2 and R3 are -CH2CH2O-Bm-An-H. To obtain alkoxylated amines (I) in which R1, R2 and R3 are -CF^CFW-Em+n-H and in which neither m nor n are 0, i.e. compounds (I) with a random distribution of the A and B repeat units, triethanolamine is reacted with a mixture of EO and PO containing EO and PO in an amount corresponding to the desired m and n. To obtain compounds wherein n is 0, triethanolamine is reacted with the necessary amount of PO only. To obtain compounds wherein m is 0, triethanolamine is reacted with the necessary amount of EO only. Alkoxylated amines in which one or both of R2 and R3 are C1-C1 s-alkyl can be obtained analogously by reacting a Ci-Ci8-alkyl-diethanolamine (if only one R2 and R3 is C1-C1 s-alkyl) with PO and/or EO as described above, or by reacting a di-(Ci-Cis-alkyl)-ethanolamine (if both of R2 and R3 are C1-C1 s-alkyl) with PO and/or EO as described above. For obtaining alkoxylated amines (I) in which Ra is different from methyl, corresponding alkylene oxides are used instead of PO, such as butylene oxide, pentylene oxide etc.
To obtain compounds (I) in which R1 as well as one of R2 and R3 is -CH2CH2O-An-Bm-H and the other of R2 and R3 is Ci -Ci s-alkyl , it is alternatively possible to react a C1-C18- alkylamine with the necessary amount of ethylene oxide (EO) and then, if m is not 0, with the necessary amount of propylene oxide (if Ra in B is methyl) or another suitable precursor of B (if Ra is different from methyl), such as butylene oxide, pentylene oxide etc.. To obtain compounds (I) in which R1 as well as one of R2 and R3 is -CH2CH2O-Bm- An-H and the other of R2 and R3 is C1-C1 s-alkyl , it is alternatively possible to react a Ci- Cis-alkylamine with the necessary amount of propylene oxide (if Ra in B is methyl) or another suitable precursor of B (if Ra is different from methyl), such as butylene oxide, pentylene oxide etc. and then, if n is not 0, with the necessary amount of ethylene oxide (EO) To obtain compounds (I) in which R1 as well as one of R2 and R3 is - CH2CH2O-Em+n-H and in which neither m nor n are 0, i.e. compounds (I) with a random distribution of the A and B repeat units, and the other of R2 and R3 is Ci-Cis-alkyl, it is alternatively possible to react a Ci-Cis-alkylamine with a mixture of EO and PO containing EO and PO (or another suitable precursor of B (if Ra is different from methyl), such as butylene oxide, pentylene oxide etc.) in an amount corresponding to the desired m and n. To obtain compounds (I) in which R1 is -CF^CFW-An-Bm-H and both of R2 and R3 are Ci -Ci s-alkyl , it is alternatively possible to react a di-(Ci-Ci8-alkyl)-amine with the necessary amount of ethylene oxide (EO) and then, if m is not 0, with the necessary amount of propylene oxide (if Ra in B is methyl) or another suitable precursor of B (if Ra is different from methyl), such as butylene oxide, pentylene oxide etc.. To obtain compounds (I) in which R1 is -CH2CH2O-Bm-An-H and both of R2 and R3 are C1-C18- alkyl, it is alternatively possible to react a di-(Ci-Ci8-alkyl)-amine with the necessary amount of propylene oxide (if Ra in B is methyl) or another suitable precursor of B (if Ra is different from methyl), such as butylene oxide, pentylene oxide etc. and then, if n is not 0, with the necessary amount of ethylene oxide (EO) To obtain compounds (I) in which R1 is -CH2CH2O-Em+n-H and in which neither m nor n are 0, i.e. compounds (I) with a random distribution of the A and B repeat units, and both of R2 and R3 are C1- C -alkyl, it is alternatively possible to react a di-(Ci-Ci8-alkyl)-amine with a mixture of EO and PO containing EO and PO (or another suitable precursor of B (if Ra is different from methyl), such as butylene oxide, pentylene oxide etc.) in an amount corresponding to the desired m and n.
As becomes apparent from the above-described synthesis methods by which the alkoxylated amines (I) are typically prepared using EO and/or PO or another alkylene oxide for alkoxylation, m and n are generally average values, since the degrees of alkoxylation are in general statistical averages which, for a specific product, may be an integer or a fraction. Just by way of example, in an alkoxylated amine (I) in which in R1 m is 14 and n is 5, some of the radicals R1 may contain more than 14 B units or less than 14 B units and/or more than 5 A units or less than 5 A units, the average number m of repeat units B being however 14 and the average number n of repeat units A being 5.
In a preferred embodiment, R2 and R3 have independently one of the meanings of R1.
In another preferred embodiment, one of R2 and R3 has one of the meanings of R1 (and the other is Ci-C -alkyl).
More preferably, however, R2 and R3 have independently one of the meanings of R1.
Preferably, in units B Ra is methyl, B thus being preferably derived from PO.
Preferably, m is 10 to 30 (on average) and n is 3 to 12 (on average); or m is 10 to 25 (on average) and n is 0. More preferably, m is 13 to 30 (on average) and n is 4 to 10 (on average); or m is 14 to 16 (on average) and n is 0. In a specific embodiment, m is 14 to 27 (on average) and n is 5 to 10 (on average); or m is 15 (on average) and n is 0. In a specific embodiment, m is 14 (on average) and n is 5 (on average); or m is 15 (on average) and n is 0.
Preferably, R1 is -CH2CH2O-An-Bm-H. Preferably, n, m and Ra in B have the above preferred meanings.
More preferably, R1, R2 and R3 are -CH2CH2O-An-Bm-H. Even more preferably, R1, R2 and R3 are -CH2CH2O-An-Bm-H, where Ra in B is methyl, m is 10 to 30 (on average) and n is 3 to 12 (on average); or m is 10 to 25 (on average) and n is 0. In particular, R1, R2 and R3 are -CH2CH2O-An-Bm-H, where Ra in B is methyl, m is 13 to 30 (on average) and n is 4 to 10 (on average); or m is 14 to 16 (on average) and n is 0. Specifically, R1, R2 and R3 are -CH2CH2O-An-Bm-H, where Ra in B is methyl, m is 14 to 27 (on average) and n is 5 to 10 (on average); or m is 15 (on average) and n is 0.
In a specific embodiment, R1, R2 and R3 are -CH2CH2O-An-Bm-H, where Ra in B is methyl, m is 10 to 20 (on average) and n is 3 to 8 (on average); or m is 10 to 25 (on average) and n is 0. More specifically, R1, R2 and R3 are -CH2CH2O-An-Bm-H, where Ra in B is methyl, m is 13 to 15 (on average) and n is 4 to 6 (on average); or m is 14 to 16 (on average) and n is 0. Very specifically, R1, R2 and R3 are -CH2CH2O-An-Bm-H, where Ra in B is methyl, m is 14 (on average) and n is 5 (on average); or m is 15 (on average) and n is 0.
The antimicrobial agent and the alkoxylated amine are preferably present in an overall weight ratio of from 100:1 to 1 :10000 (e.g. 5:1 to 1 :10000), more preferably from 50:1 to 1 :2000 (e.g. 5:1 to 1 :2000), even more preferably from 50:1 to 1 :1000 (e.g. 5:1 to 1 :1000), particularly preferably from 50:1 to 1 :500, in particular from 20:1 to 1 :500, more particularly from 10:1 to 1 :500, even more particularly from 5:1 to 1 :500, specifically from 5:1 to 1 :450, very specifically from 2:1 to 1 :450.
In a particular embodiment, the antimicrobial agent is 2-phenoxyethanol, and 2-phe- noxyethanol and the alkoxylated amine are present in an overall weight ratio of from 3:1 to 1 :5, preferably from 3:1 to 1 :3, more preferably from 2.5:1 to 1 :2.5, even more preferably from 2:1 to 1 :2.5, in particular from 1.5:1 to 1 :2.5, more particularly from 1.5:1 to 1 :2, specifically from 1.3:1 to 1 :2 and very specifically from 1 :1 to 1 :2.
In another particular embodiment, the antimicrobial agent is selected from the group consisting of 2-bromo-2-nitropropane-1 ,3-diol, glutaraldehyde and 1 ,2-benzisothiazol- 3(2H)one (BIT), and said antimicrobial agent and the alkoxylated amine are present in an overall weight ratio of from 1 : 1 to 1 :500, preferably from 1 : 1 to 1 :450, and more preferably from 1 : 100 to 1 :450. In a particularly preferred embodiment, the antimicrobial agent is selected from the group consisting of 2-phenoxyethanol, 2-bromo-2-nitropropane-1 ,3-diol, glutaraldehyde and 1 ,2-benzisothiazol-3(2H)one (BIT); in the alkoxylated amine of the formula (I) R1, R2 and R3 are independently -CF^CFW-An-Bm-H, where Ra is methyl, m is 10 to 30 and n is 3 to 12; or m is 10 to 20 and n is 0; and the antimicrobial agent and the alkoxylated amine are present in an overall weight ratio of from 3:1 to 1 :500; where specifically in the alkoxylated amine of the formula (I) R1, R2 and R3 are independently -CH2CH2O-An- Bm-H, where Ra is methyl, m is 14 to 27 and n is 5 to 10; or m is 15 and n is 0; and the antimicrobial agent and the alkoxylated amine are present in an overall weight ratio of from 2:1 to 1 :450.
In a particular embodiment, the antimicrobial agent is 2-phenoxyethanol; in the alkoxylated amine of the formula (I) R1, R2 and R3 are independently -CH2CH2O-An-Bm-H, where Ra is methyl, m is 10 to 30 and n is 3 to 12; or m is 10 to 20 and n is 0; and the antimicrobial agent and the alkoxylated amine are present in an overall weight ratio of from 3:1 to 1 :5, preferably from 3:1 to 1 :3, more preferably from 2.5:1 to 1 :2.5, even more preferably from 2:1 to 1 :2.5, in particular from 1.5:1 to 1 :2.5, specifically from 1.5:1 to 1 :2, more specifically from 1.3:1 to 1 :2 and very specifically from 1 :1 to 1 :2.
More particularly, the antimicrobial agent is 2-phenoxyethanol; in the alkoxylated amine of the formula (I) R1, R2 and R3 are independently -CH2CH2O-An-Bm-H, where Ra is methyl, m is 13 to 15 and n is 4 to 6; or m is 14 to 16 and n is 0; and the antimicrobial agent and the alkoxylated amine are present in an overall weight ratio of from 2:1 to 1 :5, preferably from 2:1 to 1 :3, more preferably from 1.5:1 to 1 :2.5, and even more preferably from 1 :1 to 1 :2.
Specifically, the antimicrobial agent is 2-phenoxyethanol; in the alkoxylated amine of the formula (I) R1, R2 and R3 are independently -CH2CH2O-An-Bm-H, where Ra is methyl, m is 14 and n is 5; or m is 15 and n is 0; and the antimicrobial agent and the alkoxylated amine are present in an overall weight ratio of from 2:1 to 1 :5, preferably from 2:1 to 1 :3, more preferably from 1.5:1 to 1 :2.5, and even more preferably from 1 :1 to 1 :2.
In another particular embodiment, the antimicrobial agent is selected from the group consisting of 2-bromo-2-nitropropane-1 ,3-diol, glutaraldehyde and 1 ,2-benzisothiazol- 3(2H)one (BIT); in the alkoxylated amine of the formula (I) R1, R2 and R3 are independently -CH2CH2O-An-Bm-H, where Ra is methyl, m is 10 to 20 and n is 3 to 8; and said antimicrobial agent and the alkoxylated amine are present in an overall weight ratio of from 1 :1 to 1 :500, preferably from 1 :1 to 1 :450, and more preferably from 1 :100 to 1 :450. More particularly, the antimicrobial agent is selected from the group consisting of 2- bromo-2-nitropropane-1 ,3-diol, glutaraldehyde and 1 ,2-benzisothiazol-3(2H)one (BIT); in the alkoxylated amine of the formula (I) R1, R2 and R3 are independently -CH2CH2O- An-Bm-H, where Ra is methyl, m is 13 to 15 and n is 4 to 6; and said antimicrobial agent and the alkoxylated amine are present in an overall weight ratio of from 1 :1 to 1 :500, preferably from 1 :1 to 1 :450, and more preferably from 1 :100 to 1 :450.
Specifically, the antimicrobial agent is selected from the group consisting of 2-bromo-2- nitropropane-1 ,3-diol, glutaraldehyde and 1 ,2-benzisothiazol-3(2H)one (BIT); in the alkoxylated amine of the formula (I) R1, R2 and R3 are independently -CF^CFW-An-Bm- H, where Ra is methyl, m is 14 and n is 5; and said antimicrobial agent and the alkoxylated amine are present in an overall weight ratio of from 1 :1 to 1 :500, preferably from 1 :1 to 1 :450, and more preferably from 1 :100 to 1 :450.
In a preferred embodiment, the composition further comprises at least one organic solvent. This is of course different from components (a) and (b). The organic solvent is preferably selected from the group consisting of Ci-Cs-alkanols, C2-Cs-alkanediols, C1- Cs-alkylmonoethers of C2-Cs-alkanediols, polyetherpolyols, Ci-Cs-alkylmonoethers of polyetherpolyols, 5-, 6- or 7-membered lactones which may be substituted by one or more C1-C12-alkyl groups; 5-, 6- or 7-membered cyclic carbonates which may be substituted by one or more Ci-Ci2-alkyl groups; aliphatic esters, carboxamides, dioxolanes which may be substituted by one or more Ci-C4-alkyl and/or Ci-C4-hydroxyalkyl groups, aliphatic, alicyclic or heterocyclic amine-N-oxides and mixtures of the aforementioned solvents.
It has to be noticed that organic solvents in this context are not restricted to “typical” solvents, i.e. to organic compounds with solvating properties which are liquid at 25°C, but encompass compounds with solvating properties having a higher melting point of at most 50°C, and also compounds which exert their solvating properties only when mixed with water, such as the above-mentioned aliphatic, alicyclic or heterocyclic amine-N-oxides, which would more correctly be termed solubilizers.
Ci-Cs-alkanols are compounds R-OH, where R is linear or branched Ci-Cs-alkyl. Examples are methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, isobutanol, tert-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 1-octanol, 2-ethylhexanol and (other) structural isomers of the four last-mentioned 1 -alkanols.
C2-Cs-alkanediols are compounds HO-A-OH, where A is linear or branched C2-Cs-al- kanediyl (or C2-Cs-alkylene), where the two OH groups are not geminally bound (i.e. are not bound to the same carbon atom). Examples are ethylene glycol (1 ,2-ethane- diol), propylene glycol (1 ,2-propanediol), 1 ,3-propanediol, 1 ,2-butanediol, 1 ,4-butane- diol, 1 ,2-pentanediol, 1 ,5-pentanediol, 1 ,2-hexanediol, 1 ,6-hexanediol, 1 ,2-heptanediol, 1 ,2-octanediol and the like.
Ci-Cs-Alkylmonoethers of C2-Cs-alkanediols are compounds RO-A-OH, where A is as defined for the alkanediols above and R is Ci-Cs-alkyl. Examples are ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol monoisopropyl ether, ethylene glycol mono-n-butyl ether (butyl glycol), ethylene glycol mono-sec-butyl ether, ethylene glycol mono-isobutyl ether, ethylene glycol mono-tert-butyl ether, ethylene glycol monopentyl ether, ethylene glycol monohexyl ether, ethylene glycol monoheptyl ether, ethylene glycol monooctyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol monoisopropyl ether, propylene glycol mono-n- butyl ether, propylene glycol mono-sec-butyl ether, propylene glycol mono-isobutyl ether, propylene glycol mono-tert-butyl ether, propylene glycol monopentyl ether, propylene glycol monohexyl ether, propylene glycol monoheptyl ether, propylene glycol monooctyl ether, 1 ,3-propanediol monomethyl ether, 1 ,3-propanediol monoethyl ether, 1 ,3-propanediol mono-n-propyl ether, 1 ,3-propanediol monoisopropyl ether, 1 ,3-propanediol mono-n-butyl ether, 1 ,3-propanediol mono-sec-butyl ether, 1 ,3-propanediol mono-isobutyl ether, 1 ,3-propanediol mono-tert-butyl ether, 1 ,3-propanediol monopentyl ether, 1 ,3-propanediol monohexyl ether, 1 ,3-propanediol monoheptyl ether, 1 ,3- propanediol monooctyl ether and the like.
Polyetherpolyols are formally the etherification products of alkanediols and thus compounds HO-A-[O-A]n-OH, where each A is independently an alkylene group, generally a C2-Cs-alkylene group, such as 1 ,2-ethylene, 1 ,2-propylene or 1 ,3-propylene, and n is from 1 to 100. Examples are polyethylene glycol, generally with a molecular weight of from 106 to ca. 4500 (the term polyethylene glycol thus including diethylene glycol, triethylene glycol and other ethylene glycol oligomers), and polypropyleneglycol, generally with a molecular weight of from 134 to ca. 6000 (the term polypropylene glycol thus including dipropylene glycol, tripropylene glycol and other propylene glycol oligomers).
Ci-Cs-Alkylmonoethers of polyetherpolyols are compounds RO-A-[O-A]n-OH, where A and n are as defined for the polyetherpolyols above and R is Ci-Cs-alkyl. Examples are polyethylene glycol monomethyl ether, polyethylene glycol monoethyl ether, polyethylene glycol mono-n-propyl ether, polyethylene glycol mono-n-butyl ether, and the like.
Examples for 5-, 6- or 7-membered lactones which may be substituted by one or more Ci-Ci2-alkyl groups are y-butyrolactone, y-valerolactone, y-octalactone, y-nonalactone, 5-valerolactone, 5-decanolactone, 5-dodecanolactone and s-caprolactone which may carry one or more Ci-Ci2-alkyl substituents. Examples for 5-, 6- or 7-membered cyclic carbonates which may be substituted by one or more Ci -Ci 2-alkyl groups are ethylene carbonate, propylene carbonate and butylene carbonate which may carry one or more Ci-Ci2-alkyl substituents.
Examples for suitable aliphatic esters are ethyl acetate, propyl acetate, butyl acetate, methylpropionate, ethyl propionate and further esters described below in context with solvent (C-2).
Examples for suitable carboxamides are carboxamides of the formula R-C(=O)-NR’R”, where R is hydrogen, Ci-Ci2-alkyl which may carry one or more hydroxyl groups, or C2- Ci2-alkenyl, and R’ and R”, independently of each other, are hydrogen or Ci-Ci2-alkyl which may carry one or more hydroxyl groups, or R’ and R” form, together with the nitrogen atom to which they are bound, a saturated 6-membered heterocyclic ring which may contain a further heteroatom as ring member selected from O and N as ring member. Examples of such rings are given above. Preferably, the ring is morpholin-4-yl, i.e. morpholinyl bound via the nitrogen ring atom to R-C(=O)-. Specific examples of carboxamide solvents are N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethyla- cetamide, N,N-dimethyloctanamide, N,N-dimethylnonanamide, N,N-dimethylde- canamide, N,N-dimethyllactamide, octanyolmorpholine and further carboxamides described below in context with solvent (C-1).
Examples for suitable dioxolanes which may be substituted by one or more Ci-C4-alkyl and/or Ci-C4-hydroxyalkyl groups are given below in context with solvent (C-9).
Examples for suitable aliphatic, alicyclic or heterocyclic amine-N-oxides are N,N-dime- thyl-N-ethylamine N-oxide, N,N,N-triethylamine N-oxide, N,N-dimethyl-N-cyclohexyla- mine N-oxide, N,N-dimethyl-N-ethanolamine N-oxide (DMEAO) and N-methylmorpho- line N-oxide.
More preferably, the solvent is selected from the group consisting of Ci-Cs-alkanols, C2-Cs-alkanediols, Ci-Cs-alkylmonoethers of C2-Cs-alkanediols, 5-, 6- or 7-membered lactones which may carry one or more C1-C12-alkyl groups, and mixtures thereof. Among the Ci-Cs-alkanols, preference is given to Ci-C4-alkanols, in particular to C2-C3- alkanols (i.e. to ethanol, n-propanol, isopropanol or a mixture thereof), and specifically to n-propanol. Among the C2-Cs-alkanediols, preference is given to C2-C4-alkanediols, in particular to C2-C3-alkanediols, such as ethylene glycol, 1 ,2-propanediol and 1 ,3-pro- panediol, and specifically to 1 ,2-propanediol (propylene glycol). Among the Ci-Cs-alkyl- monoethers of C2-Cs-alkanediols preference is given to Ci-Ce-alkylmonoethers of C2- C4-alkanediols and in particular to Ci-C4-alkylmonoethers of a C2-C3-alkanediol, such as the Ci-C4-alkylmonoethers of ethylene glycol or propylene glycol, specific examples being ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether (also termed butylglyol), propylene glycol mono-n-propyl ether, propylene glycol mono-n-bu- tyl ether and mixtures thereof. Among the 5-, 6- or 7-membered lactones which may carry one or more Ci-Ci2-alkyl groups, preference is given to y-butyrolactone, y- valerolactone, y-octalactone, y-nonalactone, s-caprolactone and mixtures thereof.
In particular, the solvent is a C2-Cs-alkanediol, more preferably a C2-C4-alkanediol, in particular a C2-C3-alkanediol, such as ethylene glycol, 1 ,2-propanediol and 1 ,3-pro- panediol, and specifically 1 ,2-propanediol (propylene glycol).
In another particular embodiment the solvent is a Ci-Cs-alkanol, more preferably a Ci- C4-alkanol, and in particular a C2-C3-alkanol (i.e. ethanol, n-propanol, isopropanol or a mixture thereof), specifically ethanol.
In particular, however, the composition additionally comprises
(c) at least one organic solvent (which is of course different from components (a) and (b)) selected from the group consisting of (c.1) carboxamides of the formula (C-1)
Figure imgf000023_0001
where
R4 is hydrogen or Ci-Cs-alkyl;
R5 is Ci-Cs-alkyl; and
R6 is Ci-Cs-alkyl or Ci-Cs-hydroxyalkyl;
(c.2) carboxylic esters of the formula (C-2)
Figure imgf000023_0002
(C- 2) where
R6 is Ci-Cs-alkyl or Ci-Cs-hydroxyalkyl; and
R7 is Ci-Cio-alkyl;
(c.3) Cs-Cs-alkanols;
(c.4) Cs-Cs-alkanediols;
(c.5) Ci-Cs-alkylmonoethers of C2-Cs-alkanediols; (c.6) diethylene glycol, dipropylene glycol, a polyethylene glycol with up to 10 repeat units or a polypropylene glycol with up to 10 repeat units;
(c.7) Ci-Cs-alkylmonoethers of diethylene glycol or dipropylene glycol;
(c.8) lactones of formula (C-8)
(C- 8)
Figure imgf000024_0001
where R8 is Ci-Cs-alkyl;
(c.9) dioxolanes of the formula (C-9)
(C- 9)
Figure imgf000024_0002
where
R9 and R10 are independently Ci-C4-alkyl or form together an oxo group; and
R11 is Ci-C4-alkyl or Ci-C4-hydroxyalkyl; and
(c.10) mono-, di- or triesters of glycerol with Ci-C4-carboxylic acids.
Examples for carboxamides of the formula (C-1) are N-methylacetamide, N,N-dime- thylacetamide, N-ethylacetamide, N,N-diethylacetamide, N-ethyl-N-methylacetamide, N-propylacetamide, N,N-dipropylacetamide, N-methyl-N-propylacetamide, N-ethyl-N- propylacetamide, N-isopropylacetamide, N,N-diisopropylacetamide, N-methyl-N-iso- propylacetamide, N-ethyl-N-isopropylacetamide, N-n-butylacetamide, N,N-di-n-butyla- cetamide, N-n-butyl-N-methylacetamide, N-n-butyl-N-ethylacetamide, N-n-butyl-N- propylacetamide, N-n-butyl-N-isopropylacetamide, N-methylpropanamide, N,N-dime- thylpropanamide, N-ethylpropanamide, N,N-diethylpropanamide, N-ethyl-N-methylpro- panamide, N-propylpropanamide, N,N-dipropylpropanamide, N-methyl-N-propylpro- panamide, N-ethyl-N-propylpropanamide, N-isopropylpropanamide, N,N-diiso- propylpropanamide, N-methyl-N-isopropylpropanamide, N-ethyl-N-isopropylpropana- mide, N-n-butylpropanamide, N,N-di-n-butylpropanamide, N-n-butyl-N-methylpropana- mide, N-n-butyl-N-ethylpropanamide, N-n-butyl-N-propylpropanamide, N-n-butyl-N-iso- propylpropanamide, N-methyllactamide (CH3CH(OH)C(O)N(H)CH3), N,N-dimethyllac- tamide, N-ethyllactamide, N,N-diethyllactamide, N-methyl-N-ethyllactamide, N-propyl- lactamide, N,N-dipropyllactamide, N-methyl-N-propyllactamide, N-ethyl-N-propyllac- tamide, N-isopropyllactamide, N,N-diisopropyllactamide, N-methyl-N-isopropyllactam- ide, N-ethyl-N-isopropyllactamide and the like. Examples for carboxylic acids of the formula (C-2) are methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, n-butyl acetate, n-hexyl acetate, 2-ethylhexyl acetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, n-butyl propionate, n-hexyl propionate, 2-ethylhexyl propionate, methyl lactate, ethyl lactate, propyl lactate, isopropyl lactate, n-butyl lactate, n-hexyl lactate, 2-ethylhexyl lactate and the like.
Cs-Cs-Alkanols (c.3) are compounds R-OH wherein R is a linear or branched Cs-Cs-al- kyl group, as defined above. Examples are n-propanol, isopropanol, n-butanol, sec-bu- tanol, isobutanol, tert-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 1-octanol, 2-ethylhex- anol and (other) structural isomers of the four last-mentioned 1-alkanols.
Cs-Cs-Alkanediols (c.4) are compounds HO-A-OH, where A is linear or branched C3- Cs-alkanediyl (or Cs-Cs-alkylene), where the two OH groups are not geminally bound (i.e. are not bound to the same carbon atom). Examples are propylene glycol (1 ,2-pro- panediol), 1 ,3-propanediol, 1 ,2-butanediol, 1 ,4-butanediol, 1 ,2-pentanediol, 1 ,5-pen- tanediol, 1 ,2-hexanediol, 1 ,6-hexanediol, 1 ,2-heptanediol, 1 ,2-octanediol and the like.
Ci-Cs-Alkylmonoethers of C2-C8-alkanediols (c.5) are compounds RO-A-OH, where A is 1 ,2-ethylene (-CH2CH2-) or is as defined for the Cs-Cs-alkanediols above, and R is Ci-Cs-alkyl. Examples are ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol monoisopropyl ether, ethylene glycol mono-n-butyl ether (butyl glycol), ethylene glycol mono-sec-butyl ether, ethylene glycol mono-isobutyl ether, ethylene glycol mono-tert-butyl ether, ethylene glycol monopentyl ether, ethylene glycol monohexyl ether, ethylene glycol monoheptyl ether, ethylene glycol monooctyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol monoisopropyl ether, propylene glycol mono-n-butyl ether, propylene glycol mono-sec- butyl ether, propylene glycol mono-isobutyl ether, propylene glycol mono-tert-butyl ether, propylene glycol monopentyl ether, propylene glycol monohexyl ether, propylene glycol monoheptyl ether, propylene glycol monooctyl ether, 1 ,3-propanediol monomethyl ether, 1 ,3-propanediol monoethyl ether, 1 ,3-propanediol mono-n-propyl ether, 1 ,3- propanediol monoisopropyl ether, 1 ,3-propanediol mono-n-butyl ether, 1 ,3-propanediol mono-sec-butyl ether, 1 ,3-propanediol mono-isobutyl ether, 1 ,3-propanediol mono-tert- butyl ether, 1 ,3-propanediol monopentyl ether, 1 ,3-propanediol monohexyl ether, 1 ,3- propanediol monoheptyl ether, 1 ,3-propanediol monooctyl ether and the like.
Polyethylene glycols with up to 10 repeat units are oligomers or polymers of the formula HO-A-[O-A]n-OH, where A is a 1 ,2-ethylene group (-CH2-CH2-), and n is from 2 to 9. Polypropylene glycols with up to 10 repeat units (falling under (c.6) are oligomers or polymers of the formula HO-A-[O-A]n-OH, where A is a 1 ,2-propylene group (-CH(CHs)- CH2- or -CH2-CH(CH3)-, and n is from 2 to 9.
Ci-Cs-Alkylmonoethers of diethylene glycol (falling under (c.7)) are compounds RO- CH2CH2-O-CH2CH2-OH, where R is Ci-Cs-alkyl. Examples are diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol monoisopropyl ether, diethylene glycol mono-n-butyl ether (also termed butyldiglycol), diethylene glycol mono-sec-butyl ether, diethylene glycol monoisobutyl ether, diethylene glycol mono-tert-butyl ether, diethylene glycol monopentyl ether, diethylene glycol monohexyl ether, diethylene glycol monoheptyl ether, diethylene glycol monooctyl ether and structural isomers thereof.
Ci-Cs-Alkylmonoethers of dipropylene glycol (falling under (c.7)) are compounds RO- CH(Ra)CH(Rb)-O- CH(Rc)CH(Rd)-OH, where R is Ci-C8-alkyl, one of Ra and Rb is H and the other is methyl, and one of Rc and Rd is H and the other is methyl. Examples are dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol monoisopropyl ether, dipropylene glycol mono-n-butyl ether, dipropylene glycol mono-sec-butyl ether, dipropylene glycol monoisobutyl ether, dipropylene glycol mono-tert-butyl ether, dipropylene glycol monopentyl ether, dipropylene glycol monohexyl ether, dipropylene glycol monoheptyl ether, dipropylene glycol monooctyl ether and structural isomers thereof.
Examples for lactones of formula (C-8) are y-valerolacton (R8 = methyl; also known as y-pentalactone), y-caprolactone (R8 = ethyl; also known as y-hexalactone), y-heptalac- tone (R8 = n-propyl), y-octalactone (R8 = n-butyl) and y-nonalactone (R8 = n-pentyl).
Examples of dioxolanes of the formula (C-9) are propylenecarbonate (4-methyl-1 ,3-di- oxolan-2-one; R9 and R10 form together an oxo group =0, R11 = methyl), 4-ethyl-1 ,3-di- oxolan-2-one (R9 and R10 form together an oxo group =0, R11 = ethyl), isopropy- lidenglycerol (R9, R10 = methyl, R11 = hydroxymethyl) and the like.
Examples of mono- di- or triesters of glycerol with Ci-C4-carboxylic acids (c.10) are glycerol monoacetate, glycerol diacetate and glycerol triacetate.
In a preferred embodiment of solvents (C-1), R6 is Ci-Cs-hydroxyalkyl, more preferably Ci-C4-hydroxyalkyl, even more preferably Ci-C2-hydroxyalkyl, specifically 1 -hydroxy- ethyl. In another preferred embodiment of solvents (C-1), R6 is Ci-C4-alkyl or Ci-C4-hy- droxyalkyl, more preferably Ci-C2-alkyl or Ci-C2-hydroxyalkyl, specifically methyl or 2- hydroxyethyl. R4 is preferably hydrogen or Ci-C4-alkyl, more preferably hydrogen or Ci-C2-alkyl, even more preferably Ci-C2-alkyl (i.e. methyl or ethyl), specifically methyl.
R5 is preferably Ci-C4-alkyl, more preferably Ci-C2-alkyl (i.e. methyl or ethyl), specifically methyl.
Specifically, solvent (c.1) of formula (C-1) is N,N-dimethyllactamide.
In a preferred embodiment of solvents (C-2), R6 is Ci-Cs-hydroxyalkyl, more preferably Ci-C4-hydroxyalkyl, even more preferably Ci-C2-hydroxyalkyl, specifically 1 -hydroxy- ethyl. In another preferred embodiment of solvents (C-2), R6 is Ci-C4-alkyl or Ci-C4-hy- droxyalkyl, more preferably Ci-C2-alkyl or Ci-C2-hydroxyalkyl, specifically methyl or 2- hydroxyethyl.
R7 is preferably C4-Cio-alkyl, more preferably Ce-C -alkyl, in particular Cs-alkyl, specifically 2-ethylhexyl.
Specifically, solvent (c.2) of formula (C-2) is 2-ethylhexyllactate.
The solvent (c.3) is preferably selected from C3-C4-alkanols, specifically from n-propa- nol and n-butanol.
Solvent (c.4) is preferably selected from C4-Ce-alkanediols, in particular from Cs-al- kanediols, specifically from 1 ,2-pentanediol and neopentylglycol.
Solvent (c.5) is preferably selected from Ci-Ce-alkylmonoethers of C2-C3-alkanediols, more preferably C2-C5-alkylmonoethers of C2-C3-alkanediols, in particular C3-C4-alkyl- monoethers of C2-C3-alkanediols, specifically from 1-butoxy-propan-2-ol, (propyleneglycol n-butyl ether) 1-butoxy-ethan-2-ol (butyl glycol; ethyleneglycol n-butyl ether) or 1- propoxy-propan-2-ol (propyleneglycol n-propyl ether).
Solvent (c.6) is preferably selected from diethylene glycol, dipropylene glycol, a polyethylene glycol (PEG) with a number-average molecular weight of up to 200 or a polypropylene glycol (PPG) with a number-average molecular weight Mn of up to 200, more preferably from dipropylene glycol or a polyethylene glycol with a number-average molecular weight of up to 200, and is specifically dipropylene glycol. The number-average molecular weight is as determined by gel permeation chromatography using PEG standards. Solvent (c.7) is preferably selected from Ci-Ce-alkylmonoethers of diethylene glycol or dipropylene glycol, specifically from diethyleneglycolmono-n-butyl ether, diethylenegly- colmono-n-hexyl ether (hexyldiglycol) or dipropyleneglycolmonomethyl ether.
In solvents (c.8) of formula (C-8), R8 is preferably linear Ci-C4-alkyl, specifically methyl.
Solvent (c.9) is preferably selected from propylene carbonate (4-methyl-1 ,3-dioxolan-2- one; R9 and R10 form together an oxo group; R11 is methyl) or isopropylidenglycerol (2,2-dimethyl-4-(hydroxymethyl)-1 ,3-dioxolane; R9 and R10 are methyl; R11 is hydroxymethyl).
Solvent (c.10) is preferably selected from glycerol monoacetate, glycerol diacetate and glycerol triacetate and is specifically glycerol triacetate (triacetine).
The organic solvent (c) is preferably selected from the group consisting of
(c.1) the carboxamide of the formula (C-1), where R4 and R5 are methyl and R6 is 1- hydroxyethyl (i.e. N,N-dimethyllactamide);
(c.5) Cs-Cs-alkylmonoethers of C2-C3-alkanediols, in particular 1-butoxy-propan-2-ol;
(c.7) Ci-Ce-alkylmonoethers of diethylene glycol or dipropylene glycol, in particular di- ethyleneglycolmono-n-butyl ether;
(c.8) the lactone of formula (C-8), where R8 is methyl (i.e. y-valerolactone); and mixtures thereof.
In particular, the organic solvent selected from the group consisting of N,N-dimethyllac- tamide, 1-butoxy-propan-2-ol, diethyleneglycolmono-n-butyl ether (also termed butyldiglycol), y-valerolactone and mixtures thereof.
The presence of solvent (c) is particularly beneficial if the antimicrobial agent is 2-phe- noxyethanol. The solvents can however of course also be used when other antimicrobials are used.
The presence of solvent (c) does not preclude the presence of other organic solvents, such as those listed above.
The antimicrobial agent and the organic solvent of component (c) are preferably present in an overall weight ratio of from 10:1 to 1 :10, more preferably from 5:1 to 1 :5, even more preferably from 3:1 to 1 :3, in particular from 2:1 to 1 :2, specifically from 2:1 to 1 :1.
In another preferred embodiment, the composition comprises water. In another preferred embodiment, the composition comprises both water and an organic solvent.
The optimum relative and absolute amounts of components (a) and (b), the presence, nature and amounts of the optionally present solvents and water depend on the nature of the composition.
The composition of the invention can be a concentrate comprising the antimicrobial (a), the alkoxylated amine (I) and optionally a carrier, such as a diluent, e.g. an organic solvent and/or water; or can be an intermediate composition, i.e. a composition which is not yet the ready-to-use composition for the end user, but already comprises a part of the other components (i.e. components different from of the antimicrobial (a), the alkoxylated amine (I) and the optional carrier) of the final ready-to-use composition; or can be a ready-to-use-composition, i.e. a composition which is used as such and does not need any further dilution or addition of further substances.
Antimicrobials find use in a vast field of application. In principle, any water-containing system or material devoid of intrinsic protection (intrinsic protection can for example be present in systems which contain a sufficiently high amount of alcohol and/or surfactant to hinder microbial infestation, etc.) is prone to microbial attack/infestation.
Examples for such systems, materials or products needing antimicrobial protection and/or exerting themselves an antimicrobial action are homecare compositions (such as laundry compositions, e.g. detergents or fabric softeners; dishwashing compositions; cleaning compositions etc.), compositions for cleaning or disinfecting on an industrial scale (in contrast to home care carried out on a distinctly smaller scale), personal care compositions (including cosmetics), process water, cooling water (e.g. in industrial plants, cooling towers), water in fish or shrimp ponds, water in drinking troughs, metal working fluids; water based raw materials, polymer solutions, polymer dispersions, polymer emulsions, inorganic slurries, organic slurries, surfactant compositions; compositions for treating animal hide; compositions for treating leather; compositions for treating textiles during the manufacturing process thereof; compositions for treating lumber; compositions for treating paper or the precursor material during papermaking processes; crop protection compositions; pharmaceutical compositions; paints, glues, adhesives, sealants, dyes, pigments and dispersions thereof, inks, wet wipes (for personal care, for homecare etc.) and the like.
The composition of the invention is thus preferably selected from the group consisting of antimicrobial concentrates, homecare compositions, compositions for cleaning or disinfecting on an industrial scale, personal care compositions, process water, cooling water, water in fish or shrimp ponds, water in drinking troughs, metal working fluids; water based raw materials, polymer solutions, polymer dispersions, polymer emulsions, inorganic slurries, organic slurries, surfactant compositions; compositions for treating animal hide; compositions for treating leather; compositions for treating textiles during the manufacturing process thereof; compositions for treating lumber; compositions for treating paper or the precursor material during papermaking processes; crop protection compositions; pharmaceutical compositions; paints, glues, adhesives, sealants, dyes, pigments and dispersions thereof, inks, and wet wipes.
Homecare compositions and compositions for cleaning or disinfecting on an industrial scale (also called industrial and institutional cleaning or l&l cleaning) overlap largely, only that l&l compositions are adapted to the use on a larger scale and are thus often more aggressive (e.g. by being more concentrated and/or by having a distinctly higher or lower pH than the respective homecare composition) and/or are less “pleasant”, e.g. in the sense of odor or aspect or touch. Moreover, they are suitable for clean-in-place (CIP), which is a method of automated cleaning the interior surfaces of pipes, vessels, equipments, filters and associated fittings and the like without major disassembly.
Examples for homecare and l&l compositions are dishwashing compositions (in liquid or gel form), laundry compositions (in liquid or gel form; for example laundry detergents, fabric softeners, rinsing compositions, bleacher compositions, stain remover compositions and the like), surface cleaning compositions (also termed hard surface cleaners; for example glass, floor, counter, bath(room), toilet bowl, sink, kitchen, appliance and furniture cleaning compositions; all-purpose cleaners; sanitary cleaners), non-cosmetic deodorants (e.g. air and/or surface deodorants), disinfectants (for example spray air disinfectants, and spray, liquid and paste/gel surface disinfectants), surface protecting and/or polishing compositions, rug shampoos, descaling agents, and compositions for wet wipes (e.g. for cleaning the floor, furniture, bath room surfaces etc.).
Personal care compositions are used for cleaning, washing, disinfecting, nurturing, grooming, protecting or embellishing the human body (and thus also include cosmetics). Examples are creams, lotions, ointments, other o/w or w/o emulsions, liquid or gellike soaps, shampoos, make-up and other decorative cosmetics, and compositions for wet wipes (e.g. for cleaning the nappy area). More specific examples are skin-washing and cleansing preparations in the form of soaps, syndets, washing gels, soapless detergents or washing pastes, bath preparations, e.g. foam baths, milks, oils, shower preparations; skin-care preparations, e.g. skin emulsions, multi-emulsions, powders, sprays or skin oils; cosmetic preparations, e.g. facial make-up in the form of day creams or powder creams, face powder (loose or pressed), rouge or cream make-up, eye-care preparations, e.g. eyeshadow preparations, mascara, eyeliner, eye creams or eye-fix creams; lip-care preparations, e.g. lipsticks, lip gloss, lip contour pencils, nail- care preparations, such as nail varnish, nail varnish removers, nail hardeners or cuticle removers; foot-care preparations, e.g. foot baths, foot powders, foot creams or foot balsams, special deodorants and antiperspirants or callus-removing preparations; light- protective preparations, such as sun milks, lotions, creams or oils, sunblocks or tropicals, pre-tanning preparations or after-sun preparations; skin-tanning preparations, e.g. self-tanning creams; depigmenting preparations, e.g. preparations for bleaching the skin or skin-lightening preparations; insect-repellents, e.g. insect-repellent oils, lotions, sprays or sticks; deodorants, such as deodorant sprays, deodorant aerosols, pump-action sprays, deodorant gels, sticks or roll-ons, also water-free deodorant aerosols or sticks; antiperspirants, e.g. antiperspirant sticks, creams or roll-ons; preparations for cleansing and caring for blemished skin, e.g. synthetic detergents (solid or liquid), peeling or scrub preparations or peeling masks; hair-removal preparations in chemical form (depilation), e.g. liquid hair-removing preparations, cream- or paste-form hair-removing preparations, hair-removing preparations in gel form or aerosol foams; shaving preparations, e.g. shaving soap, foaming shaving creams, non-foaming shaving creams, foams and gels, pre-shave preparations for dry shaving, aftershaves or aftershave lotions; fragrance preparations, e.g. fragrances (eau de Cologne, eau de toilette, eau de parfum, parfum de toilette, perfume), perfume oils or perfume creams; cosmetic hairtreatment preparations, e.g. hair-washing preparations in the form of shampoos and conditioners, hair-care preparations, e.g. pre-treatment preparations, hair tonics, styling creams, styling gels, pomades, hair rinses, treatment packs, intensive hair treatments, hair-structuring preparations, e.g. hair-waving preparations for permanent waves (hot wave, mild wave, cold wave), hair-straightening preparations, liquid hairsetting preparations, hair foams, hairsprays, bleaching preparations, e.g. hydrogen peroxide solutions, lightening shampoos, bleaching creams, bleaching powders, bleaching pastes or oils, temporary, semi-permanent or permanent hair colorants, preparations containing selfoxidising dyes, or natural hair colorants, such as henna or camomile; antidandruff preparations in the form of shampoos, conditioners, hair tonics, styling creams or gels or treatments packs; oral care preparations such as (tooth) pastes, gels, mouth washes and sprays; disinfectants for mouth or skin.
Process water is for example process water used in food, feed, pharmaceutical or cosmetic industry (cooling and process water), or process water used in paper production, wood treatment, cooling water towers, air washers, air conditioners, printing fluids or oil production.
Crop protection compositions, which are often also termed plant protection compositions, are compositions which are effective against various harmful microorganisms, harmful invertebrate pests or undesired plants relevant for agriculture, e.g. harmful fungi, harmful invertebrate pests, such as harmful insects, arachnids, nematodes or molluscs, and weeds, which cause damage to agricultural plants, plant propagation materials, such as seeds, or harvested crops. Examples for crop protection compositions are fungicidal, insecticidal, acaricidal, nematicidal, moluscicidal or herbicidal compositions. The term encompasses also plant growth regulating compositions. Plant growth regulators are plant protection products used to influence plant growth and are used, for example, for increasing the stability of cereals by shortening the stalk length, thus reducing or preventing lodging, for improving the rooting of cuttings, reducing plant height in horticulture, preventing the germination of potatoes and the like. The term encompasses moreover compositions used in material protection for combating various harmful microorganisms and invertebrate pests, such as compositions for the treatment of lumber or the surroundings of lumber material against termites or compositions for the treatment of mosquito nets against harmful insects, such as Anopheles mosquitoes, and the like.
Antimicrobial concentrate
In a preferred embodiment, the composition is an antimicrobial concentrate. Preferably, the antimicrobial concentrate comprises:
(a) 0.01 to 99.9% by weight, relative to the total weight of the composition, of an antimicrobial agent as defined above;
(b) 0.1 to 99.99% by weight, relative to the total weight of the composition, of an alkoxylated amine (I) or a mixture of different alkoxylated amines (I) as defined above;
(c) 0 to 99.8% by weight, relative to the total weight of the composition, of one or more organic solvents, preferably as defined above, the solvent more preferably comprising a solvent selected from solvents (c.1) to (c.10);
(d) 0 to 20% by weight, relative to the total weight of the composition, of at least one further additive; and
(e) 0 to 99.8% by weight, relative to the total weight of the composition, of water.
The term “concentrate” is used in this context also for compositions in which components (a) and (b) do not constitute the major part (and thus do not form a concentrate in the proper sense). Nevertheless, it signals that components different from (a), (b) and the optional diluents (d) and (e), if at all present, do not predominate. Moreover, the term signals that the composition can consist of components (a) and (b) only. Preferably however, at least a diluent (d) or (e) or mixtures thereof are present to assure an easier handling.
In case that the antimicrobial agent is 2-phenoxyethanol, phenoxyisopropanol, formic acid or a salt thereof, benzoic acid or a salt thereof, sorbic acid or a salt thereof, lactic acid or a salt thereof or N-(3-aminopropyl)-N-dodecylpropane-1,3-diamine (Diamine), this is preferably contained in an amount of 0.1 to 99.9% by weight, relative to the total weight of the composition.
Suitable and preferred components (a) and (b) and suitable and preferred weight ratios thereof are those mentioned above.
Further additives (c) are for example agents which stabilize the concentrate, such as emulsifiers and/or hydrotropic agents, activity enhancers different from component (b) and pH modifiers.
Any emulsifiers usual in such systems can be used. A few non-limiting examples are carboxylic acids and their salts, alkyl phosphates or phosphoric acid esters, ethoxylated and/or propoxylated fatty acids, ethoxylated and/or propoxylated polyethyleneglycols, ethoxylated and/or propoxylated fatty alcohols, fatty acid monoglycerides, fatty acid saccharose esters, fatty acid sorbitol esters, fatty acid sorbitan esters, fatty acid glucose esters, ethoxylated and/or propoxylated derivatives of the listed fatty acid polyol esters, fatty sulfates and sulfonates, ethoxylated amines, ethoxylated amides, polysiloxane/polyalkyl/polyether copolymers and derivatives, poly(oxyethylene)- poly(oxypropylene)-blockpolymers, zwitterionic surfactants that carry at least one quaternary ammonium group and at least one carboxylate and/or sulfonate group in the molecule.
Hydrotropic agents are compounds which solubilize hydrophobic compounds in aqueous solution by means other than micellar solubilization. Similar to surfactants, hydrotropes often (but not necessarily) consist of a hydrophilic part and a hydrophobic part, but in contrast to surfactants the hydrophobic part is generally too small to cause spontaneous self-aggregation. Examples are aromatic sulfonic acid salts, such as the alkali metal, earth alkaline metal or ammonium salts of p-toluenesulfonic acid (e.g. sodium, potassium, calcium or ammonium p-tosylate), of xylene sulfonic acids (e.g. the sodium, potassium, calcium or ammonium salts of o-, m- or p-xylene sulfonates) or of cumene sulfonic acids, generally of p-cumene sulfonic acid (e.g. the sodium, potassium, calcium or ammonium salts of p-cumenesulfonate); adenosine triphosphate (ATP); and urea.
Examples for activity enhancers different from component (b) are ethylhexylglycerine (3-(2-ethylhexyloxy)propan-1 ,2-diol) and polyethyleneimines (PEI). Further details are given below in context with homecare compositions. pH modifiers are acids, bases and also buffers. The acids can be inorganic or organic. Suitable inorganic acids are for example sulfuric acid, hydrochloric acid and phosphoric acid, where sulfuric acid is generally preferred. Suitable organic acids are for example aliphatic, saturated non-substituted Ci-Ce- mono-, di- and tri-carboxylic acids such as formic acid, acetic acid, propanoic acid, oxalic acid, succinic acid and glutaric acid; aliphatic, saturated Ci-Ce-mono-, di- and tricarboxylic acids carrying one or more OH groups, such as lactic acid, tartric acid and citric acid; aliphatic, unsaturated Ci-Ce-mono-, di- and tri-carboxylic acids such as sorbic acid; aromatic carboxylic acids, such as benzoic acid, salicylic acid and mandelic acid, and sulfonic acids, such as methanesulfonic acid or toluenesulfonic acid.
Suitable bases are in particular inorganic bases, such as the carbonates mentioned below in context with the sequestrant, e.g. sodium or potassium carbonate; further alkali metal and earth alkaline meal hydroxides, such as NaOH or KOH.
Suitable buffering agents are the typical systems, such as hydrogenphosphate/dihy- drogenphosphate buffer, carbonate/hydrogencarbonate buffer, acetic acid/acetate buffer or Tris buffer. Moreover, most of the above acids which are weak and the anion of which is not a strong salt also have buffering capacity.
Suitable organic solvents (c) are those mentioned above. Preferred organic solvents are thus Ci-Cs-alkanols, C2-C8-alkanediols, Ci-Cs-alkylmonoethers of C2-Cs-alkanedi- ols, polyetherpolyols, Ci-Cs-alkylmonoethers of polyetherpolyols, 5-, 6- or 7-membered lactones which may be substituted by one or more C1-C12-alkyl groups; 5-, 6- or 7- membered cyclic carbonates which may be substituted by one or more Ci-Ci2-alkyl groups; aliphatic esters, carboxamides, dioxolanes as defined above, aliphatic or alicyclic amine-N-oxides and mixtures of the afore-mentioned solvents. Examples for these solvent groups are mentioned above. More preferably, the solvent (c) is selected from Ci-Cs-alkanols, C2-Cs-alkanediols, Ci-Cs-alkylmonoethers of C2-Cs-alkanediols, 5-, 6- or 7-membered lactones which may carry one or more C1-C12-alkyl groups and mixtures thereof. Among the Ci-Cs-alkanols, preference is given to Ci-C4-alkanols, in particular to C2-C3-alkanols (i.e. to ethanol, n-propanol, isopropanol or a mixture thereof), and specifically to n-propanol. Among the C2-Cs-alkanediols, preference is given to C2- C4-alkanediols, in particular to C2-C3-alkanediols, such as ethylene glycol, 1 ,2-propane- diol and 1 ,3-propanediol, and specifically to 1 ,2-propanediol (propylene glycol). Among the Ci-Cs-alkylmonoethers of C2-Cs-alkanediols preference is given to Ci-Ce-alkylmo- noethers of C2-C4-alkanediols and in particular to Ci-C4-alkylmonoethers of a C2-C3-al- kanediol, such as the Ci-C4-alkylmonoethers of ethylene glycol or propylene glycol, specific examples being ethylene glycol mono-n-propyl ether, ethylene glycol mono-n- butyl ether (also termed butylglyol), propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether and mixtures thereof. Among the 5-, 6- or 7-membered lac- tones which may carry one or more Ci-Ci2-alkyl groups, preference is given to /-butyrolactone, y-valerolactone, y-octalactone, y-nonalactone, s-caprolactone and mixtures thereof.
In particular, the solvent is a C2-Cs-alkanediol, more preferably a C2-C4-alkanediol, in particular a C2-C3-alkanediol, such as ethylene glycol, 1 ,2-propanediol and 1 ,3-pro- panediol, and specifically 1 ,2-propanediol (propylene glycol).
In another particular embodiment the solvent is a Ci-Cs-alkanol, more preferably a Ci- C4-alkanol, and in particular a C2-C3-alkanol (i.e. ethanol, n-propanol, isopropanol or a mixture thereof), specifically n-propanol.
In another particular embodiment, the solvent comprises at least one of the solvents (c.1) to (c.10) as defined above, and, if desired, also another organic solvent. More particularly, the solvent comprises N,N-dimethyllactamide, 1-butoxy-propan-2-ol, diethy- leneglycolmono-n-butyl ether, y-valerolactone or a mixture of two or more of these solvents and, if desired, also a C2-C3-alkanol (i.e. ethanol, n-propanol, isopropanol or a mixture thereof) and/or a C2-C3-alkanediol, such as ethylene glycol, 1 ,2-propanediol and 1 ,3-propanediol, and specifically 1 ,2-propanediol (propylene glycol).
In a particular embodiment, the antimicrobial concentrate comprises:
(a) 1 to 99.9% by weight, relative to the total weight of the composition, of an antimicrobial agent as defined above;
(b) 0,1 to 99% by weight, relative to the total weight of the composition, of an alkox- ylated amine (I) or a mixture of different alkoxylated amines (I) as defined above;
(c) 0 to 98.9% by weight, relative to the total weight of the composition, of one or more organic solvents, preferably as defined above, the solvent more preferably comprising a solvent selected from solvents (c.1) to (c.10); and
(d) 0 to 15% by weight, relative to the total weight of the composition, of at least one further additive;
(e) 0 to 98.9% by weight, relative to the total weight of the composition, of water;
In another particular embodiment, the antimicrobial concentrate comprises:
(a) 5 to 90% by weight, relative to the total weight of the composition, of an antimicrobial agent as defined above;
(b) 10 to 95% by weight, relative to the total weight of the composition, of an alkoxylated amine (I) or a mixture of different alkoxylated amines (I) as defined above;
(c) 0 to 85% by weight, relative to the total weight of the composition, of one or more organic solvents, preferably as defined above, the solvent more preferably comprising a solvent selected from solvents (c.1) to (c.10); and (d) 0 to 10% by weight, relative to the total weight of the composition, of at least one further additive;
(e) 0 to 85% by weight, relative to the total weight of the composition, of water.
Homecare and l&l compositions
Examples for homecare and l&l compositions are listed above. Among these, preference is given to dishwashing compositions, laundry compositions, surface cleaning compositions, and rug shampoos.
Thus, in another preferred embodiment, the composition of the invention is selected from the group consisting of dishwashing compositions, laundry compositions, surface cleaning compositions, and rug shampoos. Such compositions preferably comprise:
(a) 0.001 to 7% by weight, relative to the total weight of the composition, of an antimicrobial agent as defined above;
(b) 0.001 to 7% by weight, relative to the total weight of the composition, of an alkox- ylated amine (I) or a mixture of different alkoxylated amines (I) as defined above;
(c) 0 to 15% by weight, relative to the total weight of the composition, of at least one organic solvent, preferably as defined above, the solvent more preferably comprising a solvent selected from solvents (c.1) to (c.10);
(d) 0.1 to 40% by weight, relative to the total weight of the composition, of one or more surfactants;
(e) 0 to 6 by weight, relative to the total weight of the composition, of at least one enzyme;
(f) 0 to 20% by weight, relative to the total weight of the composition, of at least one sequestrant;
(g) 0 to 8% by weight, relative to the total weight of the composition, of at least one defoamer and/or foam stabilizer;
(h) 0 to 50% by weight, relative to the total weight of the composition, of a further additive; and
(i) 10 to 99.898% by weight, relative to the total weight of the composition, of water; where components (a) to (i) add to 100% by weight.
Suitable and preferred components (a) and (b) and suitable and preferred weight ratios thereof are those mentioned above.
Suitable organic solvents (c) are those mentioned above. Preferred organic solvents are thus Ci-Cs-alkanols, C2-Cs-alkanediols, Ci-Cs-alkylmonoethers of C2-Cs-alkanedi- ols, polyetherpolyols, Ci-Cs-alkylmonoethers of polyetherpolyols, 5-, 6- or 7-membered lactones which may be substituted by one or more C1-C12-alkyl groups; 5-, 6- or 7- membered cyclic carbonates which may be substituted by one or more Ci-Ci2-alkyl groups; aliphatic esters, carboxamides, aliphatic or alicyclic amine-N-oxides and mixtures of the afore-mentioned solvents. Examples for these solvent groups are mentioned above. More preferably, the solvent (c) is selected from Ci-Cs-alkanols, C2-C8- alkanediols, Ci-Cs-alkylmonoethers of C2-Cs-alkanediols, 5-, 6- or 7-membered lactones which may carry one or more Ci -Ci 2-alkyl groups and mixtures thereof. Among the Ci-Cs-alkanols, preference is given to Ci-C4-alkanols, in particular to C2-C3-alkanols (i.e. to ethanol, n-propanol, isopropanol or a mixture thereof), and specifically to n-pro- panol. Among the C2-Cs-alkanediols, preference is given to C2-C4-alkanediols, in particular to C2-C3-alkanediols, such as ethylene glycol, 1 ,2-propanediol and 1 ,3-propane- diol, and specifically to 1 ,2-propanediol (propylene glycol). Among the Ci-Cs-alkylmo- noethers of C2-Cs-alkanediols preference is given to Ci-Ce-alkylmonoethers of C2-C4- alkanediols and in particular to Ci-C4-alkylmonoethers of a C2-C3-alkanediol, such as the Ci-C4-alkylmonoethers of ethylene glycol or propylene glycol, specific examples being ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether (also termed butylglyol), propylene glycol mono-n-propyl ether, propylene glycol mono-n-bu- tyl ether and mixtures thereof. Among the 5-, 6- or 7-membered lactones which may carry one or more Ci-Ci2-alkyl groups, preference is given to y-butyrolactone, y- valerolactone, y-octalactone, y-nonalactone, s-caprolactone and mixtures thereof.
In particular, the solvent is a C2-Cs-alkanediol, more preferably a C2-C4-alkanediol, in particular a C2-C3-alkanediol, such as ethylene glycol, 1 ,2-propanediol and 1 ,3-pro- panediol, and specifically 1 ,2-propanediol (propylene glycol).
In another particular embodiment the solvent is a Ci-Cs-alkanol, more preferably a C1- C4-alkanol, and in particular a C2-C3-alkanol (i.e. ethanol, n-propanol, isopropanol or a mixture thereof), specifically n-propanol.
In another particular embodiment, the solvent comprises at least one of the solvents (c.1) to (c.10) as defined above, and, if desired, also onother organic solvent. More particularly, the solvent comprises N,N-dimethyllactamide, 1-butoxy-propan-2-ol, diethy- leneglycolmono-n-butyl ether, y-valerolactone or a mixture of these solvents and, if desired, also a C2-C3-alkanol (i.e. ethanol, n-propanol, isopropanol or a mixture thereof) and/or a C2-C3-alkanediol, such as ethylene glycol, 1 ,2-propanediol and 1 ,3-propane- diol, and specifically 1 ,2-propanediol (propylene glycol).
Surfactants (or surface-active compounds) of component (d) can be anionic, cationic, non-ionic or amphoteric (zwitterionic).
Anionic surfactants are, for example, of the sulfate, sulfonate or carboxylate type or mixed forms thereof. Examples are alkylbenzenesulfonates, alkyl sulfates, alkyl ether sulfates, olefin sulfonates, fatty acid salts, alkyl and alkenyl ether carboxylates or to an alpha-sulfonic fatty acid salt or an ester thereof.
More specific examples are alkylbenzenesulfonates having from 10 to 20 carbon atoms in the alkyl radical (e.g. sodium dodecylbenzene sulfonate), alkyl sulfates having from 8 to 18 carbon atoms in the alkyl radical (e.g. sodium lauryl sulfate), alkyl ether sulfates having from 8 to 18 carbon atoms in the alkyl radical (e.g. sodium laureth sulfate; SLES), and fatty acid salts derived from oils or fats, e.g. from palm oil or tallow and having from 8 to 18 carbon atoms in the alkyl moiety (thus containing, inter alia, sodium oleate, linolate, palmitate, myristate, stearate etc.). The counter-cation is preferably an alkali metal cation, especially sodium or potassium, specifically sodium. Preferred carboxylates are alkali metal sarcosinates of formula R-CON(R’)CH2COO'M+ wherein R’ is Cg-Ci7-alkyl or Cg-Ci7-alkenyl, R’ is Ci-C4-alkyl and M+ is an alkali metal cation, especially Na+.
Cationic surfactants are, for example, ammonium salts such as Cs-Cie-dialkyldime- thylammonium halides, dialkoxydimethylammonium halides or imidazolinium salts with a long-chain alkyl radical.
Non-ionic surfactants are, for example, a primary or secondary alcohol ethoxylate, especially a C8-C20 aliphatic alcohol ethoxylated with an average of from 1 to 20 mol of ethylene oxide per alcohol group. Preference is given to primary and secondary C10-C15 aliphatic alcohols ethoxylated with an average of from 1 to 10 mol of ethylene oxide per alcohol group. Non-ethoxylated non-ionic surfactants, for example alkylpolyglycosides, glycerol monoethers and polyhydroxyamides (glucamide), may likewise be used.
Amphoteric surfactants are, for example, derivatives of secondary or tertiary amines, for example Ce-C -alkyl betaines (e.g. cocoamidopropyl betaine; disodium cocoam- phodiacetate (DSCADA)) or Ce-Cis-alkyl sulfobetaines, or amine oxides such as alkyldimethylamine oxides.
Examples for enzymes of component (e) are those typically used in laundry, dishwashing or cleaning compositions.
Enzyme herein means catalytically active proteins which are characterized by an amino acid sequence. Variants of an enzyme may be described by a certain sequence identity of an amino acid sequence of the variant when compared to a respective starting sequence. For calculation of sequence identities, in a first step a pairwise global sequence alignment has to be produced, meaning that two sequences have to be aligned over their complete length typically by using the algorithm of Needleman and Wunsch (J. Mol. Biol. (1979) 48, p. 443-453). Preferably, the program “NEEDLE” (The European Molecular Biology Open Software Suite (EMBOSS)) is used for the purposes of the current invention, with using the programs default parameter (gap open=10.0, gap extend=0.5 and matrix=EBLOSUM62). In a second step, % identity is calculated: Coidentity = (identical residues I length of the alignment region which is showing the respective sequence of this invention over its complete length) *100.
The enzymes are preferably selected from hydrolases, such as proteases, esterases, glucosidases, lipases, DNAses, amylases, cellulases, mannanases, other glycosylhydrolases and mixtures of the aforementioned enzymes. All these hydrolases contribute to dissolution and removal of soil from protein-, grease- or starch-containing stains/resi- dues. For bleaching, it is also possible to use oxidoreductases. Particularly suitable are active enzymatic ingredients obtained from bacterial strains or fungi, such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus and Humicola insolens.
Preferred hydrolases are selected from the group of enzymes acting on ester bonds (esterases) (E.C. 3.1), glycosylases (E.C. 3.2), and peptidases (E.C. 3.4). Enzymes acting on ester bonds (E.C. 3.1), are for example lipases and DNAses. Glycosylases (E.C. 3.2) are for example amylases, cellulases, and mannanases. Peptidases are for example proteases.
Suitable hydrolases are, for example, a-glucosidases (EC number 3.2.1.20), proteases (e.g. Ovozyme® (from Novozymes); EC number 3.2.1.20), amylases [e.g. Purastar® (from Genencor), Termamyl® (from Novozymes), Stainzyme® (from Novozymes), Du- ramyl® (from Novozymes)], mannanases [e.g. Purabrite® (from Genencor), Mannastar® (from Genencor), Mannaway® (from Novozymes)] and cellulases [e.g. Carezyme® (from Novozymes), Celluzyme® (from Novozymes), endolase, Puradax® (from Genencor)]. The suitable amylases include especially a-amylases (EC number 3.2.1.1), iso-amylases, pullulanases and pectinases. The cellulases used are preferably cellobiohydrolases, endoglucanases and p-glucosidases, which are also referred to as cellobiases, or mixtures thereof. Since different cellulase types differ by their CMCase and Avicelase activities, it is possible to establish the desired activities by means of controlled mixtures of the cellulases.
Suitable lipases are for example Lipex and Lipolase. Examples of lipolytically active enzymes are the known cutinases.
Peroxidases or oxidases have also been found to be suitable in some cases.
In one aspect, the enzymes comprise at least one protease (EC 3.4). In a preferred embodiment, at least one protease is selected from serine proteases (EC 3.4.21), more preferably from subtilisins (EC 3.4.21.62). At least one subtilisin may have SEQ ID NO:22 as described in EP 1921147 (which may be called BLAP WT herein), or is a variant thereof which is at least 80% identical SEQ ID NO:22 as described in EP 1921147 and has proteolytic activity. In one embodiment, a subtilisin is at least 80% identical to SEQ ID NO:22 as described in EP 1921147 and is characterized by having amino acid glutamic acid (E), or aspartic acid (D), or asparagine (N), or glutamine (Q), or alanine (A), or glycine (G), or serine (S) at position 101 (according to BPN’ numbering), preferably R101 E.
In one embodiment, at least one subtilisin is at least 80% identical to SEQ ID NO:22 as described in EP 1921147 having the mutations (according to BPN’ numbering) S3T + V4I + V205I. In one embodiment, at least one subtilisin is at least 80% identical to SEQ ID NO:22 as described in EP 1921147 having the mutations (according to BPN’ numbering) S3T + V4I + R101 E + V205I. In one embodiment, at least one subtilisin is at least 80% identical to SEQ ID NO:22 as described in EP 1921147 having the mutation (according to BPN’ numbering) S3T + V4I + V199M + V205I + L217D. In one embodiment, at least one subtilisin has an amino acid sequence being at least 80% identical with SEQ ID NO:22 as described in EP 1921147 having the mutations S3T + V4I + S9R + A15T + V68A + D99S + R101S + A103S + 1104V + N218D (according to the BPN’ numbering), at least one subtilisin has an amino acid sequence at least 80% identical to SEQ ID NO:22 as described in EP 1921147 and having the mutation R101 E together with one or more substitutions selected from the group consisting of S156D, L262E, Q137H, S3T, R45E,D,Q, P55N, T58W,Y,L, Q59D,M,N,T, G61 D,R, S87E, G97S, A98D,E,R, S106A.W, N117E, H120V,D,K,N, S125M, P129D, E136Q, S144W, S161T, S163A.G, Y171 L, A172S, N185Q, V199M, Y209W, M222Q, N238H, V244T, N261T.D and L262N,Q,D (as described in WO 2016/096711 and according to the BPN’ numbering).
In one aspect, the enzymes comprise at least one amylase, preferably at least one alpha-amylase (EC 3.2.1.1). Preferably, the enzymes comprise at least one alpha-amylase selected from hybrid amylases. In one embodiment, the enzymes comprise at least one hybrid amylase at least 95% identical to SEQ ID NO: 23 of WO 2014/183920. In one embodiment, the enzymes comprise at least one hybrid amylase 95% identical to SEQ ID NQ:30 of WO 2014/183921.
In one aspect, detergent formulations comprise at least one lipase, preferably at least one triacylglycerol lipase (EC 3.1.1.3).
Preferably, the enzymes comprise at least one Thermomyces lanuginosus triacylglycerol lipase. In one embodiment, said lipase at least 80% identical to amino acids 1-269 of SEQ ID NO:2 of US5869438. In one embodiment, said lipase comprises at least the amino acid substitutions T231 R and N233R. In one embodiment, the enzymes comprise at least one lipase comprising T231 R and N233R and one or more of the following amino acid exchanges when compared to amino acids 1-269 of SEQ ID NO:2 of US5869438: Q4V, V60S, A150G, L227G, P256K. In one embodiment, the enzymes comprise at least one lipase at least 95% identical to the full length polypeptide sequence of amino acids 1-269 of SEQ ID NO:1 of WO 2015/01009, preferably comprising at least the amino acid substitutions N 11 K/A18K/G23K/K24A/V77I/D130A/V154I/V187T/T189Q or N 11 K/A18K/G23K/K24A/L75R/V77I/D130A/V154I /187T/T189Q.
In one aspect, the enzymes comprise at least one cellulase, preferably at least one beta-1 ,4-glucanase (EC 3.2.1.4), also called endoglucanase herein. In one embodiment, the enzymes comprise at least one Humicola insolens DSM 1800 endoglucanase at least 80% identical to the amino acid sequence disclosed in Fig. 14A-E of WO 91/17244, preferably to the sequence according to amino acids 20-434. Preferably said endoglucanase having one or more substitutions at positions selected from 182, 223, and 231 , most preferably selected from P182S, A223V, and A231V. In one embodiment, the enzymes comprise at least one endoglucanase at least 80% identical to a polypeptide according to SEQ ID NO: 2 of WO 95/02675. In one embodiment, the enzymes comprise at least one Bacillus sp. endoglucanase which is at least 80% identical to the amino acid sequence of position 1 to position 773 of SEQ ID NO: 2 of WO 2004/053039. In one embodiment, the enzymes comprise at least one Thielavia terrestris endoglucanase which is at least 80% identical to the amino acid sequence of position 1 to position 299 of SEQ ID NO:4 of WO 2004/053039.
In one aspect, the enzymes comprise at least one mannanase, preferably at least one beta-mannanase (EC 3.2.1.78). In one embodiment, the enzymes comprise at least one beta-mannanase selected from GH5 family mannanase. In one embodiment, the enzymes comprise at least one beta-mannanase at least 90% identical to SEQ ID NO:12 of WO 2018/184767. In one embodiment, the enzymes comprise at least one beta-mannanase at least 90% identical to SEQ ID NO: 16 of WO 2018/184767. In one embodiment, the enzymes comprise at least one beta-mannanase at least 90% identical to SEQ ID NQ:20 of WO 2018/184767. Preferably, the enzymes comprise at least one mannanase 95% identical to a polypeptide sequence of SEQ ID NQ:20 of WO 2018/184767 having at least one substitution selected from A101V, E405G, and Y459F. In one embodiment, the enzymes comprise at least one beta-mannanase originating from Trichoderma organisms, such as those disclosed in WO 93/24622. Preferably, at least one beta-mannanase is 80% identical to SEQ ID NO:1 of WO 2008/009673. More preferably, the beta-mannanase according to SEQ ID NO:1 of WO 2008/009673 comprises at least one substitution selected from S3R, S66P, N113Y, V181H, L207F, A215T and F274L.
In one aspect, detergent formulations comprise at least one DNAse. In one embodiment, the enzymes comprise at least one DNAse at least 80% identical to SEQ ID NO: 1-24 and SEQ ID NO: 27-28 of WO 2019/081724 and WO 2019/081721. Preferably, the enzymes comprise at least one DNAse comprising one or both motifs selected from SEQ ID NO:25 and SEQ ID NO:26 of WO 2019/081724. In one embodiment, the enzymes comprise at least one DNAse comprising one or more motifs selected from SEQ ID NO:73, SEQ ID NO:74 and SEQ ID NO:75 of WO 2017/060493.
In case the composition is a dishwashing composition, this comprises preferably at least one protease and/or amylase. More preferably, it comprises an enzyme mixture. Preference is given, for example, to enzyme mixtures which comprise or consist of the following enzymes: protease and amylase, protease and lipase (or lipolytically active enzymes), protease and cellulase, protease and mannanase, amylase, cellulase and lipase (or lipolytically active enzymes), protease, amylase and lipase (or lipolytically active enzymes), protease, lipase (or lipolytically active enzymes) and cellulase, protease, lipase (or lipolytically active enzymes) and mannanase, protease, amylase, lipase (or lipolytically active enzymes) and mannanase.
Liquid automated dishwashing formulations usually comprise at least one subtilisin protease as disclosed herein in amounts of about 0.10% to 0.25% by weight, more preferably about 0.12% to 0.21 % by weight, all relative to the total weight of the detergent formulation.
Liquid automated dishwashing formulations usually comprise at least one alpha-amylase as disclosed herein in amounts of about 0.002% to 0.015%by weight, more preferably 0.004 to 0.01 % by weight, all relative to the total weight of the detergent formulation.
Liquid manual dishwashing formulations usually comprise at least one subtilisin protease as disclosed herein in amounts of about 0.005% to 0.15% by weight, more preferably about 0.01 % to 0.1 % by weight, all relative to the total weight of the detergent formulation.
Liquid manual dishwashing formulations usually comprise at least one alpha-amylase as disclosed herein in amounts of about 0.001% to 0.015% by weight, more preferably 0.002% to 0.015% by weight, all relative to the total weight of the detergent formulation. Liquid manual dishwashing formulations usually comprise at least one triacylglycerol lipase as disclosed herein in amounts of about 0.001% to 0.005% by weight, more preferably 0.001 % to 0.002% by weight, all relative to the total weight of the detergent formulation.
Liquid manual dishwashing formulations usually comprise at least one endoglucanase as disclosed herein in amounts of about 0.001% to 0.01 % by weight, more preferably 0.002% to 0.009% by weight, all relative to the total weight of the detergent formulation. Liquid manual dishwashing formulations usually comprise at least one beta-man- nanase as disclosed herein in amounts of about 0.0005% to 0.005% by weight, more preferably 0.0005% to 0.002% by weight, all relative to the total weight of the detergent formulation.
In case of surface cleaning compositions, similar preferences apply.
In case the composition is a laundry composition, this comprises preferably at least one of amylases, lipases, proteases and cellulases. More preferably, it comprises an enzyme mixture. A few exemplary mixtures are: protease and amylase, protease and cellulase, cellulase and amylase, amylase, cellulase and lipase (or lipolytically active enzymes), protease, amylase and lipase (or lipolytically active enzymes), protease, lipase (or lipolytically active enzymes) and cellulase, protease, lipase (or lipolytically active enzymes) and mannanase, protease, amylase, lipase (or lipolytically active enzymes) and mannanase.
Liquid laundry formulations usually comprise at least one subtilisin protease as disclosed herein in amounts of about 0.005% to 0.15% by weight, more preferably about 0.01 % to 0.1 % by weight, all relative to the total weight of the detergent formulation. Liquid laundry formulations usually comprise at least one alpha-amylase as disclosed herein in amounts of about 0.001 % to 0.015% by weight, more preferably 0.002% to 0.015% by weight, all relative to the total weight of the detergent formulation.
Liquid laundry formulations usually comprise at least one triacylglycerol lipase as disclosed herein in amounts of about 0.001% to 0.005% by weight, more preferably 0.001% to 0.002% by weight, all relative to the total weight of the detergent formulation. Liquid laundry formulations usually comprise at least one endoglucanase as disclosed herein in amounts of about 0.001 % to 0.01% by weight, more preferably 0.002% to 0.009% by weight, all relative to the total weight of the detergent formulation.
Liquid laundry formulations usually comprise at least one beta-mannanase as disclosed herein in amounts of about 0.0005% to 0.005% by weight, more preferably 0.0005% to 0.002% by weight, all relative to the total weight of the detergent formulation.
The enzymes may be adsorbed onto carriers in order to protect them from premature decomposition.
If the composition comprises one or more enzymes, it may also comprise enzyme stabilizers (for more details see component (h)). Enzymes or enzyme packages suitable for such compositions are commercially available. Examples are the Lavergy® brands from BASF.
Sequestrants (f), also termed builders, structural substances, framework substances, complexing agents, chelators, chelating agents or softeners, bind alkaline earth metals and other water-soluble metal salts without precipitating. They help to break up soil, disperse soil components, help to detach soil and in some cases themselves have a washing effect. Many of the sequenstrants listed below are multi-functional, meaning that the substances have additional functions, such as a dispersing activity or anti-grey- ing properties.
Suitable sequestrants may be either organic or inorganic in nature. Examples are aluminosilicates, carbonates, phosphates and polyphosphates, polycarboxylic acids, polycarboxylates, hydroxycarboxylic acids, phosphonic acids, e.g. hydroxyalkylphosphonic acids, phosphonates, aminopolycarboxylic acids and salts thereof, and polymeric compounds containing carboxylic acid groups and salts thereof.
Suitable inorganic sequestrants are, for example, crystalline or amorphous aluminosilicates with ion-exchanging properties, such as zeolites. Crystalline silicates suitable as sequestrants are, for example, disilicates or sheet silicates, e.g. 5-Na2Si20s or B- Na2Si2C>5 (SKS 6 or SKS 7). Suitable inorganic sequestrant substances based on carbonate are carbonates and hydrogencarbonates. These can be used in the form of their alkali metal, alkaline earth metal or ammonium salts. Customary phosphates used as inorganic sequestrants are alkali metal orthophosphates and/or polyphosphates, for example pentasodium triphosphate.
Suitable organic sequestrants are, for example, C4-C3o-di-, -tri- and -tetracarboxylic acids, for example succinic acid, propanetricarboxylic acid, butanetetracarboxylic acid, cyclopentanetetracarboxylic acid, and alkyl- and alkenylsuccinic acids with C2-C2o-alkyl or -alkenyl radicals. Suitable organic sequestrants are also hydroxycarboxylic acids and polyhydroxycarboxylic acids (sugar acids). These include C4-C20-hydroxycarboxylic acids, for example malic acid, tartaric acid, glutonic acid, mucic acid, lactic acid, glutaric acid, citric acid, tartronic acid, glucoheptonic acid, lactobionic acid, and sucrose- mono-, -di- and -tricarboxylic acid. Among these, preference is given to citric acid and salts thereof. Suitable organic sequestrants are also phosphonic acids, for example hydroxyalkylphosphonic acids or aminophosphonic acids, and the salts thereof. These include, for example, phosphonobutanetricarboxylic acid (2-phosphinobutane-1 ,2,4-tri- carboxylic acid; PBTC), aminotris-methylenephosphonic acid (N[CH2PO(OH)2]s), ami- notris(methylenephosphonate), sodium salt (ATMP; N[CH2PO(ONa)2]s), ethylenedia- minetetra(methylenephosphonic acid) (EDTMPA), hexamethylenediamine(tetramethy- lenephosphonic acid), hexamethylenediamine(tetramethylenephosphonate), potassium salt (CioH(28-x)N2KxOi2P4 (X=6)) , bis(hexamethylene)triamine(pentamethylene- phosphonic acid) ((HO2)POCH2N[(CH2)2N[CH2PO(OH)2]2]2), diethylenetriamine-penta- (methylenephosphonic acid) (DTPMP; (HO)2POCH2N[CH2CH2N[CH2PO(OH)2]2]2), di- ethylenetriaminepenta(methylenephosphonate), sodium salt (CgH^s-xjNsNaxOisPs (x=7)); tetramethylene-triamine-pentaphosphonic acid, hydroxyethylamine diphos- phonic acid, 2-hydroxyethyliminobis(methylenephosphonic acid) (HOCH2CH2N[CH2PO(OH)2]2), morpholinomethanediphosphonic acid, 1-hydroxy-Ci- to Cio-alkyl-1 ,1-diphosphonic acids such as 1-hydroxyethane-1 ,1-diphosphonic acid (HEDP; CH2C(OH)[PO(OH)2]2). Suitable organic sequestrants are moreover polyas- paratic acids. Polyaspartic acid include salts of polyaspartic acids. Salt forming cations may be monovalent or multivalent, examples being sodium, potassium, magnesium, calcium, ammonium, and the ammonium salt of mono-, di- and triethanolamine. Such polymers may be co-polymers, in particular of (a) L- or D-aspartic acid (preferably L- aspartic acid), (b) a carboxylic acid and (c) a diamone or an amino alcohol. Such copolymers generally comprise 70-95 mol% of (a), 5-30 mol% of (b) and 2-20 mol% of (c). The molar ratio of the carboxyl-containing compound (b) to the diamine or amino alcohol (c) is preferably between 5:1 and 1 :1.5 or between 3:1 and 1 :1.2, and more preferably between 3:1 and 1 :1 or 2:1 and 1 :1. Suitable organic sequestrants are additionally aminopolycarboxylic acids, such as nitrilotriacetic acid (NTA), nitrilomonoacetic dipropionic acid, nitrilotripropionic acid, p-alaninediacetic acid (p-ADA), ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid, 1 ,3-propylenediaminetet- raacetic acid, 1 ,2-propylenediaminetetraacetic acid, N-(alkyl)ethylenediaminetriacetic acid, N-(hydroxyalkyl)ethylenediaminetriacetic acid, ethylenediaminetriacetic acid, cy- clohexylene-1 ,2-diaminetetraacetic acid, iminodisuccinic acid, ethylenediaminedisuccinic acid, serinediacetic acid, isoserinediacetic acid, L-asparaginediacetic acid, L-glu- taminediacetic acid, methylglycinediacetic acid (MGDA), and the salts of the aforementioned aminopolycarboxylic acids. Suitable organic sequestrants are additionally polymeric compounds containing carboxylic acid groups, such as acrylic acid homopolymers. The term "acrylic acid homopolymer" also comprises polymers in which some or all of the carboxylic acid groups are present in neutralized form. Suitable polymeric compounds containing carboxylic acid groups are also oligomaleic acids. Suitable polymeric compounds containing carboxylic acid groups are also terpolymers of unsaturated C4-Cs-dicarboxylic acids. Suitable unsaturated C4-Cs-dicarboxylic acids in this context are, for example, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, methylenemalonic acid and citraconic acid. Suitable polymeric compounds containing carboxylic acid groups are also homopolymers of the monoethylenically unsaturated Cs-Cs-monocarboxylic acids, for example acrylic acid, methacrylic acid, crotonic acid, 2-ethylacrylic acid, 2-phenylacrylic acid, cinnamic acid, vinylacetic acid and sorbic acid, copolymers of dicarboxylic acids, for example of maleic acid and acrylic acid; terpolymers of maleic acid, acrylic acid and a vinyl ester of a Ci-Cs-carboxylic acid; and copolymers of maleic acid with C2-Cs-olefins.
Defoamer and/or foam stabilizer (g) are for example soaps, paraffins and silicone oils.
Further additives (h) are for example hydrotropic agents, acids, bases, buffering agents, enzyme stabilizers, bleaching agents, corrosion inhibitors, dyes, fragrances, thickeners, activity enhancers different from component (b) and inorganic salts.
Hydrotropic agents are compounds which solubilizes hydrophobic compounds in aqueous solution by means other than micellar solubilization. Similar to surfactants, hydrotropes often (but not necessarily) consist of a hydrophilic part and a hydrophobic part, but in contrast to surfactants the hydrophobic part is generally too small to cause spontaneous self-aggregation. Examples are aromatic sulfonic acid salts, such as the alkali metal, earth alkaline metal or ammonium salts of p-toluenesulfonic acid (e.g. sodium, potassium, calcium or ammonium p-tosylate), of xylene sulfonic acids (e.g. the sodium, potassium, calcium or ammonium salts of o-, m- or p-xylene sulfonates) or of cumene sulfonic acids, generally of p-cumene sulfonic acid (e.g. the sodium, potassium, calcium or ammonium salts of p-cumenesulfonate); adenosine triphosphate (ATP); and urea.
The acids can be inorganic or organic. Suitable inorganic acids are for example sulfuric acid, hydrochloric acd and phosphoric acid, where sulfuric acid is generally preferred. Suitable organic acids are for example aliphatic, saturated non-substituted Ci-Ce- mono-, di- and tri-carboxylic acids such as formic acid, acetic acid, propanoic acid, oxalic acid, succinic acid and glutaric acid; aliphatic, saturated Ci-Ce-mono-, di- and tricarboxylic acids carrying one or more OH groups, such as lactic acid, tartric acid and citric acid; aliphatic, unsaturated Ci-Ce-mono-, di- and tri-carboxylic acids such as sorbic acid; aromatic carboxylic acids, such as benzoic acid, salicylic acid and mandelic acid; and sulfonic acids, such as methanesulfonic acid or toluenesulfonic acid. The organic acids mainly serve for adapting the pH of the composition, but some of them, e.g. the di-and tricarboxylic acids, can also act as sequestrants.
Suitable bases are in particular inorganic bases, such as the carbonates mentioned in context with the sequestrant, e.g. sodium or potassium carbonate; further alkali metal and earth alkaline meal hydroxides, such as NaOH or KOH.
Suitable buffering agents are the typical systems, such as hydrogenphosphate/dihy- drogenphosphate buffer, carbonate/hydrogencarbonate buffer, acetic acid/acetate buffer or Tris buffer. Moreover, most of the above acids which are weak and the anion of which is not a strong salt also have buffering capacity.
If the composition comprises one or more enzymes, it may also comprise enzyme stabilizers, for example calcium propionate, sodium formate, boric acid or salts thereof, boronic acids and salts thereof, polyols, peptide aldehydes, and/or antioxidants.
Suitable boronic acids are for examples aromatic and heteroaromatic boronic acids, such as benzene boronic acid (BBA; also termed phenylboronic acid (PBA)), 4- formylphenylboronic acid (4-FPBA), 2-FPBA, 3-FPBA, 4-carboxyphenylboronic acid (4- CPBA), 4-(hydroxymethyl)-phenylboronic acid (4-HMPBA), p-tolylboronic acid (p-TBA), (2-acetamidophenyl)-boronic acid, 2-bromophenylboronic acid, 3-bromophenylboronic acid, 4-bromophenylboronic acid, 2-chlorophenylboronic acid, 3-chlorophenylboronic acid, 4-chlorophenylboronic acid, 2,4-dichlorophenylboronic acid, 3,5-dichlorophenyl- boronic acid, 4-fluorophenylboronic acid, 3-chloro-4-fluorophenylboronic acid, 1 ,3,5-tri- methylphenylboronic acid, 3,5-bis-(trifluoromethyl)-phenylboronic acid, 4-methoxy- phenylboronic acid, 4-(methylthio)-phenylboronic acid, 3-aminophenylboronic acid, 4- (trimethylsilyl)-phenylboronic acid, 4,4-biphenyl-diboronic acid, 1-naphthylboronic acid, 2-naphthylboronic acid, 6-hydroxy-2-naphthaleneboronic acid, 9-anthraceneboronic acid, 2-furanylboronic acid, 3-furanylboronic acid, 2-thienylboronic acid, 3-thienyl- boronic acid, 5-chlorothiopheneboronic acid, 3-bromothiopheneboronic acid, 5-bro- mothiopheneboronic acid, 5-methyl-2-thienylboronic acid, 4-methylthiopheneboronic acid, dimethylthiopheneboronic acid, 3-methoxy-2-thiopheneboronic acid, 2-benzo- furanylboronic acid, 4-dibenzofuranboronic acid, 1-benzothiophene-2-boronic acid, dibenzothiophene boronic acid, 1-thianthrenylboronic acid and 2-thianthrenylboronic acid. Further examples are p-methyl-phenylethylboronic acid, diphenyl boronic acid anhydride and octyl boronic acid. Suitable are also mixtures of two or more different boronic acids. Suitable salts of the above-mentioned boronic acids are for example the alkali metal salts, such as the sodium or potassium salts, the earth alkaline metal salts, such as the magnesium and calcium salts, and ammonium salts.
Suitable polyols are for example polyols containing from 2 to 6 hydroxyl groups, such as ethylene glycol, propylene glycol, 1 ,2-propanediol, 1 ,2-butanediol, 1 ,2-pentanediol, hexyleneglycol, glycerol, sorbitol, mannitol, erythriol, glucose, fructose, and lactose.
Peptide aldehydes are oligopeptides with reduced C-terminus (i.e. in which the C(O)OH group is reduced to an aldehyde [CH(O)] group) Suitable peptide aldehydes are for example di-, tri- or tetrapeptide aldehydes and aldehyde analogues (either of the form B1-BO-R wherein, R is H, CH3, CX3, CHX2, or CH2X (where X = halogen), BO is a single amino acid residue including such with an optionally substituted aliphatic or aromatic side chain; and B1 stands for one or more (e.g. 1 , 2 or 3) amino acid(s), optionally comprising an N-terminal protection group, or is a protease inhibitor of the protein type such as RASI, BASI, WASI (bifunctional alpha-amylase/ subtilisin inhibitors of rice, barley and wheat) or CI2 or SSI.
A suitable bleaching agent is hydrogen peroxide.
Moreover, as mentioned above, some enzymes have bleaching properties.
Dyes can be added to obtain a specific aesthetic appearance, but also be used as shading dyes for reducing or avoiding (auto-)oxidation of components of the composition, especially of unsaturated organic compounds, triggered by UV or visible light (e.g. if the container in which the composition is kept allows transmission of UV or visible light) and/or transition metal ion catalysis (if present). If used as shading dyes, these impart generally a violet or blue color. Shading dyes are particularly useful in laundry compositions, such as laundry detergents or textile softening compositions, where they can help avoiding yellowing of the textiles.
Examples for shading dyes are direct dyes (also known as substantive dyes; water soluble dyes with an affinity for fibres and which are taken up directly; generally azo dyes), e.g. violet 7, direct violet 9, direct violet 11 , direct violet 26, direct violet 31 , direct violet 35, direct violet 40, direct violet 41 , direct violet 51 , and direct violet 99; moreover direct violet 66; acid dyes, such as azine dyes, e.g. acid blue 98, acid violet 50, and acid blue 59, more preferably acid violet 50 and acid blue 98; or non-azine dyes, e.g. acid violet 17, acid black 1 and acid blue 29; hydrophobic dyes (dyes which do not contain any charged water solubilising group; generally selected from the groups of disperse and solvent dyes, in particular blue and violet anthraquinone and mono-azo dyes, e.g. solvent violet 13, disperse violet 27 disperse violet 26, disperse violet 28, disperse violet 63 and disperse violet 77; basic dyes (organic dyes which carry a net positive charge and deposit onto cotton), e.g. triarylmethane basic dyes, methane basic dye, anthraquinone basic dyes, basic blue 16, basic blue 65, basic blue 66, basic blue 67, basic blue 71 , basic blue 159, basic violet 19, basic violet 35, basic violet 38, basic violet 48; basic blue 3, basic blue 75, basic blue 95, basic blue 122, basic blue 124, basic blue 141 ; reactive dyes (dyes which contain an organic group capable of reacting with cellulose and linking the dye to cellulose with a covalent bond, and deposit onto cotton), e.g. reactive blue 19, reactive blue 163, reactive blue 182 and reactive blue, reactive blue 96; and dye conjugates (formed by binding direct, acid or basic dyes to polymers or particles via physical forces).
Fragrances can be of natural or synthetic origin; their nature is in general not critical. Just by way of example, natural aromatic substances are, for instance, extracts from blossom (lilies, lavender, roses, jasmine, neroli, ylang-ylang), from stems and leaves (geranium, patchouli, petitgrain), from fruit (aniseed, coriander, carraway, juniper), from fruit peel (bergamot, lemons, oranges), from roots (mace, angelica, celery, cardamom, costus, iris, calmus), from wood (pinewood, sandalwood, guaiacum wood, cedarwood, rosewood), from herbs and grasses (tarragon, lemon grass, sage, thyme), from needles and twigs (spruce, pine, Scots pine, mountain pine), from resins and balsams (galbanum, elemi, benzoin, myrrh, olibanum, opoponax). Animal raw materials also come into consideration, for example civet and castoreum. Also just by way of example, synthetic aromatic substances are, for instance, products of the ester, ether, aldehyde, ketone, alcohol or hydrocarbon type. Aromatic substance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethylmethylphenyl glycinate, allylcyclohexyl propionate, styrallyl propionate and ben-'zyl salicylate. The ethers include, for example, benzyl ethyl ether; the aldehydes include, for example, the linear alkanals having from 8 to 18 hydrocarbon atoms, citral, citronellal, citronellyl oxyacetaldehyde, cyclamen aldehyde, hy- droxycitronellal, lilial and bourgeonal; the ketones include, for example, the ionones, isomethylionone and methyl cedryl ketone; the alcohols include, for example, anethol, citronellol, eugenol, isoeugenol, geraniol, linalool, phenyl ethyl alcohol and terpinol; and the hydrocarbons include mainly the terpenes and balsams. It is preferable, however, to use mixtures of various aromatic substances that together produce an attractive scent. Ethereal oils of relatively low volatility, which are chiefly used as aroma components, are also suitable as perfume oils, e.g. sage oil, chamomile oil, clove oil, melissa oil, oil of cinnamon leaves, lime blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil, labolanum oil and lavandin oil. Preference is given to the use of bergamot oil, dihydromyrcenol, lilial, lyral, citronellol, phenyl ethyl alcohol, hexyl cinnamalde- hyde, geraniol, benzyl acetone, cyclamen aldehyde, linalool, boisambrene forte, am- broxan, indole, hedione, sandelice, lemon oil, tangerine oil, orange oil, allyl amyl glycolate, cyclovertal, lavandin oil, muscatel sage oil, damascene, bourbon geranium oil, cyclohexyl salicylate, vertofix coeur, iso-E-Super, Fixolide NP, evernyl, iraldein gamma, phenylacetic acid, geranyl acetate, benzyl acetate, rose oxide, romillat, irotyl and floramat alone or in admixture with one another.
Further examples are alpha-hexylcinnamaldehyde, 2-phenoxyethyl isobutyrate (Pheni- rat1), dihydromyrcenol (2,6-dimethyl-7-octen-2-ol), methyl dihydrojasmonate (preferably having a cis-isomer content of more than 60 wt.%) (Hedione9, Hedione HC9), 4,6,6,7,8,8-hexamethyl-1 ,3, 4, 6, 7, 8- hexahydrocyclopenta[g]benzopyran (Galaxolide3), tetrahydrolinalool (3,7-dimethyloctan-3-ol), ethyl linalool, benzyl salicylate, 2-methyl-3- (4-tertbutylphenyl)propanal (Lilial2), cinnamyl alcohol, 4,7-methano-3a,4,5,6,7,7a-hexa- hydro-5-indenyl acetate and/or 4,7-methano-3a,4,5,6,7,7a hexahydro-6-indenyl acetate (Herbaflorat1), citronellol, citronellyl acetate, tetrahydrogeraniol, vanillin, linalyl acetate, styralyl acetate (1 -phenylethyl acetate), octahydro-2, 3,8, 8-tetramethyl-2-acetonaph- thone and/or 2-acetyl-1 , 2, 3, 4,6,7, 8-octahydro-2, 3,8, 8-tetramethylnaphthalene (Iso E Super3), hexyl salicylate, 4-tert-butylcyclohexyl acetate (Oryclone1), 2-tert-butylcyclo- hexyl acetate (Agrumex HC1), alpha-ionone (4-(2,2,6-trimethyl-2-cyclohexen-1-yl)-3- buten-2-one), nalpha- methylionone, alpha-isomethylionone, coumarin, terpinyl acetate, 2-phenylethyl alcohol, 4-(4-hydroxy-4-methylpentyl)-3-cyclohexenecarboxalde- hyde (Lyral3), alphaamylcinnamaldehyde, thylene brassylate, (E)- and/or (Z)-3-methyl- cyclopentadec-5-enone (Muscenone9), 15-pentadec-11-enolide and/or 15-pentadec- 12-enolide (Globalide1), 15-cyclopentadecanolide (Macrolide1), 1-(5,6,7,8-tetrahydro- 3,5,5,6,8,8-hexamethyl-2-naphthalenyl)ethanone (Tonalide10), 2-isobutyl-4-methyltetra- hydro-2H-pyran-4-ol (Florol9), 2-ethyl-4-(2,2,3-trimethyl-3-cyclopenten-1-yl)-2-buten-1- ol (Sandolene1), cis-3-hexenyl acetate, trans-3-hexenyl acetate, trans-2-cis--6-nonadi- enol, 2,4-dimethyl-3-cyclohexenecarboxaldehyde (Vertocitral1), 2,4,4,7-tetramethyl-oct- 6-en-3-one (Claritone1), 2,6-dimethyl-5-hepten-1-al (Melonal2), borneol, 3-(3-iso- propylphenyl)butanal (Florhydral2), 2-methyl-3-(3,4-methylenedioxyphenyl)propanal (Helional3), 3-(4-ethylphenyl)-2,2-dimethylpropanal (Florazon1), 7-methyl-2H-1 ,5-ben- zodioxepin-3(4H)-one (Calone19515), 3,3,5-trimethylcyclohexyl acetate (preferably with a content of cis-isomers of 70 wt.%) or more and 2, 5,5-trimethyl- 1 , 2, 3, 4, 4a, 5,6,7- octahydronaphthalen-2-ol (Ambrinol S1).
If trade names are specified above, these refer to the following sources:
1 Trade name of Symrise GmbH, Germany;
2 Trade name of Givaudan AG, Switzerland;
3 Trade name of International Flavors & Fragrances Inc., USA;
5 Trade name of Danisco Seillans S.A., France;
9 Trade name of Firmenich S.A., Switzerland;
10 Trade name of PFW Aroma Chemicals B.V., The Netherlands.
The fragrances may optionally be incorporated in encapsulated form.
The thickeners serve to impart the desired viscosity to the composition of the invention.
Any known thickener (rheology modifier) is suitable in principle, provided that it does not exert any adverse effect on the efficacy of the composition. Suitable thickeners may either be of natural origin or of synthetic nature.
Thickeners of natural origin are mostly derived from polysaccharides. Examples are xanthan, gellan gum, carob flour, guar flour or gum, carrageenan, agar, tragacanth, gum arabic, alginates, modified starches such as hydroxyethyl starch, starch phosphate esters or starch acetates, dextrins, pectins and cellulose derivatives, such as carboxymethylcellulose, hydroxyethylcellulose, hydrophobically modified hydroxyethyl cellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, methylcellulose and the like. Further examples are bacterial cellulose, meaning any type of cellulose produced via fermentation of a bacteria of the genus Acetobacter such as CELLULON® (CPKelco U.S.) and including materials referred to as microfibrillated cellulose or reticulated bacterial cellulose; and non-bacterial cellulose, e.g. cellulosic fibers extracted from vegetables, fruits or wood, e.g. AvicelO from FMC, Citri-Fi from Fiberstar or Betafib from Cosun.
Thickeners of natural origin are also inorganic thickeners, such as polysilicic acids and clay minerals, for example sheet silicates, and also the silicates mentioned for the builders. More specific examples are listed in the following table. Most are derived from smectite clays and silica derivatives.
Examples of synthetic thickeners are polyacrylic and polymethacrylic compounds, such as (partly) crosslinked homopolymers of acrylic acid, for example homopolymers of acrylic acid which have been crosslinked with an allyl ether of sucrose or pentaerythritol, or with propylene (carbomers), for example the Carbopol® brands from BF Goodrich (e.g. Carbopol® 676, 940, 941 , 934 and the like) or the Polygel® brands from 3V Sigma (e.g. Polygel® DA), copolymers of ethylenically unsaturated mono- or dicarboxylic acids, for example terpolymers of acrylic acid, methacrylic acid or maleic acid with methyl acrylate or ethyl acrylate and a (meth)acrylate which derives from long- chain ethoxylated alcohols, for example the Acusol® brands from Rohm & Haas (e.g. Acusol® 820 or 1206A), copolymers of two or more monomers which are selected from acrylic acid, methacrylic acid and the Ci-C4-alkyl esters thereof, for example copolymers of methacrylic acid, butyl acrylate and methyl methacrylate or of butyl acrylate and methyl methacrylate, for example the Aculyn® and Acusol® brands from Rohm & Haas (e.g. Aculyn® 22, 28 or 33 and Acusol® 810, 823 and 830), or crosslinked high molecular weight acrylic acid copolymers, for example copolymers of C -Cso-alkyl acrylates with one or more comonomers selected from acrylic acid, methacrylic acid and the Ci-C4-alkyl esters thereof, said copolymers having been crosslinked with an allyl ether of sucrose or pentaerythritol (e.g. Carbopol® ETD 2623, Carbopol® 1382 or Carbopol® AQUA 30 from Rohm & Haas).
Suitable thickeners are moreover phospholipids, such as alkylated phosphatidyl choline, phosphobetaines or alkyl phosphate quaternary compounds.
Examples of synthetic thickeners are also reaction products of maleic acid polymers with ethoxylated long-chain alcohols, for example the Surfonic L series from Texaco Chemical Co. or Gantrez AN-119 from ISP; polyethylene glycols, polyamides, polyimines and polycarboxylic acids. Examples of synthetic thickeners are moreover dibenzylidene polyol acetal derivatives (DBPA derivative). These may comprise a dibenzylidene sorbitol acetal derivative (DBS). Said DBS derivative may be selected from the group consisting of: 1 ,3:2, 4- dibenzylidene sorbitol; 1 ,3:2,4-di(p-methylbenzylidene) sorbitol; 1 ,3:2,4-di(p-chloroben- zylidene) sorbitol; 1 ,3:2,4-di(2,4-dimethyldibenzylidene) sorbitol; 1 ,3:2,4-di (p-ethyl-ben- zylidene) sorbitol; 1 ,3:2,4-di(3,4-dimethyldibenzylidene) sorbitol; and mixtures thereof.
Suitable thickeners are moreover di-amido gellants, e.g. selected from those having a molecular weight from about 150g/mol to about 1,500g/mol, or even from about 500g/mol to about 900 g/mol. Such di-amido gellants may comprise at least two nitrogen atoms, wherein at least two of said nitrogen atoms form amido functional substitution groups. The amido groups may be different or identical. Examples are compounds of the formula Ra-C(=O)-NH-L-C(=O)-Rb, where Ra and Ra are amino functional end- groups or amido functional end groups, and L is a linking moiety of molecular weight from 14 to 500 g/mol. Ra and Rb may comprise a pH-tunable group, wherein the pH- tunable amido-gellant may have a pKa of from about 1 to about 30, or even from about 2 to about 10. The pH tunable group may comprise a pyridine. L may comprise a carbon chain comprising between 2 and 20 carbon atoms. L may comprise a pH-tunable group. The pH-tunable group may be a secondary amine.
Examples of synthetic thickeners are also non-polymeric crystalline, hydroxyl functional structurants . Said compound may comprise a crystallizable glyceride which can be pre-emulsified to aid dispersion into the final liquid detergent formulation. The crystallizable glycerides may comprise hydrogenated castor oil or "HCO" or derivatives thereof, provided that it is capable of crystallizing in the liquid formulation.
Also suitable are mixtures of the abovementioned thickeners.
Suitable activity enhancers different from component (b) are in particular PEI.
PEI are polymers of ethylenediamine and can be characterized by repeating groups of the empirical formula -[CH2-CH2-NH]n- wherein n ranges from approximately from 10 to 100,000, e.g. from 10 to 15000. PEI can be linear or branched (branched forms are not correctly reflected in the above formula; nevertheless the formula should also symbolize branched forms), where branching can result in dendrimers, star-like polymers, hyperbranched polymers and other branched forms. Branched polyethylenimines can be characterized by their degree of branching (DB). DB may be determined, for example, by 13C-NMR spectrometry and is defined as follows:
DB = D +T/D+T+L wherein D stands for the fraction of tertiary amino groups, L (linear) stands for the fraction of secondary amino groups, and T (terminal) stands for the fraction of primary amino groups. Preferably, DB ranges from 0.1 to 0.95, more preferably from 0.25 to 0.90, in particular from 0.30 to 0.80, and specifically from 0.5-0.8.
Preferably, the PEIs used in the present compositions have weight average molecular weight Mw of from 500 to 1 ,000,000 g/mol, more preferably from 600 to 75,000 g/mol, and in particular from 800 to 25000 g/mol, as determined by gel permeation chromatography (GPC with PEG or PMMA standard; specifically with multi angle light scattering (MALS) detector of the intermediate respective polyalkylenimine, with 1.5% by weight aqueous formic acid as eluent and cross-linked poly-hydroxyethyl methacrylate as stationary phase).
In a specific embodiment, the PEIs used in the present compositions are grafted with ethylene oxide (EG) and/or propylene oxide (PO). Typically, the PEI is grafted with 5 to 100 mol of alkylene oxide per mol of PEI.
If present, the PEI is typically contained in the homecare or l&l composition in an amount of from 0.001 to 10% by weight, preferably from 0.001 to 1% by weight, relative to the total weight of the composition.
Suitable PEIs are commercially available, e.g. under the Lupasol® and Sokolan® HP brands from BASF.
Suitable inorganic salts are for example sodium chloride and calcium chloride.
In a particular embodiment, the composition of the invention is a dishwashing composition. Dishwashing compositions preferably comprise:
(a) 0.001 to 7% by weight, relative to the total weight of the composition, of an antimicrobial agent as defined above;
(b) 0.001 to 7% by weight, relative to the total weight of the composition, of an alkox- ylated amine (I) or a mixture of different alkoxylated amines (I) as defined above;
(c) 0 to 15% by weight, relative to the total weight of the composition, of at least one organic solvent, preferably as defined above, the solvent more preferably comprising a solvent selected from solvents (c.1) to (c.10);
(d) 0.1 to 40% by weight, relative to the total weight of the composition, of one or more surfactants;
(e) 0 to 6% by weight, relative to the total weight of the composition, of at least one enzyme;
(f) 0 to 20% by weight, relative to the total weight of the composition, of at least one sequestrant;
(g) 0 to 8% by weight, relative to the total weight of the composition, of at least one defoamer and/or foam stabilizer; (h) 0 to 50% by weight, relative to the total weight of the composition, of a further additive; and
(i) 10 to 99.898% by weight, relative to the total weight of the composition, of water; where components (a) to (i) add to 100% by weight.
Such dishwashing compositions are in liquid or gel form and are suitable both for machine washing as well as for manual dishwashing. As a matter of course, manual dishwashing compositions have to be adapted so as not to present any hazard for the user. For instance, the amount of optionally present acids and/or bases is such that the resulting pH does not harm the user’s skin.
Suitable and preferred components (a) to (h) are those listed above.
Dishwashing compositions may further comprise as component (h) anti-greying polymers and scale inhibitor or scale dispersing agents.
More particularly, the composition of the invention is a dishwashing composition comprising:
(a) 0.001 to 5% by weight, relative to the total weight of the composition, of an antimicrobial agent as defined above;
(b) 0.01 to 7% by weight, relative to the total weight of the composition, of an alkox- ylated amine (I) or a mixture of different alkoxylated amines (I) as defined above;
(c) 0 to 5% by weight, relative to the total weight of the composition, of at least one organic solvent, preferably as defined above, the solvent more preferably comprising a solvent selected from solvents (c.1) to (c.10);
(d) 5 to 25% by weight, relative to the total weight of the composition, of one or more surfactants;
(e) 0 to 6% by weight, relative to the total weight of the composition, of at least one enzyme;
(f) 0 to 20% by weight, relative to the total weight of the composition, of at least one sequestrant;
(g) 0 to 8% by weight, relative to the total weight of the composition, of at least one defoamer and/or foam stabilizer;
(h) 0 to 50% by weight, relative to the total weight of the composition, of a further additive; and
(i) 10 to 94.989% by weight, relative to the total weight of the composition, of water; where components (a) to (i) add to 100% by weight. In a specific embodiment, the antimicrobial agent (a) is 2-phenoxyethanol, and this is contained in an amount of from 0.1 to 5% by weight, e.g. 0.1 to 2% by weight, relative to the total weight of the composition; and the alkoxylated amine (b) is contained in an amount of from 0.1 to 7% by weight.
In another particular embodiment, the composition of the invention is a laundry composition. Laundry compositions preferably comprise:
(a) 0.001 to 7% by weight, relative to the total weight of the composition, of an antimicrobial agent as defined above;
(b) 0.001 to 7% by weight, relative to the total weight of the composition, of an alkoxylated amine (I) or a mixture of different alkoxylated amines (I) as defined above;
(c) 0 to 15% by weight, relative to the total weight of the composition, of at least one organic solvent, preferably as defined above, the solvent more preferably comprising a solvent selected from solvents (c.1) to (c.10);
(d) 0.1 to 40% by weight, relative to the total weight of the composition, of one or more surfactants;
(e) 0 to 6% by weight, relative to the total weight of the composition, of at least one enzyme;
(f) 0 to 20% by weight, relative to the total weight of the composition, of at least one sequestrant;
(g) 0 to 8% by weight, relative to the total weight of the composition, of at least one defoamer and/or foam stabilizer;
(h) 0 to 50% by weight, relative to the total weight of the composition, of a further additive; and
(i) 10 to 99.898% by weight, relative to the total weight of the composition, of water; where components (a) to (i) add to 100% by weight.
Such laundry compositions are in liquid or gel form and are suitable both for machine washing as well as for manual laundry washing. As a matter of course, manual laundry compositions have to be adapted so as not to present any hazard for the user. For instance, the amount of optionally present acids and/or bases is such that the resulting pH does not harm the user’s skin.
Suitable and preferred components (a) to (h) are those listed above.
Examples for laundry compositions are laundry detergents, fabric softeners, rinsing compositions, bleacher compositions, and stain remover compositions.
Laundry detergents may further comprise as component (h) dye transfer inhibitors, anti-greying polymers, soil release polymers, anti-redeposition agents, anti-shrinking agents, anti-wrinkle agents, ironing aids, skin benefit agents, antistatic agents, processing aids, such as electrolyts, pearlisers, opacifiers, sunscreens, and/or antioxidants.
The terms anti-greying and anti-redeposition agents are often used interchangeably. Suitable examples for such agents are the aforementioned PEIs in grafted (alkox- ylated) or ungrafted form, other alkyleneimine polymers, such as polypropyleneimine (PPI), also in grafted or ungrafted form, further ethoxylated hexamethylene diamine polymers which are quaternized and - optionally but preferably - sulfated, and graft polymer GP comprising as a graft base a polyether and as grafted side chains copolymers comprising at least one comonomer (CM) as described below.
The ethoxylated hexamethylene diamine polymers preferably contain in average 10 to 50, more preferably 15 to 40 and even more preferably 20 to 30 EG (ethoxylate) groups per NH group, resulting in an average molecular weight Mw in the range from 2,000 to 10,000 g/mol, more preferably 3,000-8,000, most preferably 4,000-6,000. In a preferred embodiment the ethoxylated hexamethylene diamine is quaternized and also sulfated, preferably bearing 2 cationic ammonium groups and 2 anionic sulfate groups.
In the gaft polymer GP, the side chains comprise at least one comonomer (CM) selected from
CH2=CH-O-C(O)-Ra (CM-la)
CH2=CH-CH2-O-C(O)-Ra (CM-lb)
CH2=CZ-CO-ORb (CM-lc) wherein Ra is selected from Ci-C2i-alkyl, for example methyl, n-propyl, n-pentyl, n-hep- tyl, n-nonyl, iso-nonyl, n-undecyl, n-tridecyl, n-pentadecyl, n-heptadecyl, or n-non- adecyl, Rb is selected from C2-C2o-alkyl, preferably with an even number of carbon atoms, for example ethyl, n- and iso propyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl or isodecyl, n-Ci2H25, n-Ci4H2g, n-CieH33 or n-CisHs?, and Z is selected from hydrogen and methyl, hydrogen bring preferred.
In the graft polymer GP, the polyethers bear at least 5 ether groups per mole and - if at all - only hydroxyl groups, for example one, two or three hydroxyl groups per molecule. Such hydroxyl groups may be primary or secondary hydroxyl groups, primary hydroxyl groups being preferred. The polyethers are preferably polyethylene glycols, for example with an average molecular weight Mn in the range of from 500 to 25,000 g/mol, preferably 1 ,000 to 15,000 g/mole and even more preferably 1 ,500 to 10,000 g/mol, e.g. 1 ,500 to 4,000 g/mol or 4,000 to 6,000 g/mol or 5,000 to 8,000 g/mol. Alternatively, the polyethers are preferably polypropylene glycols, for example with an average molecular weight Mn in the range of from 500 to 20,000 g/mol, preferably 2,000 to 10,000 g/mol and even more preferably 4,000 to 9,000 g/mol Alternatively, the polyethers are copolymers of ethylene glycol and propylene glycol units, for example random copolymers and preferably block copolymers, for example di-block copolymers and tri-block copolymers. Preferably, copolymers of ethylene glycol and propylene glycol are block copolymers. The polyethylene glycols, polypropylene glycols and EO-PO block copolymers can be non-capped or end-capped with Ci-C2o-alkyl or C3-C2o-2-hydroxyalkyl.
Other examples for anti-greying agents are carboxymethyl cellulose (CMC), ether sulfonic acid salts of starch, ether sulfonic acid salts of cellulose, acidic sulfuric acid ester salts of cellulose, acidic sulfuric acid ester salts of starch, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose methyl hydroxyethyl cellulose, methyl carboxymethyl cellulose, ethyl hydroxyethyl cellulose and mixtures thereof.
Further examples for anti-greying agents are polyalkylene oxide polymers (ethylene oxide, propylene oxide and/or butylene oxide polymers) grafted with methyl acrylate, ethyl acrylate, methyl methacrylate and/or ethyl methacrylate.
In fabric softeners, at least a part of the detergent (c) described above is replaced by a softening agent.
Suitable softening agents are quaternary ammonium salts, especially quats or ester quats. Quats are compounds [NR1R2R3R4]+X; wherein R1, R2, R3 and R4 are alkyl groups, where at least one, generally two is/are long-chained alkyl and the others are generally methyl or ethyl, and X- is a counter anion, such as chloride. Examples are DSDMAC (distearyl dimethyl ammonium chloride, also termed DODMAC (dioctadecyl dimethyl ammonium chloride)), TDMAC (ditallow di-methyl ammonium chloride), DHTDMAC (dehydrogenated tallow alkyl) dimethyl ammonium chloride) and DDAC- C10 (didecyldimethylammonium chloride. Esterquats are derived from alkanolamines in which at least one alkanol group is esterified with a fatty acid. Typically, esterquats are derived from methyl-triethanol-ammmonium salts, where 1 , 2 or 3 of the OH groups are esterified with a fatty acid, and from dimethyl-diethanol-ammonium salts, where 1 or 2 OH groups are esterified with a fatty acid. Preference is given to esterquats.
More particularly, the composition of the invention is a laundry composition comprising:
(a) 0.001 to 5% by weight, relative to the total weight of the composition, of an antimicrobial agent as defined above;
(b) 0.01 to 7% by weight, relative to the total weight of the composition, of an alkox- ylated amine (I) or a mixture of different alkoxylated amines (I) as defined above;
(c) 0 to 5% by weight, relative to the total weight of the composition, of at least one organic solvent, preferably as defined above, the solvent more preferably comprising a solvent selected from solvents (c.1) to (c.10); (d) 4 to 30% by weight, relative to the total weight of the composition, of one or more surfactants];
(e) 0 to 6% by weight, relative to the total weight of the composition, of at least one enzyme;
(f) 0 to 20% by weight, relative to the total weight of the composition, of at least one sequestrant;
(g) 0 to 8% by weight, relative to the total weight of the composition, of at least one defoamer and/or foam stabilizer;
(h) 0 to 50% by weight, relative to the total weight of the composition, of a further additive; and
(i) 10 to 95.989% by weight, relative to the total weight of the composition, of water; where components (a) to (i) add to 100% by weight.
In a specific embodiment, the antimicrobial agent (a) is 2-phenoxyethanol, and this is contained in an amount of from 0.1 to 5% by weight, e.g. 0.1 to 2% by weight, relative to the total weight of the composition; and the alkoxylated amine (b) is contained in an amount of from 0.1 to 7% by weight.
In a particular embodiment, the composition of the invention is a surface cleaning composition. Surface cleaning compositions preferably comprise:
(a) 0.001 to 7% by weight, relative to the total weight of the composition, of an antimicrobial agent as defined above;
(b) 0.001 to 7% by weight, relative to the total weight of the composition, of an alkoxylated amine (I) or a mixture of different alkoxylated amines (I) as defined above;
(c) 0 to 15% by weight, relative to the total weight of the composition, of at least one organic solvent, preferably as defined above, the solvent more preferably comprising a solvent selected from solvents (c.1) to (c.10);
(d) 0.1 to 40% by weight, relative to the total weight of the composition, of one or more surfactants;
(e) 0 to 6% by weight, relative to the total weight of the composition, of at least one enzyme;
(f) 0 to 20% by weight, relative to the total weight of the composition, of at least one sequestrant;
(g) 0 to 8% by weight, relative to the total weight of the composition, of at least one defoamer and/or foam stabilizer;
(h) 0 to 50% by weight, relative to the total weight of the composition, of a further additive; and
(i) 10 to 99.898% by weight, relative to the total weight of the composition, of water; where components (a) to (i) add to 100% by weight. Such surface cleaning compositions are in liquid or gel form and are suitable for manual use. As a matter of course, surface cleaning compositions for household use have to be adapted so as not to present any hazard for the user. For instance, the amount of optionally present acids and/or bases is such that the resulting pH does not harm the user’s skin.
Suitable and preferred components (a) to (h) are those listed above.
Surface cleaning compositions may further comprise as component (h) anti-greying polymers and scale inhibitor or scale dispersing agents.
More particularly, the composition of the invention is a surface cleaning compositioncomprising:
(a) 0.001 to 5% by weight, relative to the total weight of the composition, of an antimicrobial agent as defined above;
(b) 0.001 to 5% by weight, relative to the total weight of the composition, of an alkox- ylated amine (I) or a mixture of different alkoxylated amines (I) as defined above;
(c) 0 to 8% by weight, relative to the total weight of the composition, of at least one organic solvent, preferably as defined above, the solvent more preferably comprising a solvent selected from solvents (c.1) to (c.10);
(d) 0.1 to 30% by weight, relative to the total weight of the composition, of one or more surfactants;
(e) 0 to 3% by weight, relative to the total weight of the composition, of at least one enzyme;
(f) 0 to 10% by weight, relative to the total weight of the composition, of at least one sequestrant;
(g) 0 to 4% by weight, relative to the total weight of the composition, of at least one defoamer and/or foam stabilizer;
(h) 0 to 25% by weight, relative to the total weight of the composition, of a further additive; and
(i) 10 to 99.898% by weight, relative to the total weight of the composition, of water; where components (a) to (i) add to 100% by weight.
Even more particularly, the composition of the invention is a surface cleaning composition comprising:
(a) 0.001 to 5% by weight, relative to the total weight of the composition, of an antimicrobial agent as defined above;
(b) 0.01 to 5% by weight, relative to the total weight of the composition, of an alkoxylated amine (I) or a mixture of different alkoxylated amines (I) as defined above; (c) 0 to 5% by weight, relative to the total weight of the composition, of at least one organic solvent, preferably as defined above, the solvent more preferably comprising a solvent selected from solvents (c.1) to (c.10);
(d) 0.1 to 25% by weight, relative to the total weight of the composition, of one or more surfactants;
(e) 0 to 3% by weight, relative to the total weight of the composition, of at least one enzyme;
(f) 0 to 10% by weight, relative to the total weight of the composition, of at least one sequestrant;
(g) 0 to 4% by weight, relative to the total weight of the composition, of at least one defoamer and/or foam stabilizer;
(h) 0 to 25% by weight, relative to the total weight of the composition, of a further additive; and
(i) 10 to 99.739% by weight, relative to the total weight of the composition, of water; where components (a) to (i) add to 100% by weight.
In a specific embodiment, the antimicrobial agent (a) is 2-phenoxyethanol, and this is contained in an amount of from 0.1 to 5% by weight, e.g. 0.1 to 2% by weight, relative to the total weight of the composition; and the alkoxylated amine (b) is contained in an amount of from 0.1 to 7% by weight.
In a particular embodiment, the homecare or l&l composition is a refill concentrate. Refill concentrates contain all ingredients of the final ready-to-use product, but for water which is either essentially absent (“essentially” taking account of the fact that some of the ingredients may contain some residual water) or contained in amounts far below those of the final ready-to-use product. The end user has just to fill the refill concentrate into a suitable container and add the indicated amount of water.
Such refill concentrates preferably comprise:
(a) 0.01 to 10% by weight, relative to the total weight of the composition, of an antimicrobial agent as defined above;
(b) 0.01 to 10% by weight, relative to the total weight of the composition, of an alkoxylated amine (I) or a mixture of different N alkoxylated amines (I) as defined above;
(c) 0 to 30% by weight, relative to the total weight of the composition, of at least one organic solvent, the solvent more preferably comprising a solvent selected from solvents (c.1) to (c.10);
(d) 0.1 to 60% by weight, relative to the total weight of the composition, of one or more surfactants; (e) 0 to 10% by weight, relative to the total weight of the composition, of at least one enzyme;
(f) 0 to 10% by weight, relative to the total weight of the composition, of at least one sequestrant;
(g) 0 to 10% by weight, relative to the total weight of the composition, of at least one defoamer and/or foam stabilizer;
(h) 0 to 50% by weight, relative to the total weight of the composition, of a further additive; and
(i) 0 to 20% by weight, relative to the total weight of the composition, of water; where components (a) to (i) add to 100% by weight.
In a specific embodiment, the antimicrobial agent (a) is 2-phenoxyethanol, and this is contained in an amount of from 0.1 to 10% by weight, relative to the total weight of the composition; and the alkoxylated amine (b) is contained in an amount of from 0.1 to 10% by weight.
Figure imgf000061_0001
The combination of the antimicrobial agent and the alkoxylated amine (I) in crop protection compositions generally serves for preserving said composition. Crop protection compositions needing preservation generally contain water.
Examples for such compositions are e. g. solutions, emulsions, suspensions, pastes, capsules, and mixtures thereof. Examples for composition types are suspensions (e.g. SC, OD, FS), emulsifiable concentrates (e.g. EC), emulsions (e.g. EW, EO, ES, ME), capsules (e.g. CS, ZC), pastes, as well as gel formulations for the treatment of plant propagation materials such as seeds (e.g. GF). These and further compositions types are defined in the "Catalogue of pesticide formulation types and international coding system", Technical Monograph No. 2, 6th Ed. May 2008, CropLife International.
The compositions are prepared in a known manner, such as described by Mollet and Grubemann, Formulation technology, Wiley VCH, Weinheim, 2001 ; or Knowles, New developments in crop protection product formulation, Agrow Reports DS243, T&F Informa, London, 2005.
Suitable auxiliaries are solvents, liquid carriers, surfactants, dispersants, emulsifiers, wetters, adjuvants, solubilizers, penetration enhancers, protective colloids, adhesion agents, thickeners, humectants, repellents, attractants, feeding stimulants, compatibilizers, anti-freezing agents, anti-foaming agents, colorants, tackifiers and binders.
Suitable solvents and liquid carriers are water and organic solvents, such as mineral oil fractions of medium to high boiling point, e.g. kerosene, diesel oil; oils of vegetable or animal origin; aliphatic, cyclic and aromatic hydrocarbons, e. g. toluene, paraffin, tetrahydronaphthalene, alkylated naphthalenes; alcohols, e.g. ethanol, propanol, butanol, benzylalcohol, cyclo-'hexanol; glycols; DMSO; ketones, e.g. cyclo-'hexanone; esters, e.g. lactates, carbonates, fatty acid esters, gamma-butyrolactone; fatty acids; phospho- nates; amines; amides, e.g. fatty acid dhmethylamides; and mixtures thereof.
Suitable surfactants are surface-active compounds, such as anionic, cationic, nonionic and amphoteric surfactants, block polymers, polyelectrolytes, and mixtures there_,of. Such surfactants can be used as emusifier, dispersant, solubilizer, wetter, penetration enhancer, protective colloid, or adjuvant. Examples of surfactants are listed in McCutcheon's, Vol.1 : Emulsifiers & Detergents, McCutcheon's Directories, Glen Rock, USA, 2008 (International Ed. or North American Ed.).
Suitable anionic surfactants are alkali, alkaline earth or ammonium salts of sulf-'onates, sulfates, phosphates, carboxylates, and mixtures thereof. Examples of sulf-'onates are alkylarylsulfonates, diphenylsulfonates, alpha-olefin sulfonates, lignine sulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of alkoxylated arylphenols, sulfonates of condensed naphthalenes, sulf-'onates of dodecyl- and tridecylbenzenes, sulfonates of naphthalenes and alkyhnaphtha-'lenes, sulfosuccinates or sulfosuccinamates. Examples of sulfates are sulfates of fatty acids and oils, of ethoxylated alkylphenols, of alcohols, of ethoxylated alcohols, or of fatty acid esters. Examples of phosphates are phosphate esters. Examples of carboxylates are alkyl carboxylates, and carboxylated alcohol or alkylphenol ethoxylates.
Suitable nonionic surfactants are alkoxylates, N-subsituted fatty acid amides, amine oxides, esters, sugar-based surfactants, polymeric surfactants, and mixtures thereof. Examples of alkoxylates are compounds such as alcohols, alkylphenols, amines, amides, arylphenols, fatty acids or fatty acid esters which have been alkoxylated with 1 to 50 equivalents. Ethylene oxide and/or propylene oxide may be employed for the alkoxyla- tion, preferably ethylene oxide. Examples of N-subsititued fatty acid amides are fatty acid glucamides or fatty acid alkanolamides. Examples of esters are fatty acid esters, glycerol esters or monoglycerides. Examples of sugar-based surfactants are sorbitans, ethoxylated sorbitans, sucrose and glucose esters or alkylpolyglucosides. Examples of polymeric surfactants are home- or copolymers of vinylpyrrolidone, vinylalcohols, or vinylacetate.
Suitable cationic surfactants are quaternary surfactants, for example quaternary am-rnonium compounds with one or two hydrophobic groups, or salts of long-chain primary amines. Suitable amphoteric surfactants are alkylbetains and imidazolines. Suitable block polymers are block polymers of the A-B or A-B-A type comprising blocks of polyethylene oxide and polypropylene oxide, or of the A-B-C type comprising alkanol, polyethylene oxide and polypropylene oxide. Suitable polyelectrolytes are polyacids or polybases. Examples of polyacids are alkali salts of polyacrylic acid or polyacid comb polymers. Examples of polybases are polyvinylamines or polyethyleneamines. Suitable adjuvants are compounds which have a neglectable or even no pesticidal activity themselves, and which improve the biological performance of the polymeric, ionic compound comprising imidazolium groups on the target. Examples are surfactants, mineral or vegetable oils, and other auxilaries. Further examples are listed by Knowles, Adjuvants and additives, Agrow Reports DS256, T&F Informa UK, 2006, chapter 5. Suitable thickeners are polysaccharides (e.g. xanthan gum, carboxymethylcellu-'lose), anorganic clays (organically modified or unmodified), polycarboxylates, and silicates. Suitable anti-freezing agents are ethylene glycol, propylene glycol, urea and glycerin. Suitable anti-foaming agents are silicones, long chain alcohols, and salts of fatty acids. Suitable colorants (e.g. in red, blue, or green) are pigments of low water solubility and water-soluble dyes. Examples are inorganic colorants (e.g. iron oxide, titan oxide, iron hexacyanoferrate) and organic colorants (e.g. alizarin-, azo- and phthalocyanine colorants).
Suitable tackifiers or binders are polyvinylpyrrolidons, polyvinylacetates, polyvinyl alcohols, polyacrylates, biological or synthetic waxes, and cellulose ethers.
The crop protection compositions contain of course at least one active agent suitable for combating harmul microorganisms, invertebrate pests or weeds, e.g. at least one fungicide, insecticide, acaricide, nematicide, moluscicide and/or herbicide; or for regulating the growth of plants.
Examples of fungicidally active substances comprise:
• acylalanines, such as benalaxyl, metalaxyl, ofurace or oxadixyl;
• amine derivatives, such as aldimorph, dodine, dodemorph, fenpropimorph, fenpropidin, guazatine, iminoctadine, spiroxamine or tridemorph;
• anilinopyrimidines, such as pyrimethanil, mepanipyrim or cyprodinil;
• antibiotics, such as cycloheximide, griseofulvin, kasugamycin, natamycin, polyoxin and streptomycin;
• azoles, such as bitertanol, bromoconazole, cyproconazole, difenoconazole, dini- conazole, epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imazalil, ipconazole, metconazole, myclobutanil, penconazole, pro- piconazole, prochloraz, prothioconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triflumizole or triticonazole;
• 2-methoxybenzophenones, such as those disclosed in EP-A 897 904 by the general formula (I), e.g. metrafenone;
• dicarboximides, such as iprodione, myclozolin, procymidone or vinclozolin;
• dithiocarbamates, such as ferbam, nabam, maneb, mancozeb, metam, metiram, propineb, polycarbamate, thiram, ziram or zineb;
• heterocyclic compounds, such as anilazine, benomyl, boscalid, carbendazim, carboxin, oxycarboxin, cyazofamid, dazomet, dithianon, famoxadone, fenamidone, fenarimol, fuberidazole, flutolanil, furametpyr, isoprothiolane, mepronil, nuarimol, picobenzamid, probenazole, proquinazid, pyrifenox, pyroquilon, quinoxyfen, silthi- ofam, thiabendazole, thifluzamide, thiophanate-methyl, tiadinil, tricyclazole or tri- forine; • nitrophenyl derivatives, such as binapacryl, dinocap, dinobuton or nitrothal-isopro- pyi;
• phenylpyrroles, such as fenpiclonil or fludioxonil;
• unclassified fungicides, such as acibenzolar-S-methyl, benthiavalicarb, carpropa- mid, chlorothalonil, cyflufenamid, cymoxanil, diclomezine, diclocymet, diethofencarb, edifenphos, ethaboxam, fenhexamid, fentin acetate, fenoxanil, ferimzone, fluazinam, fosetyl, fosetyl-aluminum, iprovalicarb, hexachlorobenzene, met- rafenone, pencycuron, propamocarb, phthalide, tolclofos-methyl, quintozene or zoxamide;
• strobilurins, such as those disclosed in WO 03/075663 by the general formula (I), for example azoxystrobin, dimoxystrobin, fluoxastrobin, kresoxim-methyl, metom- inostrobin, orysastrobin, picoxystrobin, pyraclostrobin and trifloxystrobin;
• sulfenic acid derivatives, such as captafol, captan, dichlofluanid, folpet or tol- ylfluanid;
• cinnamamides and analogous compounds, such as dimethomorph, flumetover or flumorph;
• 6-aryl-[1 ,2,4]triazolo[1,5-a]pyrimidines, such as those disclosed, e.g., in
WO 98/46608, WO 99/41255 or WO 03/004465, in each case by the general formula (I);
• amide fungicides, such as cyflufenamid and (Z)-N-[D-(cyclopropylmethoxyimino)- 2,3-difluoro-6-(difluoromethoxy)benzyl]-2-phenylacetamide.
Examples of herbicides comprise:
• 1,3,4-thiadiazoles, such as buthidazole and cyprazole;
• amides, such as allidochlor, benzoylprop-ethyl, bromobutide, chlorthiamid, dimepiperate, dimethenamid, diphenamid, etobenzanid, flamprop-methyl, fosa- mine, isoxaben, metazachlor, monalide, naptalam, pronamide or propanil;
• aminophosphoric acids, such as bilanafos, buminafos, glufosinate-ammonium, glyphosate or sulfosate;
• aminotriazoles, such as amitrole, or anilides, such as anilofos or mefenacet;
• aryloxyalkanoic acid, such as 2,4-D, 2,4-DB, clomeprop, dichlorprop, dichlorprop- P, fenoprop, fluroxypyr, MCPA, MCPB, mecoprop, mecoprop-P, napropamide, naproanilide or triclopyr;
• benzoic acids, such as chloramben or dicamba;
• benzothiadiazinones, such as bentazon;
• bleachers, such as clomazone, diflufenican, fluorochloridone, flupoxam, fluridone, pyrazolate or sulcotrione;
• carbamates, such as carbetamide, clorbufam, chlorpropham, desmedipham, phen- medipham or vernolate;
• quinolinecarboxylic acids, such as quinclorac or quinmerac;
• dichloropropionic acids, such as dalapon; • dihydrobenzofurans, such as ethofumesate;
• dhydrofuran-3-ones, such as flurtamone;
• dinitroanilines, such as benefin, butralin, dinitramine, ethalfluralin, fluchloralin, isopropalin, nitralin, oryzalin, pendimethalin, prodiamine, profluralin, trifluralin;
• dinitrophenols, such as bromofenoxim, dinoseb, dinoseb acetate, dinoterb, DNOC or minoterb acetate;
• diphenyl ethers, such as acifluorfen-sodium, aclonifen, bifenox, chlornitrofen, dif- enoxuron, ethoxyfen, fluorodifen, fluoroglycofen-ethyl, fomesafen, furyloxyfen, lactofen, nitrofen, nitrofluorfen or oxyfluorfen;
• dipyridyls, such as cyperquat, difenzoquat metilsulfate, diquat or paraquat dichloride;
• imidazoles, such as isocarbamid;
• imidazolinones, such as imazamethapyr, imazapyr, imazaquin, imazethabenzme- thyl, imazethapyr, imazapic or imazamox;
• oxadiazoles, such as methazole, oxadiargyl or oxadiazone;
• oxiranes, such as tridiphane;
• phenols, such as bromoxynil or ioxynil;
• phenoxyphenoxypropionic acid esters, such as clodinafop, cyhalofop-butyl, diclo- fop-methyl, fenoxaprop-ethyl, fenoxaprop-P-ethyl, fenthiaprop-ethyl, fluazifop-butyl, fluazifop-P-butyl, haloxyfop-ethoxyethyl, haloxyfop-methyl, haloxyfop-P-methyl, isoxapyrifop, propaquizafop, quizalofop-ethyl, quizalofop-P-ethyl or quizalofop-P- tefuryl;
• phenylacetic acids, such as chlorfenac;
• phenylpropionic acids, such as chlorphenprop-methyl;
• ppi-active substances (ppi = preplant incorporated), such as benzofenap, flumiclorac-pentyl, flumioxazin, flumipropyn, flupropacil, pyrazoxyfen, sulfentrazone or thidiazimin;
• pyrazoles, such as nipyraclofen;
• pyridazines, such as chloridazon, maleic hydrazide, norflurazon or pyridate;
• pyridinecarboxylic acids, such as clopyralid, dithiopyr, picloram or thiazopyr;
• pyrimidyl ethers, such as pyrithiobac acid, pyrithiobac-sodium, KIH-2023 or KIH- 6127;
• sulfonamides, such as flumetsulam or metosulam;
• triazolecarboxamides, such as triazofenamide;
• uracils, such as bromacil, lenacil or terbacil;
• furthermore benazolin, benfuresate, bensulide, benzofluor, bentazon, butamifos, cafenstrole, chlorthal-dimethyl, cinmethylin, dichlobenil, endothall, fluorbentranil, mefluidide, perfluidone, piperophos, topramezone and prohexadione-calcium; • sulfonylureas, such as amidosulfuron, azimsulfuron, bensulfuron-methyl, chlo- rimuron-ethyl, chlorsulfuron, cinosulfuron, cyclosulfamuron, ethametsulfuron-me- thyl, flazasulfuron, halosulfuron-methyl, imazosulfuron, metsulfuron-methyl, nico- sulfuron, primisulfuron, prosulfuron, pyrazosulfuron-ethyl, rimsulfuron, sulfome- turon-methyl, thifensulfuron-methyl, triasulfuron, tribenuron-methyl, triflusulfuron- methyl or tritosulfuron;
• plant protection active substances of the cyclohexenone type, such as alloxydim, clethodim, cloproxydim, cycloxydim, sethoxydim and tralkoxydim. Very particularly preferred herbicidal active substances of the cyclohexenone type are: tepraloxydim (cf. AGROW, No. 243, 11.3.95, page 21, caloxydim) and 2-(1-[2-{4-chlorphenoxy}- propyloxyimino]butyl)-3-hydroxy-5-(2H-tetrahydrothiopyran-3-yl)-2-cyclohexen-1- one, and of the sulfonylurea type is: N-(((4-methoxy-6-[trifluoromethyl]-1,3,5-tria- zin-2-yl)amino)carbonyl)-2-(trifluoromethyl)benzenesulfonamide.
Examples of insecticides comprise:
• organophosphates, such as acephate, azinphos-methyl, chlorpyrifos, chlorfenvinphos, diazinon, dichlorvos, dimethylvinphos, dioxabenzofos, dicrotophos, dimethoate, disulfoton, ethion, EPN, fenitrothion, fenthion, isoxathion, malathion, methamidophos, methidathion, methyl parathion, mevinphos, monocrotophos, ox- ydemeton-methyl, paraoxon, parathion, phenthoate, phosalone, phosmet, phos- phamidon, phorate, phoxim, pirimiphos-methyl, profenofos, prothiofos, pirimiphos- ethyl, pyraclofos, pyridaphenthion, sulprophos, triazophos, trichlorfon, tetrachlor- vinphos or vamidothion;
• carbamates, such as alanycarb, benfuracarb, bendiocarb, carbaryl, carbofuran, carbosulfan, fenoxycarb, furathiocarb, indoxacarb, methiocarb, methomyl, oxamyl, pirimicarb, propoxur, thiodicarb or triazamate; pyrethroids, such as bifenthrin, cyfluthrin, cycloprothrin, cypermethrin, deltame- thrin, esfenvalerate, etofenprox, fenpropathrin, fenvalerate, cyhalothrin, lambda- cyhalothrin, permethrin, silafluofen, tau-fluval inate, tefluthrin, tralomethrin, alpha- cypermethrin or zeta-cypermethrin; arthropodal growth regulators: a) chitin synthesis inhibitors, e.g. benzoylureas, such as chlorfluazuron, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, teflubenzuron, triflumuron, buprofezin, diofenolan, hexythi- azox, etoxazole or clofentezine; b) ecdysone antagonists, such as halofenozide, methoxyfenozide or tebufenozide; c) juvenile hormone mimics, such as pyriproxyfen, methoprene or fenoxycarb; d) lipid biosynthesis inhibitors such as spirodiclofen; neonicotinoids, such as flonicamid, clothianidin, dinotefuran, imidacloprid, thia- methoxam, nitenpyram, nithiazine, acetamiprid or thiacloprid; additional unclassified insecticides, such as abamectin, acequinocyl, acetamiprid, amitraz, azadirachtin, bensultap, bifenazate, cartap, chlorfenapyr, chlordimeform, cyromazine, diafenthiuron, dinotefuran, diofenolan, emamectin, endosulfan, ethiprole, fenazaquin, fipronil, formetanate, formetanate hydrochloride, gamma- HCH, hydramethylnon, imidacloprid, indoxacarb, isoprocarb, metolcarb, pyridaben, pymetrozine, spinosad, tebufenpyrad, thiamethoxam, thiocyclam, XMC and xy- lylcarb;
• N-phenylsemicarbazones, such as those disclosed in EP-A 462 456 by the general formula (I), especially compounds of the general formula (A)
Figure imgf000067_0001
in which R2 and R3 represent, independently of one another, hydrogen, halogen, CN, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 haloalkyl or Ci-C4 haloalkoxy and R4 represents C1-C4 alkoxy, C1-C4 haloalkyl or C1-C4 haloalkoxy, e.g. compound IV, in which R2 represents 3-CF3, R3 represents 4-CN and R4 represents 4-OCF3.
Examples for plant growth regulators comprise chlormequat chloride, mepiquat chloride, prohexadione-calcium, trinexapac ethyl or the group of the gibberellins. These include, e.g. the gibberellin GA1, GA3, GA4, GA5 and GA7, and the like, and the corresponding exo-16,17-dihydrogibberellins, and also the derivatives thereof, e.g. the esters with C1-C4 carboxylic acids.
Water-soluble concentrates (SL, LS) comprise for example:
(a) 0.01 to 3% by weight, relative to the total weight of the composition, of an antimicrobial agent as defined above;
(b) 0.01 to 5% by weight, relative to the total weight of the composition, of an alkox- ylated amine (I) or a mixture of different alkoxylated amines (I) as defined above;
(c) 5 to 60% by weight, relative to the total weight of the composition, of the active substances;
(d) 5 to 15% by weight, relative to the total weight of the composition, of a wetting agent (e.g. alcohol alkoxylates);
(e) 3 to 15% by weight, relative to the total weight of the composition, of an antifreezing agent;
(f) water or a mixture of water and a water-soluble solvent (e.g. an alcohol) ad 100% by weight.
Emulsions (EW, EO, ES) comprise for example:
(a) 0.01 to 3% by weight, relative to the total weight of the composition, of an antimicrobial agent as defined above; (b) 0.01 to 5% by weight, relative to the total weight of the composition, of an alkox- ylated amine (I) or a mixture of different alkoxylated amines (I) as defined above;
(c) 5 to 40% by weight, relative to the total weight of the composition, of the active substance;
(d) 1 to 10% by weight, relative to the total weight of the composition, of one or more emulsifiers (e.g. calcium dodecylbenzenesulfonate and castor oil ethoxylate);
(e) 3 to 15% by weight, relative to the total weight of the composition, of an antifreezing agent;
(f) 20 to 40% by weight, relative to the total weight of the composition, of a waterinsoluble organic solvent (e.g. aromatic hydrocarbon);
(g) water ad 100% by weight.
Suspensions (SC, OD, FS) comprise for example:
(a) 0.01 to 3% by weight, relative to the total weight of the composition, of an antimicrobial agent as defined above;
(b) 0.01 to 5% by weight, relative to the total weight of the composition, of an alkoxylated amine (I) or a mixture of different alkoxylated amines (I) as defined above;
(c) 5 to 60% by weight, relative to the total weight of the composition, of the active substance;
(d) 2 to 10% by weight, relative to the total weight of the composition, of dispersants and/or wetting agents (e.g. sodium lignosulfonate and alcohol ethoxylate);
(e) 0.1 to 2% by weight, relative to the total weight of the composition, of a thickener (e.g. xanthan gum);
(f) 3 to 15% by weight, relative to the total weight of the composition, of an antifreezing agent;
(g) water ad 100% by weight.
For FS type composition up to 40 wt% binder (e.g. polyvinylalcohol) is contained.
Gels (GW, GF) comprise for example:
(a) 0.01 to 3% by weight, relative to the total weight of the composition, of an antimicrobial agent as defined above;
(b) 0.01 to 5% by weight, relative to the total weight of the composition, of an alkoxylated amine (I) or a mixture of different alkoxylated amines (I) as defined above;
(c) 5 to 50% by weight, relative to the total weight of the composition, of the active substance;
(d) 3 to 10% by weight, relative to the total weight of the composition, of one or more dispersants (e.g. sodium lignosulfonate);
(e) 1 to 5% by weight, relative to the total weight of the composition, of a thickener (e.g. carboxymethylcellulose);
(f) 3 to 15% by weight, relative to the total weight of the composition, of an antifreezing agent; (g) water ad 100% by weight.
Microemulsions (ME) comprise for example:
(a) 0.01 to 3% by weight, relative to the total weight of the composition, of an antimicrobial agent as defined above;
(b) 0.01 to 5% by weight, relative to the total weight of the composition, of an alkox- ylated amine (I) or a mixture of different alkoxylated amines (I) as defined above;
(c) 5 to 50% by weight, relative to the total weight of the composition, of the active substance;
(d) 5 to 30% by weight, relative to the total weight of the composition, of an organic solvent blend (e.g. fatty acid dimethylamide and cyclohexanone);
(e) 10 to 25% by weight, relative to the total weight of the composition, of surfactant blend (e.g. alcohol ethoxylate and arylphenol ethoxylate);
(f) 3 to 15% by weight, relative to the total weight of the composition, of an antifreezing agent;
(g) water ad 100% by weight.
The above crop protection compositions may optionally comprise further auxiliaries, such as 0.1-1 wt% other bactericides, 0.1-1 wt% anti-foaming agents, and 0.1-1 wt% colorants.
Pharmaceutical
Figure imgf000069_0001
Suitable pharmaceutical compositions may exist in a wide variety of forms, for example in the form of liquid preparations as a W/O, O/W, O/W/O, W/O/W or PIT emulsion and all kinds of microemulsions; in the form of a non-emulsified, water-based liquid, in the form of a gel, in the form of an oil, a cream, milk or lotion, in the form of a spray (spray with propellant gas or pump-action spray) or an aerosol, in the form of a foam, in the form of a paste, in the form of a wet wipe (such as for cleaning the nappy area).
The pharmaceutical compositions may be, for example, creams, gels, lotions, alcoholic and aqueous/alcoholic solutions, emulsions, wax/fat compositions, or ointments.
Personal care
Figure imgf000069_0002
Preserving personal care products from microbial degradation is imperative and simultaneously challenging, since most topical cosmetics and dermatological products contain significant amounts of water, thus providing a very hospitable environment for microbial growth. Many other ingredients in personal care products can also be a good source of nutrients to microbes. Moreover, shelf-life and pot life of personal care products are rather long as compared to, for example, food products. Generally, personal care products are neither sterilized and nor packed in hermetic conditions, and thus the presence of preservatives can hardly be dispensed with. On the other hand, the public regards preservatives in personal care products as problematic. The consumers expect the preservatives to be not only effective, but extremely mild during the whole shelf and pot life. Public opinion makes it very difficult to use formaldehyde donors, halogenated organic molecules and recently also parabens in personal care products. It is at least expected that the amounts of these preservatives is reduced to a minimum. Antimicrobials which are not or at least less hazardous, like 2- phenoxyethanol, are often not very effective and need to be used in rather high concentrations to achieve an acceptable antimicrobial effect. In personal care applications, high concentrations are however not acceptable. The present combination of antimicrobials (a) and alkoxylated amines (I) allows to reduce the amount of antimicrobial substantially, without compromising the desired antimicrobial effect.
This notwithstanding, in personal care compositions, the antimicrobial is preferably 2- phenoxyethanol.
Personal care compositions can be such for hygienic or cosmetic use. Examples for suitable personal care compositions are given above.
Suitable personal care compositions may exist in a wide variety of forms, for example in the form of liquid preparations as a W/O, O/W, O/W/O, W/O/W or PIT emulsion and all kinds of microemulsions; in the form of a non-emulsified, water-based liquid, in the form of a gel, in the form of an oil, a cream, milk or lotion, in the form of a spray (spray with propellant gas or pump-action spray) or an aerosol, in the form of a foam, in the form of a paste, in the form of a wet wipe (such as for cleaning the nappy area).
The personal care compositions may be, for example, creams, gels, lotions, alcoholic and aqueous/alcoholic solutions, emulsions, wax/fat compositions, or ointments.
Ingredients typically present in such personal care compositions and their amounts vary according to the specific formulation. Examples for such ingredients are solvents, surfactants, emulsifiers, rheology modifiers (generally thickeners), conditioners, emollients, skin caring ingredients, lubricants, fillers, antioxidants, dermatologically active ingredients, fragrances and water.
For instance, in form of water- and oil-containing emulsions (e.g. W/O, O/W, O/W/O and W/O/W emulsions or microemulsions) the preparations generally contain at least one oil component, at least one emulsifier, water and optionally at least one further cosmetically acceptable adjuvants; for example, from 0.1 to 30% by weight, preferably from 0.1 to 15% by weight and especially from 0.5 to 10% by weight, based on the total weight of the composition, from 1 to 60% by weight, especially from 5 to 50% by weight and preferably from 10 to 35% by weight, based on the total weight of the composition, of at least one oil component, from 0 to 30% by weight, especially from 1 to 30% by weight und preferably from 4 to 20% by weight, based on the total weight of the composition, of at least one emulsifier, from 10 to 90% by weight, especially from 30 to 90% by weight, based on the total weight of the composition, of water, and from 0 to 88.9% by weight, especially from 1 to 50% by weight, of further cosmetically acceptable adjuvants.
Preparation intended mainly for cleaning, such as soaps, shower gels and shampoos, contain at least one or more surfactants, often of the anionic type, optionally in combination with such of the zwitterionic type; and water. Furthermore, they generally contain at least one of following components: emulsifier, sequestrant, fragrance, pH modifier (generally an organic acid and/or an inorganic base), inorganic salt (mostly NaCI), dye,
Of special importance are cosmetic preparations for the hair, especially with the purpose of antidandruff treatment, especially hair-washing preparations in the form of shampoos, hair conditioners, hair-care preparations, e.g. pre-treatment preparations, hair tonics, styling creams, styling gels, pomades, hair rinses, treatment packs, intensive hair treatments, hair-straightening preparations, liquid hair-setting preparations, hair foams and hairsprays. Of special interest are hair-washing preparations in the form of shampoos. Of special interest are moreover shower gels.
Shampoos as well as shower gels generally contain water and at least one anionic surfactant.
Suitable anionic surfactants are principally all those described above in context with homecare and l&l compositions which are cosmetically acceptable. In shampoos and in shower gels, it is useful to use surfactants which are good foam-formers.
Examples of suitable anionic surfactants in this context are alkyl sulfates, alkyl ether sulphates, alkaryl sulfonates, alkanoyl isethionates, alkyl succinates, alkyl sulfosuccinates, alkyl ether sulfosuccinates, N-alkyl sarcosinates, alkyl phosphates, alkyl ether phosphates, and alkyl ether carboxylic acids and salts thereof, especially sodium, magnesium, ammonium and mono-, di- and triethanolamine salts. The alkyl and acyl groups generally contain from 8 to 18, preferably from 10 to 16 carbon atoms and may be unsaturated. The alkyl ether sulfates, alkyl ether sulfosuccinates, alkyl ether phosphates and alkyl ether carboxylic acids and salts thereof may contain from 1 to 20 ethylene oxide or propylene oxide units per molecule. Typical surfactants for use in shampoo compositions include sodium oleyl succinate, ammonium lauryl sulfosuccinate, sodium lauryl sulfate, sodium lauryl ether sulfate (sodium laureth sulfate), sodium lauryl ether sulfosuccinate, ammonium lauryl sulfate, ammonium lauryl ether sulfate, sodium dodecylbenzene sulfonate, triethanolamine dodecylbenzene sulfonate, sodium cocoyl isethionate, sodium lauryl isethionate, lauryl ether carboxylic acid and sodium N-lauryl sarcosinate. Mixtures of any of the foregoing anionic surfactants are also suitable. The overall amount of anionic surfactant in the shampoo compositions of the invention generally ranges from 0.5 to 45% by weight, e.g. from 1.5 to 35% by weight, based on the total weight of the composition.
The shampoo or shower gel composition can moreover include non-ionic, amphoteric and/or cationic co-surfactants, which help impart aesthetic, haptic, combing, physical or cleansing properties to the composition.
Suitable non-ionic surfactants are those listed above, e.g. ethoxylated fatty alcohols, mono- or di-alkyl alkanolamides, such as coco mono- or di-ethanolamide and coco monoisopropanolamide; or alkyl polyglycosides (APGs) such as Oramix NS10 ex Seppic; Plantaren 1200 and Plantaren 2000 ex Henkel. The overall amount of non-ionic surfactant in the shampoo or shower gel compositions of the invention generally ranges from 0.5 to 8% by weight, preferably from 2 to 5% by weight, based on the total weight of the composition.
Suitable amphoteric or zwitterionic surfactants are those listed above, e.g. alkyl amine oxides, alkyl betaines, alkyl amidopropyl betaines, alkyl sulfobetaines (sultaines), alkyl glycinates, alkyl carboxyglycinates, alkyl amphoacetates, alkyl amphopropionates, al- kylamphoglycinates, alkyl amidopropyl hydroxysultaines, acyl taurates and acyl glutamates, wherein the alkyl and acyl groups have from 8 to 19 carbon atoms. Specific examples are lauryl amine oxide, cocodimethyl sulfopropyl betaine, lauryl betaine, co- camidopropyl betaine and sodium cocoamphoacetate. Mixtures of the foregoing amphoteric or zwitterionic surfactants are also suitable. The overall amount of amphoteric or zwitterionic surfactant in the shampoo or shower gel compositions of the invention generally ranges from 0.5 to 8% by weight, preferably from 1 to 4% by weight, based on the total weight of the composition.
Suitable cationic polymers are those listed above. Examples are copolymers of vinyl monomers having cationic amine or quaternary ammonium functionalities with water soluble spacer monomers such as (meth)acrylamide, alkyl and dialkyl (methacrylamides, alkyl (meth)acrylate, vinyl caprolactone and vinyl pyrrolidine. The alkyl and dialkyl substituted monomers preferably have Ci-C?-alkyl groups, more preferably C1-C3- alkyl groups. Other suitable spacers include vinyl esters, vinyl alcohol, maleic anhydride, propylene glycol and ethylene glycol. The cationic amines can be primary, secondary or tertiary amines, depending upon the particular species and the pH of the composition. In general secondary and tertiary amines, especially tertiary, are preferred. Other examples are cationic polysaccharide polymers, such as cationic cellulose derivatives, cationic starch derivatives, and cationic guar gum derivatives. The overall amount of cationic surfactant in the shampoo or shower gel compositions of the invention generally ranges from 0.05 to 1% by weight, more preferably from 0.08 to 0.5% by weight, based on the total weight of the composition.
The total amount of surfactant (including any co-surfactant and/or any emulsifier) in a shampoo or shower gel composition is generally from 1 to 50% by weight, preferably from 2 to 40% by weight, more preferably from 10 to 25% by weight, based on the total weight of the composition.
Other components which may be present in the shampoo or shower gel are for example suspending agents, such as polyacrylic acids, cross-linked polymers of acrylic acid, copolymers of acrylic acid with a hydrophobic monomer, copolymers of carboxylic acidcontaining monomers and acrylic esters, cross-linked copolymers of acrylic acid and acrylate esters, heteropolysaccharide gums and crystalline long chain acyl derivatives, the latter being preferably selected from ethylene glycol stearate, alkanolamides of fatty acids having from 16 to 22 carbon atoms and mixtures thereof; fragrances, dyes and pigments, pH adjusting agents, pearlescers or opacifiers, viscosity modifiers, and salts, such as as NaCI; in shampoos moreover natural hair nutrients or dermatologically active ingredients, such as botanicals, fruit extracts, caffeine, panthenol, sugar derivatives, amino acids, such as hydrolized keratine or glycine, vegetable or hydrogenated vegetable oils.
In ready-to-use compositions in which the antimicrobial agent (in combination with the alkoxylated amine (I)) is to exert a preservative effect, the antimicrobial agent and the alkoxylated amine (I) are of course contained in a preservative effective amount denotes. This is an amount that is sufficient to reduce the cell population of an unwanted microorganism under a predetermined threshold value to obtain shelf-stability over a certain period of time.
Thus, a "preservative-effective amount" can be e.g. defined as an amount sufficient to reduce the cell population by, for example, at least one, preferably at least two, in particular at least three log orders of the at least one of following microorganisms: Alcali- geneses faecalis, Aspergillus niger, Burkholderia cepacia, Candida albicans, Escherichia coli, Pseudomonas aeruginosa, Pseudomonas putida and Staphylococcus aureus, and in particular at least one of following microorganisms: Alcaligeneses faecalis, Burkholderia cepacia, Escherichia coli, Pseudomonas aeruginosa, Pseudomonas putida and Staphylococcus aureus. Alternatively or additionally, a "preservative-effective amount" can be e.g. defined as an amount sufficient to reduce the cell population by, for example, at least one, preferably at least two, in particular at least three log orders of the at least one of following microorganisms: Aspergillus brasiliensis, Rhodotorula mucilaginosa and Yarrowia lipolytica.
The composition of the invention has a pH of preferably from 2 to 11, more preferably from 4 to 10, and in particular from 4 to 9.
In the following, some exemplary formulations of the invention are listed to illustrate typical compositions.
(I) All Purpose Cleaner 1
Figure imgf000075_0001
(II) All Purpose Cleaner 2
Figure imgf000075_0002
(Ill) All Purpose Cleaner 3
Figure imgf000076_0001
(IV) All Purpose Cleaner 4
Figure imgf000076_0002
(V) All Purpose cleaner 5
Figure imgf000077_0001
(VI) All Purpose Cleaner 6
Figure imgf000077_0002
(VII) Hard Surface Cleaner 1
Figure imgf000078_0001
(VIII) Hard Surface Cleaner 2
Figure imgf000078_0002
(IX) Surface cleaner spray 1
Figure imgf000079_0001
(X) Surface cleaner spray 2
Figure imgf000079_0002
(XI) Surface cleaner spray 3
Figure imgf000080_0001
(XII) Surface cleaner spray 4
Figure imgf000080_0002
(XIII) Surface cleaner spray 5
Figure imgf000081_0001
(XIV) Wet wipes 1
Figure imgf000081_0002
(XV) Wet wipes 2
Figure imgf000082_0001
(XVI) Wet Wipes 3 (for personal care)
Figure imgf000082_0002
(XVII) Window Cleaner
Figure imgf000083_0001
(XVIII) Toilet cleaner
Figure imgf000083_0002
(XIX) Shoe deodorant
Figure imgf000084_0001
(XX) Dishwashing liquid 1
Figure imgf000084_0002
(XXI) Dishwashing Liquid 2
Figure imgf000085_0001
(XXII) Dish washing liquid 3
Figure imgf000085_0002
(XXIII) Dishwashing liquid 4
Figure imgf000086_0001
(XXIV) Liquid Laundry Detergent 1
Figure imgf000086_0002
(XXV) Liquid Detergent 2
Figure imgf000087_0001
(XXVI) Liquid Laundry Detergent 3
Figure imgf000087_0002
(XXVII) Liquid Laundry Detergent 4
Figure imgf000088_0001
(XXVIII) Fabric Softener 1
Figure imgf000088_0002
(XXIX) Fabric Softener 2
Figure imgf000089_0001
(XXX) Fabric Softener 3
Figure imgf000089_0002
(XXXI) Fabric Softener 4
Figure imgf000090_0001
(XXXII) Polymer emulsion
Figure imgf000090_0002
(XXXIII) Cellulose pulp
Figure imgf000091_0001
(XXXIV) CaCO3 Slurry
Figure imgf000091_0002
(XXXV) Kaolin Slurry
Figure imgf000091_0003
(XXXVI) Starch solution
Figure imgf000092_0001
(XXXVII) Pigment Slurry
Figure imgf000092_0002
(XXXVIII) Paint
Figure imgf000093_0001
PERSONAL CARE FORMULATIONS (XXXIX) O/W Emulsion for skin care
Figure imgf000093_0002
(XL) W/0 Lotion
Figure imgf000094_0001
(XLI) Roll-on Deodorant
Figure imgf000095_0001
(XLII) Shower Gel
Figure imgf000095_0002
(XLIII) Shampoo
Figure imgf000096_0001
INDUSTRIAL LIQUIDS
(XLIV) Metal Working Fluid (in use)
Figure imgf000097_0001
(XLV) Drilling Mud 1
Figure imgf000097_0002
(XLVI) Drilling Mud 2
Figure imgf000098_0001
(XLVII) Workover Fluid used in Oilfield
Figure imgf000098_0002
(XLVIII) Cooling water
Figure imgf000099_0001
(XLIX) Plant protection Product 1
Figure imgf000099_0002
(L) Plant protection Product 2
Figure imgf000100_0001
In the above tables (I) to (L), “compound of formula (I)” means alkoxylated amine of the above-depicted formula (I). Preferably, in the alkoxylated amine (I) R1, R2 and R3 are independently -CH2CH2O-An-Bm-H, where Ra is methyl, m is 10 to 30 and n is 3 to 12; or m is 10 to 20 and n is 0. More preferably, in the alkoxylated amine (I) R1, R2 and R3 are independently -CH2CH2O-An-Bm-H, where Ra is methyl, m is 13 to 28 and n is 4 to 11 ; or m is 14 to 16 and n is 0. Specifically, in the alkoxylated amine (I) R1, R2 and R3 are independently -CH2CH2O-An-Bm-H, where Ra is methyl, m is 14 to 27 and n is 5 to 10; or m is 15 and n is 0. Very specifically, in the alkoxylated amine (I) R1, R2 and R3 are independently -CH2CH2O-An-Bm-H, where Ra is methyl, m is 14 and n is 5; or m is 15 and n is 0.
In each of the above formulations 1 to 10 in each of the above tables I to L one of the following antimicrobial agents is used in each case: 2-phenoxyethanol, phenoxyisopropanol, 4,4’-dichloro 2’-hydroxydiphenylether, 2-bromo-2-nitropropane-1 ,3-diol, glutaraldehyde, 2,4-dichlorobenzylalcohol, 1 ,3,5-tris-(2-hydroxyethyl)-1 ,3,5-hexahydrotriazine, formic acid and salts thereof, benzoic acid and salts thereof, sorbic acid and salts thereof, lactic acid and salts thereof, isothiazolinones selected from the group consisting of 1 ,2-benzisothiazol-3(2H)-one (BIT), 2-methyl-2H-isothiazol-3-one (MIT), 2-octyl- 2H-isothiazol-3-one (OIT), 5-chloro-2-methyl-2H-isothiazol-3-one (CMIT), and 2-butyl- benzo[d]isothiazol-3-one (BBIT); 3-iodo-2-propynylbutylcarbamate (IPBC), benzyl alcohol, pyridine-2-thiol 1 -oxide and salts thereof; 2,2-dibromo-2-cyanoacetamide (DBNPA), N-(3-aminopropyl)-N-dodecylpropane-1 ,3-diamine (Diamine), tetrakis(hy- droxymethyl)phosphonium sulphate(2:1) (THPS), 2,2-dithiobis[N-methylbenzamide] (DTBMA) and 2-bromo-2-(bromomethyl)pentanedinitril (DBDCB). Specifically, 2-phe- noxyethanol, 4,4’-dichloro 2’-hydroxydiphenylether (diclosan), 2-bromo-2-nitropropane- 1 ,3-diol, glutaraldehyde or 1 ,2-benzisothiazol-3(2H)-one (BIT) is used. More specifically, 2-phenoxyethanol, 2-bromo-2-nitropropane-1 ,3-diol, glutaraldehyde or 1 ,2-ben- zisothiazol-3(2H)-one (BIT) is used. Very specifically, 2-phenoxyethanol is used. In another more specific embodiment, phenoxyisopropanol is used.
Each of these antimicrobial agents is combined in each of the above formulations with one or more of the alkoxylated (I) as defined above. In particular, one of the following alkoxylated amines (I) is used as compound (I): an alkoxylated amine (I) wherein R1, R2 and R3 are independently -CH2CH2O-An-Bm-H, where Ra is methyl, m is 10 to 30 and n is 3 to 12; or m is 10 to 20 and n is 0. More particularly, one of the following alkoxylated amines (I) is used as compound (I): an alkoxylated amine (I) wherein R1, R2 and R3 are independently -CH2CH2O-An-Bm-H, where Ra is methyl, m is 13 to 28 and n is 4 to 11 ; or m is 14 to 16 and n is 0. Specifically, one of the following alkoxylated amines (I) is used as compound (I): an alkoxylated amine (I) wherein R1, R2 and R3 are independently - CH2CH2O-An-Bm-H, where Ra is methyl, m is 14 to 27 and n is 5 to 10; or m is 15 and n is 0. Very specifically, one of the following alkoxylated amines (I) is used as compound (I): an alkoxylated amine (I) wherein R1, R2 and R3 are independently -CF^CFW-An-Bm- H, where Ra is methyl, m is 14 and n is 5; or m is 15 and n is 0.
Specifically, in each of the above formulations 1 to 10 in each of the above tables I to L 2-phenoxyethanol is used as the antimicrobial agent and one of the following alkoxylated amines (I) is used as compound (I): an alkoxylated amine (I) wherein R1, R2 and R3 are independently -CH2CH2O-An-Bm-H, where Ra is methyl, m is 13 to 28 and n is 4 to 11 ; or m is 14 to 16 and n is 0. More specifically, in each of the above formulations 1 to 10 in each of the above tables I to L 2-phenoxyethanol is used as the antimicrobial agent and one of the following alkoxylated amines (I) is used as compound (I): an alkoxylated amine (I) wherein R1, R2 and R3 are independently -CH2CH2O-An-Bm-H, where Ra is methyl, m is 14 to 27 and n is 5 to 10; or m is 15 and n is 0.
Specifically, in each of the above formulations 1 to 10 in each of the above tables I to L 2-phenoxyethanol, bromo-2-nitropropane-1 ,3-diol, glutaraldehyde or 1 ,2-benzisothiazol- 3(2H)-one (BIT) is used as the antimicrobial agent and one of the following alkoxylated amines (I) is used as compound (I): an alkoxylated amine (I) wherein R1, R2 and R3 are independently -CH2CH2O-An-Bm-H, where Ra is methyl, m is 13 to 15 and n is 4 to 6. More specifically, in each of the above formulations 1 to 10 in each of the above tables I to L bromo-2-nitropropane-1 ,3-diol, glutaraldehyde or 1 ,2-benzisothiazol-3(2H)-one (BIT) is used as the antimicrobial agent and one of the following alkoxylated amines (I) is used as compound (I): an alkoxylated amine (I) wherein R1, R2 and R3 are independently -CH2CH2O-An-Bm-H, where Ra is methyl, m is 14 and n is 5. If a solvent is used in the above formulations, this is as defined above. Specifically, the solvent is ethanol, n-propanol, isopropanol, ethylene gycol, propylene glycol, ethylene glycol mono-n-butylether, propylene glycol mono-n-butylether, y-butyrolactone, y- valerolactone, y-octalactone, y-nonalactone or s-caprolactone.
In another specific embodiment, the solvent is or comprises N,N-dimethyllactamide, 1- butoxy-propan-2-ol, diethyleneglycolmono-n-butyl ether, y-valerolactone or a mixture thereof. If the solvent comprises N,N-dimethyllactamide, 1-butoxy-propan-2-ol, diethy- leneglycolmono-n-butyl ether, y-valerolactone or a mixture thereof, the solvent may further comprise one or more of ethanol, n-propanol, isopropanol, ethylene gycol, propylene glycol, ethylene glycol mono-n-butylether and propylene glycol mono-n-butylether.
In the above tables, the % w/w are relative to the overall weight of the respective composition.
The invention relates moreover to a kit of parts comprising at least two parts, where the first part comprises at least one antimicrobial agent as defined above; the second part comprises at least one alkoxylated amine (I) as defined above and optionally at least one organic solvent [of course different from the alkoxylated amine (I) and from said antimicrobial agent], preferably as defined above; and an optional third part comprises at least one organic solvent [of course different from the alkoxylated amine (I) and from said antimicrobial agent], preferably as defined above; where the first part does not comprise any alkoxylated amine (I); where the second part does not comprise any antimicrobial agent as defined above; where the optional third part does not comprise any antimicrobial agent as defined above nor any alkoxylated amine (I); and where the first and second parts contain the at least one antimicrobial agent as defined above and the at least one alkoxylated amine (I) in such amounts that when the first and the second part are mixed the resulting overall weight ratio is as defined above, i.e. 100:1 to 1 :10000, preferably from 50:1 to 1:2000, more preferably from 50:1 to 1 :1000, even more preferably from 50:1 to 1 :500, in particular from 20:1 to 1 :500, more particularly from 10:1 to 1 :450, even more particularly from 5:1 to 1:450, and specifically from 2:1 to 1 :450.
To be more specific, in case of 2-phenoxyethanol as antimicrobial agent, the resulting overall weight ratio of antimicrobial agent and alkoxylated amine (I) is preferably from 3:1 to 1:5, more preferably from 3:1 to 1 :3, even more preferably from 2.5:1 to 1:2.5, in particular from 2:1 to 1:2.5, specifically from 1.3:1 to 1 :2 and very specifically from 1:1 to 1:2.
To be more specific, in case of 2-bromo-2-nitropropane-1,3-diol, glutaraldehyde and 1,2-benzisothiazol-3(2H)one (BIT) as antimicrobial agent, the resulting overall weight ratio of antimicrobial agent and alkoxylated amine (I) is preferably from 1 :1 to 1 :500, more preferably from 1:1 to 1 :450, and in particular from 1:100 to 1 :450. While in the above-described compositions components (a) and (b) are present as a physical mixture, in a kit of parts they are formulated separately, but provided in such a form that they nevertheless form a functional unity. They form thus a true combination through a purpose-directed application. The functional unity is expressed for example in the fact that the parts contain the antimicrobial agent and the alkoxylated amine (I) in such amounts that when mixed, they result in the desired weight ratio. Another way to express functional unity may be a use instruction explaining the combined use of the two or more parts of the kit. Yet another way to express functional unity may be a physical connection. For instance, the different parts of the kit may be bond to each other via an adhesive tape or strap or any other type of tie, or may be assembled in a common container, such as a box, package, basket etc. or packed together in a plastic foil.
In a preferred embodiment, the kit of parts is a kit of two parts, where the first part comprises at least one antimicrobial agent as above; and the second part comprises at least one alkoxylated amine (I) as defined above and at least one organic solvent [different from the alkoxylated amine (I) and from said antimicrobial agent], where the organic solvent has preferably one of the above preferred meanings.
In an alternatively preferred embodiment, the kit of parts is a kit of three parts, where the first part comprises at least one antimicrobial agent as defined above; the second part comprises at least one alkoxylated amine (I) as defined above; and the third part comprises at least one organic solvent [different from the alkoxylated amine (I) and from said antimicrobial agent], where the organic solvent has preferably one of the above preferred meanings.
The invention relates moreover to the use of an alkoxylated amine (I) as defined above for enhancing the antimicrobial, in particular the preserving, activity of the antimicrobial agent as defined above, and in particular for enhancing the antimicrobial, in particular the preserving, activity of the antimicrobial agent in an aqueous liquid homecare composition as defined above.
Regarding preferred alkoxylated amines (I), antimicrobial agents, weight ratios thereof, compositions in which these are used, materials for which these are used, etc., reference is made to the above details.
Preferably, the invention relates to the use of an alkoxylated amine (I) as defined above for enhancing the antimicrobial, in particular the preserving, activity of 2-phenoxy- ethanol, 2-bromo-2-nitropropane-1 ,3-diol (bronopol), glutaraldehyde or 1 ,2-benzisothia- zol-3(2H)one (BIT); specifically of 2-phenoxyethanol. More preferably, the invention relates to the use of an alkoxylated amine (I), wherein R1, R2 and R3 are independently -CH2CH2O-An-Bm-H, where Ra is methyl, m is 10 to 30 and n is 3 to 12; or m is 10 to 20 and n is 0, for enhancing the antimicrobial, in particular the preserving, activity of 2-phenoxyethanol, 2-bromo-2-nitropropane-1 ,3-diol (bronopol), glutaraldehyde or 1 ,2-benzisothiazol-3(2H)one (BIT); specifically of 2-phe- noxyethanol. Even more preferably, the invention relates to the use of an alkoxylated amine (I), wherein R1, R2 and R3 are independently -CH2CH2O-An-Bm-H, where Ra is methyl, m is 13 to 28 and n is 4 to 11 ; or m is 14 to 16 and n is 0, for enhancing the antimicrobial, in particular the preserving, activity of 2-phenoxyethanol, 2-bromo-2-nitro- propane-1 ,3-diol (bronopol), glutaraldehyde or 1 ,2-benzisothiazol-3(2H)one (BIT); specifically of 2-phenoxyethanol. In particular, the invention relates to the use of an alkoxylated amine (I), wherein R1, R2 and R3 are independently -CH2CH2O-An-Bm-H, where Ra is methyl, m is 14 to 27 and n is 5 to 10; or m is 15 and n is 0, for enhancing the antimicrobial, in particular the preserving, activity of 2-phenoxyethanol, 2-bromo-2-nitro- propane-1 ,3-diol (bronopol), glutaraldehyde or 1 ,2-benzisothiazol-3(2H)one (BIT); specifically of 2-phenoxyethanol.
Specifically, the invention relates to the use of an alkoxylated amine (I), wherein R1, R2 and R3 are independently -CH2CH2O-An-Bm-H, where Ra is methyl, m is 14 to 27 and n is 5 to 10; or m is 14 to 16 and n is 0, for enhancing the antimicrobial, in particular the preserving, activity of 2-phenoxyethanol. Very specifically, the invention relates to the use of an alkoxylated amine (I), wherein R1, R2 and R3 are independently -CH2CH2O- An-Bm-H, where Ra is methyl, m is 14 and n is 5; or m is 15 and n is 0, for enhancing the antimicrobial, in particular the preserving, activity of 2-phenoxyethanol.
Specifically, the invention relates to the use of an alkoxylated amine (I), wherein R1, R2 and R3 are independently -CH2CH2O-An-Bm-H, where Ra is methyl, m is 13 to 15 and n is 4 to 6; or m is 14 to 16 and n is 0, for enhancing the antimicrobial, in particular the preserving, activity of 2-phenoxyethanol, 2-bromo-2-nitropropane-1 ,3-diol (bronopol), glutaraldehyde or 1 ,2-benzisothiazol-3(2H)one (BIT). Very specifically, the invention relates to the use of an alkoxylated amine (I), wherein R1, R2 and R3 are independently - CH2CH2O-An-Bm-H, where Ra is methyl, m is 14 and n is 5, for enhancing the antimicrobial, in particular the preserving, activity of 2-bromo-2-nitropropane-1 ,3-diol (bronopol), glutaraldehyde or 1 ,2-benzisothiazol-3(2H)one (BIT).
The antimicrobial activity is in particular directed against fungi and bacteria as they typically occur in the compositions to be preserved against attack/infestation by microbes or on substrates, surfaces or materials to be disinfected, some few examples for fungi being Aspergillus brasiliensis, Rhodotorula mucilaginosa or Yarrowia lipolytica, and some few examples for bacteria being Escherichia coli, Alcaligenes faecalis, Pseudomonas aeruginosa, Staphylococcus aureus, Burkholderia cepacia, Pseudomonas putida, to name just a few. The invention is now illustrated by the following examples.
EXAMPLES
Alkoxylated amine (I):
Plurafac® LF 1430 from BASF (abbreviated as PLF): Triethanolamine alkoxylated with 5 EO on average and 14 PO on average per OH group of triethanolamine; to be more precise a compound (I) wherein R1, R2 and R3 are -CH2CH2O-An-Bm-H, where Ra is methyl, m is 14 and n is 5.
TEA-15 PO: Triethanolamine alkoxylated with 15 PO on average per OH group of triethanolamine, to be more precise a compound (I) wherein R1, R2 and R3 are - CH2CH2O-An-Bm-H, where Ra is methyl, m is 15 and n is 0.
TEA-20PO/5EO: Triethanolamine alkoxylated with 5 EO on average and 20 PO on average per OH group of triethanolamine; to be more precise a compound (I) wherein R1, R2 and R3 are -CH2CH2O-An-Bm-H, where Ra is methyl, m is 20 and n is 5.
TEA-20PO/7.5EO: Triethanolamine alkoxylated with 7.5 EO on average and 20 PO on average per OH group of triethanolamine; to be more precise a compound (I) wherein R1, R2 and R3 are -CH2CH2O-An-Bm-H, where Ra is methyl, m is 20 and n is 7.5.
TEA-27PO/10EO: Triethanolamine alkoxylated with 10 EO on average and 27 PO on average per OH group of triethanolamine; to be more precise a compound (I) wherein R1, R2 and R3 are -CH2CH2O-An-Bm-H, where Ra is methyl, m is 27 and n is 10
Solvents:
A: y-Valerolactone
B: N,N-Dimethyllactamide
C: Butyldiglycol : diethylene glycol-mono-n-butyl ether
D: Butoxy-2-propanol: 1-butoxy-2-propanol; propylene glycol-mono-n-butyl ether
All solvents are commercially available.
Example 1 Antimicrobial activity against fungi
1.1 Preservative activity in a phosphate buffer solution using 2-phenoxyethanol (PE) as antimicrobial agent in combination with PLF
A phosphate buffer solution of pH 7.0 was used.
The samples were contaminated with a fungal mix consisting of:
Aspergillus brasiliensis DSM 1988
Rhodotorula mucilaginosa DSM 13621
Yarrowia lipolytica DSM 8218 The samples were inoculated with the fungal mix at day 0 to obtain 1 - 3 x10E+05 CFU/ml inoculation in the test sample consisting of the above-defined phosphate buffer solution and stored at 25°C for 7 days. CFU was determined at day 7.
Any CFU value at d7 obtained with a phosphate buffer solution sample of the invention containing 2-phenoxyethanol (PE) and Plurafac® LF 1430 (PLF) (phosphate buffer solution + 0.5% by weight of PE + 1.0% by weight of PLF) lower than the respective value of the “comparative 1” example (phosphate buffer solution + 0.5% by weight of PE) or the “comparative 2” example (phosphate buffer solution + 1.0% by weight of PLF) indicates a better performance of the inventive combination of 2-phenoxyethanol with the alkoxylated amine. All percentages are % by weight and are relative to the total weight of the respective composition (here the phosphate buffer solution sample).
Table 1.1
Figure imgf000106_0001
The results at d7 show that the combination of 2-phenoxyethanol and alkoxylated amine overadditively enhances the preservative activity of 2-phenoxyethanol alone.
1.2 Preservative activity in a phosphate buffer solution using 2-phenoxyethanol (PE) as antimicrobial agent in combination with PLF or TEA-15 PO
A phosphate buffer solution of pH 7.0 was used.
The samples were contaminated with a fungal mix consisting of:
Aspergillus brasiliensis DSM 1988
Rhodotorula mucilaginosa DSM 13621
Yarrowia lipolytica DSM 8218
The samples were inoculated with the fungal mix at day 0 and day 7 to obtain 1 - 3 x10E+05 CFU/ml inoculation in the test sample consisting of the above-defined phosphate buffer solution and stored at 25°C for 21 days. CFU was determined before reinoculation at day 7, and at day 14 and day 21.
Any CFU value at d7, d14 and d21 obtained with a phosphate buffer solution sample of the invention containing 2-phenoxyethanol (PE) and Plurafac® LF 1430 (PLF) or TEA- 15 PO lower than the respective value of the “comparative 1” example (phosphate buffer solution + 0.5% by weight of 2-phenoxyethanol), “comparative 2” example (phosphate buffer solution + 1.0% PLF) or “comparative 3” example (phosphate buffer solution + 1.0% TEA-15 PO) indicates a better performance of the inventive combination of 2-phenoxyethanol with the alkoxylated amine. All percentages are % by weight and are relative to the total weight of the respective composition (here the phosphate buffer solution sample).
Table 1.2
Figure imgf000107_0001
The results at d7, d14 and d21 show that the combination of 2-phenoxyethanol and alkoxylated amine overadditively enhances the preservative activity of 2-phenoxy- ethanol alone.
1.3 Preservative activity in a hard surface cleaner composition using 2-phenoxy- ethanol (PE) as antimicrobial agent in combination with PLF
A manual hard surface cleaner (HSC) of pH 7.0 containing the following components was used:
Figure imgf000107_0002
The samples were contaminated with a fungal mix consisting of: Aspergillus brasiliensis DSM 1988 Rhodotorula mucilaginosa DSM 13621 Yarrowia lipolytica DSM 8218
The samples were inoculated with the fungal mix at day 0 and 7 to obtain 1 - 3 x10E+05 CFU/ml inoculation in the test sample consisting of the above-defined hard surface cleaner HSC and stored at 25°C for 14 days. CFU was determined before re-inoculation at day 7, and on day 14.
Any CFU value at d7 or d14 obtained with a HSC sample of the invention containing 2- phenoxyethanol (PE) and Plurafac® LF 1430 (PLF) (HSC + 1.0% PE + 1.0% of PLF) lower than the respective value of the “comparative 1” example (HSC + 1.0% by weight of 2-phenoxyethanol) or the “comparative 2” example (HSC + 2.0% by weight of PLF) indicates a better performance of the inventive combination of 2-phenoxyethanol with the alkoxylated amine. All percentages are % by weight and are relative to the total weight of the respective composition (here the HSC sample).
Table 1.3
Figure imgf000108_0001
The results at d7 and d14 show that the combination of 2-phenoxyethanol and alkoxylated amine overadditively enhances the preservative activity of 2-phenoxyethanol alone.
1.4 Preservative activity in a surfactant-containing phosphate buffer solution using 2- phenoxyethanol (PE) as antimicrobial agent in combination with PLF
A phosphate buffer solution of pH 7.0 was used. Where indicated in table 1.4 below, this contained additionally 1.5% by weight of the following surfactant:
Surfactant:
Lutensol XP 70 - C10 alcohol ethoxylated with 7 EO from BASF
The samples were contaminated with a fungal mix consisting of:
Aspergillus brasiliensis DSM 1988
Rhodotorula mucilaginosa DSM 13621
Yarrowia lipolytica DSM 8218 The samples were inoculated with the fungal mix at day 0 to obtain 1 - 3 x10E+05 CFU/ml inoculation in the test sample consisting of the above-defined phosphate buffer solution and stored at 25°C for 7 days. CFU was determined at day 7.
Any CFU value at d7 obtained with a surfactant-containing phosphate buffer solution sample containing 2-phenoxyethanol (PE) and Plurafac® LF 1430 (PLF) lower than the respective value of the comparative examples indicates a better performance of the inventive combination of 2-phenoxyethanol with the alkoxylated amine. All percentages are % by weight and are relative to the total weight of the respective composition (here the phosphate buffer solution sample).
Table 1.4
Figure imgf000109_0001
The results at d7 show that the combination of 2-phenoxyethanol and alkoxylated amine overadditively enhances the preservative activity of 2-phenoxyethanol alone. Moreover, the comparison of comparative example 4 with comparative example 1 shows that the effect of PE is thwartet by the presence of Lutensol XP 70. This thwarting effect is completely overcome by the presence of PLF, as show the results obtained with the composition of the invention.
1.5 Preservative activity in a phosphate buffer solution using 2-phenoxyethanol (PE) as antimicrobial agent in combination with various alkoxylated amines
A phosphate buffer solution of pH 7.0 was used.
The samples were contaminated with a fungal mix consisting of:
Aspergillus brasiliensis DSM 1988
Rhodotorula mucilaginosa DSM 13621
Yarrowia lipolytica DSM 8218 The samples were inoculated with the fungal mix at days 0 and 7 to obtain 1 - 5 x10E+05 CFU/ml inoculation in the test sample consisting of the above-defined phosphate buffer solution and stored at 25°C for 14 days. CFU was determined at day 7 before re-inoculation, and at day 14.
Any CFU value at d7 and d14 obtained with a phosphate buffer solution sample of the invention containing 2-phenoxyethanol (PE) and the indicated alkoxylated amine (phosphate buffer solution + 0.5% by weight of PE + 0.5% by weight of the indicated alkoxylated amine) lower than the respective value of the “comparative 1” example (phosphate buffer solution + 0.5% by weight of PE) or the “comparative 2” to “comparative 4” examples (phosphate buffer solution + 1 .0% by weight of the indicated alkoxylated amine) indicates a better performance of the inventive combination of 2-phenoxyethanol with the alkoxylated amine. All percentages are % by weight and are relative to the total weight of the respective composition (here the phosphate buffer solution sample).
Table 1.5
Figure imgf000110_0001
The results at d7 and d14 show that the combination of 2-phenoxyethanol and alkoxylated amine overadditively enhances the preservative activity of 2-phenoxyethanol alone.
1.6 Preservative activity in a phosphate buffer solution using 2-bromo-2-nitropro- pane-1 ,3-diol (bronopol) as antimicrobial agent in combination with PLF
A phosphate buffer solution of pH 7.0 was used. The samples were contaminated with a fungal mix consisting of:
Aspergillus brasiliensis DSM 1988
Rhodotorula mucilaginosa DSM 13621
Yarrowia lipolytica DSM 8218
The samples were inoculated with the fungal mix at days 0 and 7 to obtain 1 - 5 x10E+05 CFU/ml inoculation in the test sample consisting of the above-defined phosphate buffer solution and stored at 25°C for 14 days. CFU was determined at day 7 before re-inoculation, and at day 14.
Any CFU value at d7 and d14 obtained with a phosphate buffer solution sample of the invention containing bronopol and Plurafac® LF 1430 (PLF) lower than the respective value of the “comparative 1” example (phosphate buffer solution + 40 ppm bronopol), or “comparative 2” example (phosphate buffer solution + 1.0% PLF) indicates a better performance of the inventive combination of bronopol with the alkoxylated amine. All percentages are % by weight and are relative to the total weight of the respective composition (here the phosphate buffer solution sample), ppm is also by weight and relative to the total weight of the respective composition (here the phosphate buffer solution sample).
Table 1.6
Figure imgf000111_0001
The results at d7 and d14 show that the combination of bronopol and alkoxylated amine overadditively enhances the preservative activity of bronopol alone.
1.7 Preservative activity in a phosphate buffer solution using 1 ,2-benzisothiazol- 3(2H)-one (BIT) as antimicrobial agent in combination with PLF
A phosphate buffer solution of pH 7.0 was used.
The samples were contaminated with a fungal mix consisting of:
Aspergillus brasiliensis DSM 1988 Rhodotorula mucilaginosa DSM 13621 Yarrowia lipolytica DSM 8218
The samples were inoculated with the fungal mix at day 0 to obtain 1 - 5 x10E+05 CFU/ml inoculation in the test sample consisting of the above-defined phosphate buffer solution and stored at 25°C for 7 days. CFU was determined at day 7.
Any CFU value at d7 obtained with a phosphate buffer solution sample of the invention containing BIT and Plurafac® LF 1430 (PLF) lower than the respective value of the “comparative 1” example (phosphate buffer solution + 25 ppm BIT) or “comparative 2” example (phosphate buffer solution + 1.0% PLF) indicates a better performance of the inventive combination of BIT with the alkoxylated amine. All percentages are % by weight and are relative to the total weight of the respective composition (here the phosphate buffer solution sample), ppm is also by weight and relative to the total weight of the respective composition (here the phosphate buffer solution sample).
Table 1.7
Figure imgf000112_0001
The results at d7 show that the combination of BIT and alkoxylated amine overaddi- tively enhances the preservative activity of BIT alone.
1.8 Preservative activity in PEG 6000 (50% solution in water) using 2-phenoxy- ethanol (PE) as antimicrobial agent in combination with PLF and additionally solvent A (y-valerolactone)
A 50% polyethylene glycol 6000 (PEG 6000) solution of pH 7.0 was used.
The samples were contaminated with Aspergillus brasiliensis DSM 1988
The samples were inoculated with the fungal mix at days 0 and 15 to obtain 1 - 3 x10E+05 CFU/ml inoculation in the test sample consisting of the above-defined PEG solution and stored at 25°C for 7 days. CFU was determined at days 0, 2, 7, 14, 15 and 29.
Table 1.8
Figure imgf000113_0001
As the results show, the presence of solvent A further enhances and accelerates the preservative activity of the combination of PE + PLF. 1.9 Preservative activity in PEG 6000 (50% solution in water) using 2-phenoxy- ethanol (PE) as antimicrobial agent in combination with PLF and additionally solvent B (N,N-dimethyllactamide) or solvent C (butyldiglycol) or solvent D (butoxy-2-propanol)
A 50% polyethylene glycol 6000 (PEG 6000) solution of pH 7.0 was used.
The samples were contaminated with Aspergillus brasiliensis DSM 1988
The samples were inoculated with the fungal mix at days 0 and 15 to obtain 1 - 3 x10E+05 CFU/ml inoculation in the test sample consisting of the above-defined PEG so- lution and stored at 25°C for 7 days. CFU was determined at days 0, 2, 7, 14, 15 and 29.
Table 1.9
Figure imgf000113_0002
Figure imgf000114_0001
As the results show, the presence of solvent B, C or D further enhances and accelerates the preservative activity of the combination of PE + PLF.
Example 2 Antimicrobial activity against bacteria
2.1 Preservative activity in a phosphate buffer solution using 2-phenoxyethanol (PE) as antimicrobial agent in combination with PLF
A phosphate buffer solution of pH 7.0 was used.
The samples were contaminated with a bacterial mix consisting of:
Escherichia coli DSM 1576
Alcaligenes faecalis DSM 13644
Pseudomonas aeruginosa ATCC 15442
Staphylococcus aureus ATCC 6538
Burkholderia cepacia DSM 7288
Pseudomonas putida DSM 12735
The samples were inoculated with the bacterial mix at day 0 to obtain 10E+06 to 10E+07 CFU/ml inoculation in the test samples and stored at 25°C for 7 days. CFU was determined at day 7. Any CFU value at d7 obtained with a phosphate buffer solution sample of the invention containing 2-phenoxyethanol (PE) and Plurafac® LF 1430 (PLF) (phosphate buffer solution + 0.5% by weight of PE + 1.0% by weight of PLF) lower than the respective value of the “comparative 1” example (phosphate buffer solution + 0.5% by weight of PE) or the “comparative 2” example (phosphate buffer solution + 1.0% by weight of PLF) indicates a better performance of the inventive combination of 2-phenoxyethanol with the alkoxylated amine. All percentages are % by weight and are relative to the total weight of the respective composition (here the phosphate buffer solution sample).
Table 2.1
Figure imgf000115_0001
The results at d7 show that the combination of 2-phenoxyethanol and alkoxylated amine overadditively enhances the preservative activity of 2-phenoxyethanol alone.
2.2 Preservative activity in a phosphate buffer solution using 1 ,2-benzisothiazol- 3(2H)-one (BIT) as antimicrobial agent in combination with PLF
A phosphate buffer solution of pH 7.0 was used.
The samples were contaminated with a bacterial mix consisting of:
Escherichia coli DSM 1576
Alcaligenes faecalis DSM 13644
Pseudomonas aeruginosa ATCC 15442
Staphylococcus aureus ATCC 6538
Burkholderia cepacia DSM 7288
Pseudomonas putida DSM 12735
The samples were inoculated with the bacterial mix at day 0 to obtain 10E+06 to 10E+07 CFU/ml inoculation in the test samples and stored at 25°C for 7 days. CFU was determined at day 7.
Any CFU value at d7 obtained with a phosphate buffer solution sample of the invention containing benzoisothiazolinone (BIT) and Plurafac® LF 1430 (PLF) (phosphate buffer solution + 75 ppm BIT + 1 .0% by weight of PLF) lower than the respective value of the “comparative 1” example (phosphate buffer solution + 75 ppm of BIT) or the “comparative 2” example (phosphate buffer solution + 1.0% by weight of PLF) indicates a better performance of the inventive combination of BIT with the alkoxylated amine. All percentages are % by weight and are relative to the total weight of the respective composition (here the phosphate buffer solution sample), ppm is also by weight and relative to the total weight of the respective composition (here the phosphate buffer solution sample).
Table 2.2
Figure imgf000116_0001
The results at d7 show that the combination of BIT and alkoxylated amine overaddi- tively enhances the preservative activity of BIT alone.
2.3 Preservative activity in a phosphate buffer solution using glutaraldehyde (used as 50% solution in water) as antimicrobial agent in combination with PLF
A phosphate buffer solution of pH 7.0 was used.
The samples were contaminated with a bacterial mix consisting of: Escherichia coli DSM 1576
Alcaligenes faecalis DSM 13644
Pseudomonas aeruginosa ATCC 15442
Staphylococcus aureus ATCC 6538
Burkholderia cepacia DSM 7288
Pseudomonas putida DSM 12735
The samples were inoculated with the bacterial mix at day 0 to obtain 10E+06 to 10E+07 CFU/ml inoculation in the test samples and stored at 25°C for 7 days. CFU was determined at day 7.
Any CFU value at d7 obtained with a phosphate buffer solution sample of the invention containing glutaraldehyde 50% and Plurafac® LF 1430 (PLF) (phosphate buffer solution + 50 ppm glutaraldehyde 50% + 1 .0% by weight of PLF) lower than the respective value of the “comparative 1” example (phosphate buffer solution + 50 ppm of glutaraldehyde 50%) or the “comparative 2” example (phosphate buffer solution + 1.0% by weight of PLF) indicates a better performance of the inventive combination of glutaraldehyde with the alkoxylated amine. All percentages are % by weight and are relative to the total weight of the respective composition (here the phosphate buffer solution sample), ppm is also by weight and relative to the total weight of the respective composition (here the phosphate buffer solution sample).
Table 2.3
Figure imgf000117_0001
The results at d7 show that the combination of glutaraldehyde and alkoxylated amine overadditively enhances the preservative activity of glutaraldehyde alone.

Claims

Claims
1. A composition comprising
(a) at least one antimicrobial agent selected from the group consisting of 2-phenoxyethanol, phenoxyisopropanol, 4,4’-dichloro 2’-hydroxydiphe- nylether, 2-bromo-2-nitropropane-1 ,3-diol, glutaraldehyde, 2,4-dichloroben- zylalcohol, 1 ,3,5-tris-(2-hydroxyethyl)-1 ,3,5-hexahydrotriazine, formic acid and salts thereof, benzoic acid and salts thereof, sorbic acid and salts thereof, lactic acid and salts thereof, isothiazolinones selected from the group consisting of 1 ,2-benzisothiazol-3(2H)-one (BIT), 2-methyl-2H-isothi- azol-3-one (MIT), 2-octyl-2H-isothiazol-3-one (OIT), 5-chloro-2-methyl-2H- isothiazol-3-one (CMIT), and 2-butyl-benzo[d]isothiazol-3-one (BBIT); 3- iodo-2-propynylbutylcarbamate (IPBC), benzyl alcohol, pyridine-2-thiol 1- oxide and salts thereof; 2,2-dibromo-2-cyanoacetamide (DBNPA), N-(3- aminopropyl)-N-dodecylpropane-1 ,3-diamine (Diamine), tetrakis(hy- droxymethyl)phosphonium sulphate(2:1) (THPS), 2,2-dithiobis[N- methylbenzamide] (DTBMA), 2-bromo-2-(bromomethyl)pentanedinitril (DBDCB); and mixtures thereof; and
(b) an alkoxylated amine of the formula (I)
NR1R2R3 (I) where
R1 is -CH2CH2O-An-Bm-H; -CH2CH2O-Bm-An-H or -CH2CH2O-Em+n-H; where
A is -CH2CH2O-;
B is -CH(Ra)-CH2-O- or -CH2-CH(Ra)-O-;
E is randomly distributed A and B;
Ra is Ci-C -alkyl; m is 0 to 30; and n is 0 to 15; where the sum of m + n is 5 to 40; and
R2 and R3 have independently one of the definitions given for R1 or are Ci- Cis-alkyl.
2. The composition according to claim 1 , where the antimicrobial agent is selected from the group consisting of 2-phenoxyethanol, phenoxyisopropanol, 4,4’-di- chloro 2’-hydroxydiphenylether, 2-bromo-2-nitropropane-1 ,3-diol, glutaraldehyde, benzoic acid and salts thereof and isothiazolinones selected from the group consisting of 1 ,2-benzisothiazol-3(2H)-one (BIT), 2-methyl-2H-isothiazol-3-one (MIT), 2-octyl-2H-isothiazol-3-one (OIT), 5-chloro-2-methyl-2H-isothiazol-3-one (CMIT) and 2-butyl-benzo[d]isothiazol-3-one (BBIT); and preferably from the group consisting of 2-phenoxyethanol, phenoxyisopropanol, 4,4’-dichloro 2’-hydroxydiphe- nylether, 2-bromo-2-nitropropane-1 ,3-diol and 1 ,2-benzisothiazol-3(2H)one (BIT).
3. The composition according to claim 2, where the antimicrobial agent is selected from the group consisting of 2-phenoxyethanol, 2-bromo-2-nitropropane-1 ,3-diol, glutaraldehyde and 1 ,2-benzisothiazol-3(2H)one (BIT).
4. The composition according to claim 3, where the antimicrobial agent is 2-phenox- yethanol.
5. The composition according to any of the preceding claims, where R2 and R3 have independently one of the meanings of R1.
6. The composition according to any of the preceding claims, where Ra is methyl.
7. The composition according to any of the preceding claims, where m is 10 to 30 and n is 3 to 12; or m is 10 to 25 and n is 0.
8. The composition according to any of the preceding claims, where R1 is -CH2CH2O-An-Bm-H.
9. The composition according to any of the preceding claims, where the antimicrobial agent and the alkoxylated amine are present in an overall weight ratio of from 100:1 to 1 :10000, preferably from 50:1 to 1 :2000, more preferably from 50:1 to 1 :1000, even more preferably from 50:1 to 1 :500, particularly preferably from 20:1 to 1 :500, in particular from 10:1 to 1 :500, specifically from 2:1 to 1 :450.
10. The composition according to claim 9, where in case that the antimicrobial agent is 2-phenoxyethanol, 2-phenoxyethanol and the alkoxylated amine are present in an overall weight ratio of from 3:1 to 1 :3, preferably from 2.5:1 to 1 :2.5, and specifically from 2:1 to 1 :2.
11. The composition according to claim 9, where in case that the antimicrobial agent is selected from the group consisting of 2-bromo-2-nitropropane-1 ,3-diol, glutaraldehyde and 1 ,2-benzisothiazol-3(2H)one (BIT), said antimicrobial agent and the alkoxylated amine are present in an overall weight ratio of from 1 :1 to 1 :500, preferably from 1 :1 to 1 :450, and more preferably from 1 :100 to 1 :450.
12. The composition according to any of the preceding claims, where the antimicrobial agent is selected from the group consisting of 2-phenoxyethanol, 2-bromo-2- nitropropane- 1 ,3-diol, glutaraldehyde and 1 ,2-benzisothiazol-3(2H)one (BIT); in the alkoxylated amine of the formula (I) R1, R2 and R3 are independently -CH2CH2O-An-Bm-H, where Ra is methyl, m is 10 to 30 and n is 3 to 12; or m is 10 to 20 and n is 0; and the antimicrobial agent and the alkoxylated amine are present in an overall weight ratio of from 3:1 to 1 :500; where preferably in the alkoxylated amine of the formula (I) R1, R2 and R3 are independently -CH2CH2O-An-Bm-H, where Ra is methyl, m is 14 to 27 and n is 5 to 10; or m is 15 and n is 0; and the antimicrobial agent and the alkoxylated amine are present in an overall weight ratio of from 2:1 to 1 :450.
13. The composition according to claim 12, where the antimicrobial agent is 2-phe- noxyethanol; in the alkoxylated amine of the formula (I) R1, R2 and R3 are independently -CH2CH2O-An-Bm-H, where Ra is methyl, m is 10 to 30, preferably 14 to 27, and n is 3 to 12, preferably 5 to 10; or m is 10 to 20, preferably 15, and n is 0; and 2-phenoxyethanol and the alkoxylated amine are present in an overall weight ratio of from 3:1 to 1 :3, preferably from 2.5:1 to 1 :2.5, and more preferably from 2:1 to 1 :2.
14. The composition according to claim 12, where the antimicrobial agent is selected from the group consisting of 2-bromo-2-nitropropane-1 ,3-diol, glutaraldehyde and 1 ,2-benzisothiazol-3(2H)one (BIT); in the alkoxylated amine of the formula (I) R1, R2 and R3 are independently -CH2CH2O-An-Bm-H, where Ra is methyl, m is 10 to 20, preferably 14, and n is 3 to 8, preferably 5; and said antimicrobial agent and the alkoxylated amine are present in an overall weight ratio of from 1 :1 to 1 :500, preferably from 1 :1 to 1 :450, and more preferably from 1 :100 to 1 :450.
15. The composition according to any of the preceding claims, further comprising (c) at least one organic solvent selected from the group consisting of
(c.1) carboxamides of the formula (C-1)
Figure imgf000120_0001
where
R4 is hydrogen or Ci-Cs-alkyl;
R5 is Ci-Cs-alkyl; and
R6 is Ci-Cs-alkyl or Ci-Cs-hydroxyalkyl;
(c.2) carboxylic esters of the formula (C-2)
Figure imgf000121_0001
(C- 2) where
R6 is Ci-Cs-alkyl or Ci-Cs-hydroxyalkyl; and
R7 is Ci-C -alkyl;
(c.3) Cs-Cs-alkanols;
(c.4) Cs-Cs-alkanediols;
(c.5) Ci-Cs-alkylmonoethers of C2-Cs-alkanediols;
(c.6) diethylene glycol, dipropylene glycol, a polyethylene glycol with up to
10 repeat units or a polypropylene glycol with up to 10 repeat units;
(c.7) Ci-Cs-alkylmonoethers of diethylene glycol or dipropylene glycol;
(c.8) lactones of formula (C-8)
Figure imgf000121_0002
where R8 is Ci-Cs-alkyl;
(c.9) dioxolanes of the formula (C-9)
(C- 9)
Figure imgf000121_0003
where
R9 and R10 are independently Ci-C4-alkyl or form together an oxo group; and
R11 is Ci-C4-alkyl or Ci-C4-hydroxyalkyl; and
(c.10) mono-, di- or triesters of glycerol with Ci-C4-carboxylic acids.
16. The composition according to claim 15, where the organic solvent of component (c) is selected from the group consisting of
(c.1) the carboxamide of the formula (C-1), where R4 and R5 are methyl, and R6 is 1 -hydroxyethyl;
(c.5) Cs-Cs-alkylmonoethers of C2-C3-alkanediols, in particular 1-butoxy-propan- 2-ol; (c.7) Ci-Ce-alkylmonoethers of diethylene glycol or dipropylene glycol, in particular diethyleneglycolmono-n-butyl ether; and
(c.8) the lactone of formula (C-8), where R8 is methyl.
17. The composition according to any of claims 15 and 16, where the antimicrobial agent and the organic solvent of component (c) are present in an overall weight ratio of from 10:1 to 1:10, preferably from 5:1 to 1 :5, more preferably from 3:1 to 1:3, in particular from 2:1 to 1:2, specifically from 2:1 to 1:1.
18. The composition according to any of the preceding claims, which is selected from the group consisting of antimicrobial concentrates, homecare compositions, compositions for cleaning or disinfecting on an industrial scale, personal care compositions, process water, cooling water, water in fish or shrimp ponds, water in drinking troughs, metal working fluids; water based raw materials, polymer solutions, polymer dispersions, polymer emulsions, inorganic slurries, organic slurries, surfactant compositions; compositions for treating animal hide; compositions for treating leather; compositions for treating textiles during the manufacturing process thereof; compositions for treating lumber; compositions for treating paper or the precursor material during papermaking processes; crop protection compositions; pharmaceutical compositions; paints, glues, adhesives, sealants, dyes, pigments and dispersions thereof, inks, and wet wipes.
19. Kit of parts comprising at least two parts, where the first part comprises at least one antimicrobial agent as defined in any of claims 1 to 4; the second part comprises an alkoxylated amine as defined in any of claims 1 and 5 to 8 and optionally at least one organic solvent; and an optional third part comprises at least one organic solvent; where the first part does not comprise an alkoxylated amine as defined in any of claims 1 and 5 to 8; where the second part does not comprise any antimicrobial agent as defined in any of claims 1 to 4; where the optional third part does not comprise any antimicrobial agent as defined in any of claims 1 to 4 nor an alkoxylated amine as defined in any of claims 1 and 5 to 8; and where the first and second parts contain the at least one antimicrobial agent as defined in any of claims 1 to 4 and the alkoxylated amine as defined in any of claims 1 and 5 to 8 in such amounts that when the first and the second part are mixed the resulting overall weight ratio is as defined in claim 9 to 11.
20. The use of an alkoxylated amine as defined in any of claims 1 and 5 to 8 for enhancing the antimicrobial, in particular the preserving, activity of the antimicrobial agent as defined in any of claims 1 to 4.
21. The use according to claim 20, of an alkoxylated amine as defined in any of claims 1 and 5 to 8 for enhancing the antimicrobial, in particular the preserving, activity of 2-phenoxyethanol.
22. The use according to any of claims 20 or 21 , for enhancing the antimicrobial, in particular the preserving, activity of the antimicrobial agent in an aqueous liquid homecare composition.
PCT/EP2024/060367 2023-04-17 2024-04-17 Composition comprising an antimicrobial agent and an alkoxylated amine Pending WO2024218124A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP23168300 2023-04-17
EP23168300.4 2023-04-17

Publications (1)

Publication Number Publication Date
WO2024218124A1 true WO2024218124A1 (en) 2024-10-24

Family

ID=86052405

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2024/060367 Pending WO2024218124A1 (en) 2023-04-17 2024-04-17 Composition comprising an antimicrobial agent and an alkoxylated amine

Country Status (1)

Country Link
WO (1) WO2024218124A1 (en)

Citations (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4983185A (en) * 1988-05-28 1991-01-08 Basf Aktiengesellschaft Dyeing of leather with pigments
WO1991017244A1 (en) 1990-05-09 1991-11-14 Novo Nordisk A/S An enzyme capable of degrading cellulose or hemicellulose
EP0462456A1 (en) 1990-06-16 1991-12-27 Nihon Nohyaku Co., Ltd. Hydrazinecarboxamide derivatives, a process for production thereof, and uses thereof
WO1993024622A1 (en) 1992-05-22 1993-12-09 Alko Ltd. Mannanase enzymes, genes coding for them, methods for isolating the genes, and methods for bleaching lignocellulosic pulps
WO1995002675A1 (en) 1993-07-12 1995-01-26 Novo Nordisk A/S A detergent composition comprising two cellulase components
US5622554A (en) * 1996-07-19 1997-04-22 Tomah Products, Inc. Asphalt-based coating composition with alkoxylated amine-derived salt surfactant
WO1998046608A1 (en) 1997-04-14 1998-10-22 American Cyanamid Company Fungicidal trifluoromethylalkylamino-triazolopyrimidines
US5869438A (en) 1990-09-13 1999-02-09 Novo Nordisk A/S Lipase variants
EP0897904A1 (en) 1997-08-20 1999-02-24 American Cyanamid Company Fungicidal 2-methoxybenzophenones
WO1999041255A1 (en) 1998-02-11 1999-08-19 American Cyanamid Company Fungicidal 7-alkyl-triazolopyrimidines
WO2003004465A2 (en) 2001-07-05 2003-01-16 Basf Aktiengesellschaft Fungicidal triazolopyrimidines, method for the production thereof and use thereof in controlling noxious fungi and agents containing said compounds
WO2003075663A1 (en) 2002-03-11 2003-09-18 Basf Aktiengesellschaft Method for immunizing plants against bacterioses
WO2004053039A2 (en) 2002-12-11 2004-06-24 Novozymes A/S Detergent composition comprising endo-glucanase
US20050032668A1 (en) * 2003-08-04 2005-02-10 Pedersen Daniel E. Antimicrobial compositions including carboxylic acids and alkoxylated amines
WO2008009673A2 (en) 2006-07-18 2008-01-24 Direvo Industrial Biotechnology Gmbh Mannanases
EP1921147A2 (en) 1994-02-24 2008-05-14 Henkel Kommanditgesellschaft auf Aktien Improved enzymes and detergents containing them
WO2011086115A2 (en) * 2010-01-18 2011-07-21 Basf Se Compound comprising a pesticide and an alkoxylate of 2-propylheptyl amine
WO2014183921A1 (en) 2013-05-17 2014-11-20 Novozymes A/S Polypeptides having alpha amylase activity
WO2014183920A1 (en) 2013-05-17 2014-11-20 Novozymes A/S Polypeptides having alpha amylase activity
WO2015001009A1 (en) 2013-07-05 2015-01-08 Assa Abloy Ab Access control communication device, method, computer program and computer program product
WO2016096711A2 (en) 2014-12-15 2016-06-23 Novozymes A/S Subtilase variants
WO2017060493A1 (en) 2015-10-07 2017-04-13 Novozymes A/S Polypeptides
WO2018184767A1 (en) 2017-04-05 2018-10-11 Henkel Ag & Co. Kgaa Detergent compositions comprising bacterial mannanases
WO2019081721A1 (en) 2017-10-27 2019-05-02 Novozymes A/S Dnase variants

Patent Citations (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4983185A (en) * 1988-05-28 1991-01-08 Basf Aktiengesellschaft Dyeing of leather with pigments
WO1991017244A1 (en) 1990-05-09 1991-11-14 Novo Nordisk A/S An enzyme capable of degrading cellulose or hemicellulose
EP0462456A1 (en) 1990-06-16 1991-12-27 Nihon Nohyaku Co., Ltd. Hydrazinecarboxamide derivatives, a process for production thereof, and uses thereof
US5869438A (en) 1990-09-13 1999-02-09 Novo Nordisk A/S Lipase variants
WO1993024622A1 (en) 1992-05-22 1993-12-09 Alko Ltd. Mannanase enzymes, genes coding for them, methods for isolating the genes, and methods for bleaching lignocellulosic pulps
WO1995002675A1 (en) 1993-07-12 1995-01-26 Novo Nordisk A/S A detergent composition comprising two cellulase components
EP1921147A2 (en) 1994-02-24 2008-05-14 Henkel Kommanditgesellschaft auf Aktien Improved enzymes and detergents containing them
US5622554A (en) * 1996-07-19 1997-04-22 Tomah Products, Inc. Asphalt-based coating composition with alkoxylated amine-derived salt surfactant
WO1998046608A1 (en) 1997-04-14 1998-10-22 American Cyanamid Company Fungicidal trifluoromethylalkylamino-triazolopyrimidines
EP0897904A1 (en) 1997-08-20 1999-02-24 American Cyanamid Company Fungicidal 2-methoxybenzophenones
WO1999041255A1 (en) 1998-02-11 1999-08-19 American Cyanamid Company Fungicidal 7-alkyl-triazolopyrimidines
WO2003004465A2 (en) 2001-07-05 2003-01-16 Basf Aktiengesellschaft Fungicidal triazolopyrimidines, method for the production thereof and use thereof in controlling noxious fungi and agents containing said compounds
WO2003075663A1 (en) 2002-03-11 2003-09-18 Basf Aktiengesellschaft Method for immunizing plants against bacterioses
WO2004053039A2 (en) 2002-12-11 2004-06-24 Novozymes A/S Detergent composition comprising endo-glucanase
US20050032668A1 (en) * 2003-08-04 2005-02-10 Pedersen Daniel E. Antimicrobial compositions including carboxylic acids and alkoxylated amines
WO2008009673A2 (en) 2006-07-18 2008-01-24 Direvo Industrial Biotechnology Gmbh Mannanases
WO2011086115A2 (en) * 2010-01-18 2011-07-21 Basf Se Compound comprising a pesticide and an alkoxylate of 2-propylheptyl amine
WO2014183921A1 (en) 2013-05-17 2014-11-20 Novozymes A/S Polypeptides having alpha amylase activity
WO2014183920A1 (en) 2013-05-17 2014-11-20 Novozymes A/S Polypeptides having alpha amylase activity
WO2015001009A1 (en) 2013-07-05 2015-01-08 Assa Abloy Ab Access control communication device, method, computer program and computer program product
WO2016096711A2 (en) 2014-12-15 2016-06-23 Novozymes A/S Subtilase variants
WO2017060493A1 (en) 2015-10-07 2017-04-13 Novozymes A/S Polypeptides
WO2018184767A1 (en) 2017-04-05 2018-10-11 Henkel Ag & Co. Kgaa Detergent compositions comprising bacterial mannanases
WO2019081721A1 (en) 2017-10-27 2019-05-02 Novozymes A/S Dnase variants
WO2019081724A1 (en) 2017-10-27 2019-05-02 Novozymes A/S Dnase variants

Non-Patent Citations (8)

* Cited by examiner, † Cited by third party
Title
"Technical Monograph No. 2", May 2008, CROPLIFE INTERNATIONAL, article "Catalogue of pesticide formulation types and international coding system"
CHLEBICKI J ET AL: "Synthesis and Surface Properties of Nonionic and Cationic Surfactants Formed from Aminoisopropanols", TENSIDE DETERGENTS,, no. 4, 1 July 1981 (1981-07-01), pages 206 - 210, XP001390760 *
EVONIK: "Tomamine Ethoxylated", 1 June 2017 (2017-06-01), XP093088872, Retrieved from the Internet <URL:https://azeliscanada.com/wp-content/uploads/2019/11/Tomamine-E-14-2.-TDS.-06.01.17.pdf> [retrieved on 20231005] *
KNOWLES: "Adjuvants and additives", AGROW REPORTS DS256, T&F INFORMA, 2006
KNOWLES: "New developments in crop protection product formulation", AGROW REPORTS DS243, T&F INFORMA, 2005
MCCUTCHEON'S: "Emulsifiers & Detergents", vol. 1, 2008
MOLLETGRUBEMANN: "Formulation technology", 2001, WILEY VCH
NEEDLEMANWUNSCH, J. MOL. BIOL., vol. 48, 1979, pages 443 - 453

Similar Documents

Publication Publication Date Title
US12171851B2 (en) Antimicrobial compositions containing cationic active ingredients
AU2015296250B2 (en) Antimicrobial foaming compositions containing cationic active ingredients
CN109640656A (en) The synergistic combination of biocide
AU2016307243A1 (en) Antimicrobial polymer
MX2014011364A (en) Liquid cleaning and disinfecting compositions.
FR2744332A1 (en) MIXTURE, PHYTOSANITARY PRODUCTS CONTAINING THE MIXTURE AND THEIR USE
EP3510867A1 (en) Antimicrobial polymer
AU2019417293A1 (en) Synergistic disinfectant compositions having enhanced antimicrobial efficacy and stability, and methods of using the same
EP4447675A1 (en) Composition comprising an antimicrobial agent and a carboxamide
WO2024218124A1 (en) Composition comprising an antimicrobial agent and an alkoxylated amine
WO2025157800A1 (en) Biocidal composition comprising an alkoxylated amine and an organic solvent
EP4447676A1 (en) Lactones for enhancing the activity of antimicrobial agents
EP4385328A1 (en) Alpha-hydroxyketones for enhancing the activity of antimicrobial agents
EP4289273A1 (en) Composition comprising an antimicrobial agent and a n-cyclohexyldiazeniumdioxy salt
Ozdal et al. Applications of Microbial Biosurfactants in Detergents
CN119998430A (en) Detergents and cleaning compositions with improved degreasing power
US20180371369A1 (en) Fabric treatment
KR20250095622A (en) Detergents and cleaning compositions with improved cleaning performance
AU2023400116A1 (en) Disinfectant composition
CN119998432A (en) Detergent and/or cleaning composition for malodor reduction and fragrance enhancement

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 24719544

Country of ref document: EP

Kind code of ref document: A1

点击 这是indexloc提供的php浏览器服务，不要输入任何密码和下载