+

WO2001061099A1 - Sachet d'additifs de blanchisserie - Google Patents

Sachet d'additifs de blanchisserie Download PDF

Info

Publication number
WO2001061099A1
WO2001061099A1 PCT/US2001/004694 US0104694W WO0161099A1 WO 2001061099 A1 WO2001061099 A1 WO 2001061099A1 US 0104694 W US0104694 W US 0104694W WO 0161099 A1 WO0161099 A1 WO 0161099A1
Authority
WO
WIPO (PCT)
Prior art keywords
preferred
acid
compositions
alkyl
laundry additive
Prior art date
Application number
PCT/US2001/004694
Other languages
English (en)
Other versions
WO2001061099A8 (fr
Inventor
Valerio Del Duca
Mario Albanesi
Gina Isoldi
Original Assignee
The Procter & Gamble Company
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
Priority claimed from EP00870124A external-priority patent/EP1126070B1/fr
Priority claimed from PCT/US2000/019619 external-priority patent/WO2002008370A2/fr
Application filed by The Procter & Gamble Company filed Critical The Procter & Gamble Company
Priority to US10/204,259 priority Critical patent/US7351683B2/en
Priority to MXPA02008067A priority patent/MXPA02008067A/es
Priority to EP01910655A priority patent/EP1255887A2/fr
Priority to JP2001559930A priority patent/JP5000060B2/ja
Priority to AU2001238240A priority patent/AU2001238240A1/en
Priority to BR0108441-0A priority patent/BR0108441A/pt
Priority to CA002396931A priority patent/CA2396931A1/fr
Publication of WO2001061099A1 publication Critical patent/WO2001061099A1/fr
Publication of WO2001061099A8 publication Critical patent/WO2001061099A8/fr

Links

Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06F—LAUNDERING, DRYING, IRONING, PRESSING OR FOLDING TEXTILE ARTICLES
    • D06F39/00—Details of washing machines not specific to a single type of machines covered by groups D06F9/00 - D06F27/00 
    • D06F39/02—Devices for adding soap or other washing agents
    • D06F39/024—Devices for adding soap or other washing agents mounted on the agitator or the rotating drum; Free body dispensers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0004—Non aqueous liquid compositions comprising insoluble particles
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
    • C11D17/042—Water soluble or water disintegrable containers or substrates containing cleaning compositions or additives for cleaning compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
    • C11D17/042—Water soluble or water disintegrable containers or substrates containing cleaning compositions or additives for cleaning compositions
    • C11D17/045—Multi-compartment
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/30—Amines; Substituted amines ; Quaternized amines
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3945—Organic per-compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/43—Solvents
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic compounds
    • C11D3/3917—Nitrogen-containing compounds

Definitions

  • the present invention relates to the field of laundry additive products, designed to be used in conjunction with a conventional laundry detergent. Such laundry additives are usually designed to boost the performance of the conventional detergent.
  • the present laundry additive are provided in the form of a water- soluble sachet comprising at least two compartments.
  • Laundry additive products are well known in the art. Such products have commonly been used to boost the performance of the conventional, main wash detergent, most commonly by providing an additional bleaching performance.
  • Conventional laundry additives are in the form of powders, liquids or gels, however more recently additives in the form of tablets have been introduced onto the market. Tablets are found to be attractive to consumers because more precise dosing is possible and wasteful overdosing or underdosing are reduced. Moreover consumers are attracted to such single dose products because they are less likely to result in spillage or dripping.
  • the Applicants have found that whilst such tablets are preferred by consumers the desire still exists for a product where the user does not have to come into direct contact with the ingredients of the composition.
  • an object of the present invention is to provide a unit dosage laundry additive composition, where the user does not come into direct contact with the ingredients of the composition.
  • a laundry additive sachet comprising a liquid laundry additive composition.
  • ingredients especially aggressive ingredients such as bleaching agents, can either dissolve or damage the materials making up the sachet, resulting in the premature dissolution of the sachet and release of the liquid laundry additive composition.
  • some liquid ingredients can simply leak through the sachet wall, draining the composition from the sachet such that at the time of use, the amount of laundry additive composition is not the correct dose.
  • a laundry additive in the form of a sachet comprising at least two compartments and comprising at least one liquid composition.
  • a laundry additive sachet comprising one or more liquid compositions, wherein the sachet comprises two or more compartments made of substantially water-soluble film or sheet material.
  • a process of treating fabrics with a laundry additive sachet according to the present invention in conjunction with a conventional laundry detergent in the presence of water According to a further aspect of the present invention there is provided the use of a sachet according to according to the present invention as a laundry additive. In addition there is provided the use of a sachet according to the present invention to clean and/or soften fabric. Finally, there is provided the use of sachet according to the present invention to clean and/or provide and easy ironing benefit.
  • the present invention relates to a laundry additive sachet comprising one or more liquid compositions, described in more detail later.
  • the sachet comprises at least two compartments and is made from a substantially water-soluble film or sheet material.
  • Sachets comprising liquid or particulate compositions, have been discussed in the prior art. However the sachets were typically either insoluble such that they could be removed after the end of the wash, or were unsatisfactorily water- soluble.
  • the most commonly discussed water-soluble sachets of the prior art are made using polyvinyl alcohol (PVA).
  • PVA polyvinyl alcohol
  • sachets made using PVA are sensitive to bleaching agents, such that if a composition, especially a liquid composition comprising a bleaching agent were to be filled into the sachet, the sachet would degrade and burst prior to use by the consumer due to the effect of the bleaching agent on the PVA.
  • the Applicants have addressed this problem by using particulate, bleaching agents in either a particulate but preferably a liquid matrix.
  • the Applicants have also addressed the known problem of PVA sachets gelling on contact with water.
  • This gelling phenomenon occurs where the outer surface of the PVA sachet dissolves in water, but instead of dissipating into the surrounding water, it forms a gel surrounding the sachet, preventing the further dissolution on the sachet. The result is that the sachet does not totally dissolve, leaving residues of sachet on the fabrics.
  • HPMC hydroxy propyl methyl cellulose
  • Sachets can be prepared according to the known methods in the art. More specifically, the sachets are prepared by first cutting an appropriately sized piece of film/sheet. The fold the sheet to form the necessary number and size of compartments and seal the edges using any suitable technology, for example heat sealing.
  • the sachet as described above comprises at least two compartments. At least one of the compartments is filled, at least to some extent, with at least one liquid laundry additive composition.
  • the other compartment may be filled with the same or a different liquid composition, or alternatively a particulate composition. Most preferably the compartments are filled, at least to some extent with different composition.
  • different composition it is meant that the first and/or second compositions comprise at least one ingredient that is not preset in the other composition.
  • the compartment(s) may be filled at least to some extent with a third or subsequent composition which is different to any of the other composition, for example the first or second composition, in the case where a third composition exists.
  • the first composition is a liquid or particulate, preferably particulate composition comprising ingredients selected from the group listed under laundry Additive Ingredients.
  • the second composition comprises a bleaching agent, different from that in the first composition if present, and is in liquid form.
  • Bleaching agents are described in more detail below, however the preferred bleaching agent for use in the second composition of this embodiment is a particulate peracid.
  • the peracid is selected from the range of pre-formed mono peroxycarboxylic acid described in more detail below.
  • the pre-formed peracid is phthaloyl a ido peroxyhexanoic acid, known as PAP.
  • PAP ido peroxyhexanoic acid
  • the liquid matrix where present is substantially non-aqueous meaning that it does not comprise a level of water that would result in the dissolution of the material making up the sachet.
  • the preferred ingredients used to suspend the PAP are solvents which do not either dissolve or damage the material making up the sachet over time. More preferably the suspending agent is a long chain, low polarity solvent.
  • long chain it is meant solvents comprising a carbon chain of greater than 6 carbon atoms and by low polarity it is meant a solvent having a dielectric constant of less than 40.
  • Preferred solvents include C12-14 paraffin and more preferably C12-14 isoparaffin. The benefit of the present embodiment is the significant improvement in bleachable soil removal provided by the laundry additive.
  • the second composition is the same as that described above, however the first composition is a fabric softening composition, comprising an ingredient which softens fabric and also renders the fabrics treated easier to iron.
  • the first composition of this embodiment may be in liquid, but is preferably in particulate form.
  • the softening ingredient can be present in an amount of from 20% to 80% by weight of the first composition.
  • Remaining ingredients can be selected from any of those listed under Laundry Additive Ingredients.
  • the preceding embodiment may be altered such that the performance delivering ingredient in the first composition instead of a softening ingredient is for example, one or more enzymes, especially carezyme, an organic polymeric compound, soil suspending polymer, dye transfer inhibitor a brightener and mixtures thereof.
  • a softening ingredient is for example, one or more enzymes, especially carezyme, an organic polymeric compound, soil suspending polymer, dye transfer inhibitor a brightener and mixtures thereof.
  • a sachet laundry additive following the same compositional structure as that described in the first embodiment above, in which an additional element other than a softening ingredient, for example as defined in the preceding paragraph may be added to the first, second or first and second compositions.
  • the liquid composition of the present invention where used to suspend a particulate component, may also comprise other structuring ingredients in order to stabilise the matrix.
  • a preferred structuring agent is a combination of sodium alkyl benzene sulphonate (LAS) and sodium sulphate which has been dehydrated to form a crystalline structure.
  • Fabrics treated with the compositions of the present inventions comprising a softening ingredient not only improve the softness of the fabrics, but also make the fabrics easier to iron. This easy ironing benefit is perceived as the fabrics not only having less wrinkles, but also as the wrinkles being easier to remove for example when ironing.
  • compositions used may include a variety of different ingredients including builder compounds, surfactants, enzymes, bleaching agents, alkalinity sources, colourants, perfume, lime soap dispersants, organic polymeric compounds including polymeric dye transfer inhibiting agents, crystal growth inhibitors, heavy metal ion sequestrants, metal ion salts, enzyme stabilisers, corrosion inhibitors, suds suppressers, solvents, fabric softening agents, optical brighteners and hydrotropes.
  • builder compounds surfactants, enzymes, bleaching agents, alkalinity sources, colourants, perfume, lime soap dispersants
  • organic polymeric compounds including polymeric dye transfer inhibiting agents, crystal growth inhibitors, heavy metal ion sequestrants, metal ion salts, enzyme stabilisers, corrosion inhibitors, suds suppressers, solvents, fabric softening agents, optical brighteners and hydrotropes.
  • compositions of the present invention preferably contain a builder compound, typically present at a level of from 1% to 80% by weight, preferably from 10% to 70% by weight, most preferably from 20% to 60% by weight of the composition of active detergent components.
  • Suitable water-soluble builder compounds include the water soluble monomeric polycarboxylates, or their acid forms, homo or copolymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxylic radicals separated from each other by not more that two carbon atoms, carbonates, bicarbonates, borates, phosphates, and mixtures of any of the foregoing.
  • the carboxylate or polycarboxylate builder can be monomeric or oligomeric in type although monomeric polycarboxylates are generally preferred for reasons of cost and performance.
  • Suitable carboxylates containing one carboxy group include the water soluble salts of lactic acid, glycolic acid and ether derivatives thereof.
  • Polycarboxylates containing two carboxy groups include the water-soluble salts of succinic acid, malonic acid, (ethyl enedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid, as well as the ether carboxylates and the sulfinyl carboxylates.
  • Polycarboxylates containing three carboxy groups include, in particular, water-soluble citrates, aconitrates and citraconates as well as succinate derivatives such as the carboxymethyloxysuccinates described in British Patent No.
  • Polycarboxylates containing four carboxy groups include oxydisuccinates disclosed in British Patent No. 1 ,261 ,829, 1 ,1 ,2,2-ethane tetracarboxylates, 1 ,1 ,3,3-propane tetracarboxylates and 1 ,1 ,2,3-propane tetracarboxylates.
  • Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives disclosed in British Patent Nos. 1 ,398,421 and 1 ,398,422 and in U.S. Patent No. 3,936,448, and the sulfonated pyrolysed citrates described in British Patent No. 1 ,439,000.
  • Alicyclic and heterocyclic polycarboxylates include cyclopentane-cis,cis,cis- tetracarboxylates, cyclopentadienide pentacarboxylates, 2,3,4,5-tetrahydrofuran - cis, cis, cis-tetracarboxylates, 2,5-tetrahydrofuran - cis - dicarboxylates, 2,2,5,5- tetrahydrofuran - tetracarboxylates, 1 ,2,3,4,5,6-hexane - hexacarboxylates and carboxymethyl derivatives of polyhyd c alcohols such as sorbitol, mannitol and xylitol.
  • Aromatic polycarboxylates include mellitic acid, pyromellitic acid and the phthalic acid derivatives disclosed in British Patent No. 1 ,425,343.
  • the preferred polycarboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule, more particularly citrates.
  • the parent acids of the monomeric or oligomeric polycarboxylate chelating agents or mixtures thereof with their salts, e.g. citric acid or citrate/citric acid mixtures are also contemplated as useful builder components.
  • Borate builders, as well as builders containing borate-forming materials that can produce borate under detergent storage or wash conditions can also be used but are not preferred at wash conditions less that 50°C, especially less than 40°C.
  • carbonate builders are the alkaline earth and alkali metal carbonates, including sodium carbonate and sesqui-carbonate and mixtures thereof with ultra-fine calcium carbonate as disclosed in German Patent Application No. 2,321 ,001 published on November 15, 1973.
  • Highly preferred builder compounds for use in the present invention are water- soluble phosphate builders.
  • water-soluble phosphate builders are the alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphate, sodium and potassium and ammonium pyrophosphate, sodium and potassium orthophosphate, sodium polymeta/phosphate in which the degree of polymerisation ranges from 6 to 21 , and salts of phytic acid.
  • water-soluble phosphate builders are the alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphate, sodium and potassium and ammonium pyrophosphate, sodium and potassium orthophosphate, sodium polymeta/phosphate in which the degree of polymerization ranges from 6 to 21 , and salts of phytic acid.
  • Partially soluble or insoluble builder compound Partially soluble or insoluble builder compound
  • compositions of the present invention may contain a partially soluble or insoluble builder compound.
  • partially water soluble builders include the crystalline layered silicates as disclosed for example, in EP-A-0164514, DE-A-3417649 and DE-A-3742043.
  • Preferred are the crystalline layered sodium silicates of general formula NaMSi x ⁇ 2+ ⁇ NH2O
  • Crystalline layered sodium silicates of this type preferably have a two dimensional 'sheet' structure, such as the so called ⁇ -layered structure, as described in EP 0 164514 and EP 0 293640. Methods for preparation of crystalline layered silicates of this type are disclosed in DE-A-3417649 and DE- A-3742043.
  • x in the general formula above has a value of 2,3 or 4 and is preferably 2.
  • the most preferred crystalline layered sodium silicate compound has the formula 5-Na2Si2 ⁇ 5, known as NaSKS-6 (trade name), available from Hoechst AG.
  • the crystalline layered sodium silicate material is preferably present in granular detergent compositions as a particulate in intimate admixture with a solid, water- soluble ionisable material as described in PCT Patent Application No. WO92/18594.
  • the solid, water-soluble ionisable material is selected from organic acids, organic and inorganic acid salts and mixtures thereof, with citric acid being preferred.
  • Examples of largely water insoluble builders include the sodium aluminosilicates.
  • Suitable aluminosilicates include the aluminosilicate zeolites having the unit cell formula Na z [(AIO2)z(SiO2)y]. XH2O wherein z and y are at least 6; the molar ratio of z to y is from 1.0 to 0.5 and x is at least 5, preferably from 7.5 to 276, more preferably from 10 to 264.
  • the aluminosilicate material are in hydrated form and are preferably crystalline, containing from 10% to 28%, more preferably from 18% to 22% water in bound form.
  • the aluminosilicate zeolites can be naturally occurring materials, but are preferably synthetically derived. Synthetic crystalline aluminosilicate ion exchange materials are available under the designations Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeolite HS and mixtures thereof.
  • a preferred method of synthesizing aluminosilicate zeolites is that described by
  • the colloidal aluminosilicate zeolite particles should preferably be such that no more than 5% of the particles are of size greater than 1 ⁇ m in diameter and not more than 5% of particles are of size less then 0.05 ⁇ m in diameter.
  • the aluminosilicate zeolite particles have an average particle size diameter of between 0.01 ⁇ m and 1 ⁇ m, more preferably between 0.05 ⁇ m and 0.9 ⁇ m, most preferably between 0.1 ⁇ m and 0.6 ⁇ m.
  • Zeolite A has the formula
  • Zeolite X has the formula NQQQ [( l ⁇ 2)86(Si ⁇ 2)i 06l- 276 2°- Zeolite MAP, as disclosed in EP-B-384,070 is a preferred zeolite builder herein.
  • Preferred aluminosilicate zeolites are the colloidal aluminosilicate zeolites.
  • colloidal aluminosilicate zeolites especially colloidal zeolite A, provide enhanced builder performance in terms of providing improved stain removal.
  • Enhanced builder performance is also seen in terms of reduced fabric encrustation and improved fabric whiteness maintenance; problems believed to be associated with poorly built detergent compositions.
  • mixed aluminosilicate zeolite detergent compositions comprising colloidal zeolite A and colloidal zeolite Y provide equal calcium ion sequestration performance versus an equal weight of commercially available zeolite A.
  • Another surprising finding is that mixed aluminosilicate zeolite detergent compositions, described above, provide improved magnesium ion sequestration performance versus an equal weight of commercially available zeolite A.
  • Suitable surfactants are selected from anionic, cationic, nonionic ampholytic and zwitterionic surfactants and mixtures thereof.
  • the surfactant is typically present at a level of from 0.2% to 30% by weight, more preferably from 0.5% to 10% by weight, most preferably from 1% to 5% by weight of the composition of active detergent components.
  • nonionic surfactants useful for detersive purposes can be included in thecompositions.
  • Preferred, non-limiting classes of useful nonionic surfactants are listed below.
  • alkyl ethoxylate condensation products of aliphatic alcohols with from 1 to 25 moles of ethylene oxide are suitable for use herein.
  • the alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from 6 to 22 carbon atoms.
  • Particularly preferred are the condensation products of alcohols having an alkyl group containing from 8 to 20 carbon atoms with from 2 to 10 moles of ethylene oxide per mole of alcohol.
  • a suitable endcapped alkyl alkoxylate surfactant is the epoxy-capped poly(oxyalkylated) alcohols represented by the formula:
  • R-j is a linear or branched, aliphatic hydrocarbon radical having from 4 to 18 carbon atoms
  • R2 is a linear or branched aliphatic hydrocarbon radical having from 2 to 26 carbon atoms
  • x is an integer having an average value of from 0.5 to 1.5, more preferably 1
  • y is an integer having a value of at least 15, more preferably at least 20.
  • the surfactant of formula I at least 10 carbon atoms in the terminal epoxide unit [CH2CH(OH)R2J.
  • Suitable surfactants of formula I, according to the present invention are Olin Corporation's POLY-TERGENT® SLF-18B nonionic surfactants, as described, for example, in WO 94/22800, published October 13, 1994 by Olin Corporation.
  • Preferred surfactants for use herein include ether-capped poly(oxyalkylated) alcohols having the formula:
  • R ⁇ and R 2 are linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having from 1 to 30 carbon atoms;
  • R 3 is H, or a linear aliphatic hydrocarbon radical having from 1 to 4 carbon atoms;
  • x is an integer having an average value from 1 to 30, wherein when x is 2 or greater R 3 may be the same or different and k and j are integers having an average value of from 1 to 12, and more preferably 1 to 5.
  • R1 and R 2 are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having from 6 to 22 carbon atoms with 8 to 18 carbon atoms being most preferred. H or a linear aliphatic hydrocarbon radical having from 1 to 2 carbon atoms is most preferred for R 3 .
  • x is an integer having an average value of from 1 to 20, more preferably from 6 to 15.
  • R 3 may be the same or different. That is, R 3 may vary between any of the alklyeneoxy units as described above. For instance, if x is 3, R 3 may be be selected to form ethlyeneoxy(EO) or propyleneoxy(PO) and may vary in order of (EO)(PO)(EO), (EO)(EO)(PO); (EO)(EO)(EO); (PO)(EO)(PO); (PO)(PO)(EO) and (PO)(PO)(PO).
  • integer three is chosen for example only and the variation may be much larger with a higher integer value for x and include, for example, mulitple (EO) units and a much small number of (PO) units.
  • Particularly preferred surfactants as described above include those that have a low cloud point of less than 20°C. These low cloud point surfactants may then be employed in conjunction with a high cloud point surfactant as described in detail below for superior grease cleaning benefits.
  • ether-capped poly(oxyalkylated) alcohol surfactants are those wherein k is 1 and j is 1 so that the surfactants have the formula:
  • R1 , R 2 and R 3 are defined as above and x is an integer with an average value of from 1 to 30, preferably from 1 to 20, and even more preferably from 6 to 18.
  • Most preferred are surfactants wherein R ⁇ and R 2 range from 9 to 14, R 3 is H forming ethyleneoxy and x ranges from 6 to 15.
  • the ether-capped poly(oxyalkylated) alcohol surfactants comprise three general components, namely a linear or branched alcohol, an alkylene oxide and an alkyl ether end cap.
  • the alkyl ether end cap and the alcohol serve as a hydrophobic, oil-soluble portion of the molecule while the alkylene oxide group forms the hydrophilic, water-soluble portion of the molecule.
  • surfactants exhibit significant improvements in spotting and filming characteristics and removal of greasy soils, when used in conjunction with high cloud point surfactants, relative to conventional surfactants.
  • the ether-capped poly(oxyalkylene) alcohol surfactants of the present invention may be produced by reacting an aliphatic alcohol with an epoxide to form an ether which is then reacted with a base to form a second epoxide. The second epoxide is then reacted with an alkoxylated alcohol to form the novel compounds of the present invention. Examples of methods of preparing the ether-capped poly(oxyalkylated) alcohol surfactants are described below:
  • the ethoxylated C ⁇ -C-i ⁇ fatty alcohols and CQ-C ⁇ Q mixed ethoxylated/propoxylated fatty alcohols are suitable surfactants for use herein, particularly where water soluble.
  • the ethoxylated fatty alcohols are the C-10-C18 ethoxylated fatty alcohols with a degree of ethoxylation of from 3 to 50, most preferably these are the Ci2 ⁇ Cl8 ethoxylated fatty alcohols with a degree of ethoxylation from 3 to 40.
  • the mixed ethoxylated/propoxylated fatty alcohols have an alkyl chain length of from 10 to 18 carbon atoms, a degree of ethoxylation of from 3 to 30 and a degree of propoxylation of from 1 to 10.
  • the condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol are suitable for use herein.
  • the hydrophobic portion of these compounds preferably has a molecular weight of from 1500 to 1800 and exhibits water insolubility.
  • Examples of compounds of this type include certain of the commercially-available PluronicT surfactants, marketed by BASF.
  • condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamine are suitable for use herein.
  • the hydrophobic moiety of these products consists of the reaction product of ethylenediamine and excess propylene oxide, and generally has a molecular weight of from 2500 to 3000.
  • this type of nonionic surfactant include certain of the commercially available TetronicTM compounds, marketed by BASF.
  • anionic surfactants useful for detersive purposes are suitable. These can include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts) of the anionic sulfate, sulfonate, carboxylate and sarcosinate surfactants. Anionic sulfate surfactants are preferred.
  • anionic surfactants include the isethionates such as the acyl isethionates,
  • N-acyl taurates fatty acid amides of methyl tauride, alkyl succinates and sulfosuccinates, monoesters of sulfosuccinate (especially saturated and unsaturated o monoesters) diesters of sulfosuccinate (especially saturated and unsaturated Cg-C 14 diesters), N-acyl sarcosinates.
  • Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tallow oil.
  • Anionic sulfate surfactants suitable for use herein include the linear and branched primary and secondary alkyl sulfates, alkyl ethoxysulfates, fatty oleoyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, the C5-C-17 acyl-N-
  • Alkyl sulfate surfactants are preferably selected from the linear and branched primary C10-C18 a 'ky' sulfates, more preferably the C-j 1-C-15 branched chain alkyl sulfates and the C12-C14 linear chain alkyl sulfates.
  • Alkyl ethoxysulfate surfactants are preferably selected from the group consisting of the C-J0-C18 a 'ky' su 'f ates which have been ethoxylated with from 0.5 to 20 moles of ethylene oxide per molecule. More preferably, the alkyl ethoxysulfate surfactant is a C-j I -C-I Q, most preferably C11-C15 alkyl sulfate which has been ethoxylated with from 0.5 to 7, preferably from 1 to 5, moles of ethylene oxide per molecule.
  • a particularly preferred aspect of the invention employs mixtures of the preferred alkyl sulfate and alkyl ethoxysulfate surfactants. Such mixtures have been disclosed in PCT Patent Application No. WO 93/18124.
  • Anionic sulfonate surfactant Anionic sulfonate surfactant
  • Anionic sulfonate surfactants suitable for use herein include the salts of C5-C20 linear alkylbenzene sulfonates, alkyl ester sulfonates, C6-C22 primary or secondary alkane sulfonates, C5-C24 olefin sulfonates, sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfonates, and any mixtures thereof.
  • Anionic carboxylate surfactant include the salts of C5-C20 linear alkylbenzene sulfonates, alkyl ester sulfonates, C6-C22 primary or secondary alkane sulfonates, C5-C24 olefin sulfonates, sulfonated polycarboxylic acids, alky
  • Suitable anionic carboxylate surfactants include the alkyl ethoxy carboxylates, the alkyl polyethoxy polycarboxylate surfactants and the soaps ('alkyl carboxyls'), especially certain secondary soaps as described herein.
  • Suitable alkyl ethoxy carboxylates include those with the formula RO(CH2CH2 ⁇ ) x CH2C00 ⁇ M + wherein R is a Cg to C-f s 'kyl group, x ranges from O to 10, and the ethoxylate distribution is such that, on a weight basis, the amount of material where x is 0 is less than 20 % and M is a cation.
  • Suitable alkyl polyethoxy polycarboxylate surfactants include those having the formula RO-(CHR-
  • R ⁇ l and R2 are selected from the group consisting of hydrogen, methyl acid radical, succinic acid radical, hydroxysuccinic acid radical, and mixtures thereof
  • R3 is selected from the group consisting of hydrogen, substituted or unsubstituted hydrocarbon having between 1 and 8 carbon atoms, and mixtures thereof.
  • Suitable soap surfactants include the secondary soap surfactants which contain a carboxyl unit connected to a secondary carbon.
  • Preferred secondary soap surfactants for use herein are water-soluble members selected from the group consisting of the water-soluble salts of 2-methyl-1-undecanoic acid, 2-ethyl-1- decanoic acid, 2-propyl-1-nonanoic acid, 2-butyl-1-octanoic acid and 2-pentyl-1- heptanoic acid. Certain soaps may also be included as suds suppressors.
  • Suitable anionic surfactants are the alkali metal sarcosinates of formula R-
  • R is a C5-C17 linear or branched alkyl or alkenyl group
  • R ⁇ is a C1-C4 alkyl group
  • M is an alkali metal ion.
  • Preferred examples are the myristyl and oleoyl methyl sarcosinates in the form of their sodium salts.
  • Suitable amphoteric surfactants for use herein include the amine oxide surfactants and the alkyl amphocarboxylic acids.
  • Suitable amine oxides include those compounds having the formula R 3 (OR4) ⁇ N 0 (R5)2 wherein R 3 is selected from an alkyl, hydroxyalkyl, acylamidopropoyl and alkyl phenyl group, or mixtures thereof, containing from 8 to 26 carbon atoms; R ⁇ is an alkylene or hydroxyalkylene group containing from 2 to 3 carbon atoms, or mixtures thereof; x is from 0 to 5, preferably from 0 to 3; and each R ⁇ is an alkyl or hydroxyalkyl group containing from 1 to 3, or a polyethylene oxide group containing from 1 to 3 ethylene oxide groups.
  • Preferred are C10-C18 a 'ky' dimethylamine oxide, and C-J O-18 acylamido alkyl dimethylamine oxide.
  • a suitable example of an alkyl aphodicarboxylic acid is Miranol(TM) C2M Cone, manufactured by Miranol, Inc., Dayton, NJ.
  • Zwitterionic surfactants can also be incorporated into the detergent compositions hereof. These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. Betaine and sultaine surfactants are exemplary zwitterionic surfactants for use herein.
  • Suitable betaines are those compounds having the formula R(R')2N + R 2 COO ⁇ wherein R is a CQ-C* Q hydrocarbyl group, each R1 is typically C1-C3 alkyl, and R 2 is a C1-C5 hydrocarbyl group.
  • Preferred betaines are C-J2-18 dimethyl- ammonio hexanoate and the C10-I 8 acylamidopropane (or ethane) dimethyl (or diethyl) betaines.
  • Complex betaine surfactants are also suitable for use herein.
  • Cationic ester surfactants used in this invention are preferably water dispersible compound having surfactant properties comprising at least one ester (i.e. -COO-) linkage and at least one cationically charged group.
  • suitable cationic ester surfactants including choline ester surfactants, have for example been disclosed in US Patents No.s 4228042, 4239660 and 4260529.
  • Suitable cationic surfactants include the quaternary ammonium surfactants selected from mono CQ-C- ⁇ Q, preferably Cg-Cio N-alkyl or alkenyl ammonium surfactants wherein the remaining N positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups.
  • the softening ingredients of the present invention may be selected from any known ingredients that provides a fabric softening benefit.
  • Clay minerals used to provide the softening properties of the instant compositions can be described as expandable, three-layer clays, i.e., aluminosilicates and magnesium silicates, having an ion exchange capacity of at least 50 meq/100g. of clay.
  • the term "expandable” as used to describe clays relates to the ability of the layered clay structure to be swollen, or expanded, on contact with water.
  • the three-layer expandable clays used herein are those materials classified geologically as smectites.
  • smectite-type clays There are two distinct classes of smectite-type clays; in the first, aluminum oxide is present in the silicate crystal lattice; in the second class of smectites, magnesium oxide is present in the silicate crystal lattice.
  • the general formulas of these smectites are AI 2 (Si 2 O 5 ) 2 (OH) 2 and Mg 3 (Si 2 O 5 ) (OH) 2 for the aluminum and magnesium oxide type clay, respectively. It is to be recognised that the range of the water of hydration in the above formulas can vary with the processing to which the clay has been subjected.
  • the three-layer, expandable alumino-silicates useful herein are further characterised by a dioctahedral crystal lattice, while the expandable three-layer magnesium silicates have a trioctahedral crystal lattice.
  • the clays employed in the compositions of the instant invention contain cationic counterions such as protons, sodium ions, potassium ions, calcium ion, magnesium ion, and the like. It is customary to distinguish between clays on the basis of one cation predominantly or exclusively absorbed. For example, a sodium clay is one in which the absorbed cation is predominantly sodium. Such absorbed cations can become involved in exchange reactions with cations present in aqueous solutions.
  • a typical exchange reaction involving a smectite-type clay is expressed by the following equation:
  • cation exchange capacity (sometimes termed “base exchange capacity") in terms of milliequivalents per 100 g. of clay (meq./100 g.).
  • base exchange capacity cation exchange capacity
  • the cation exchange capacity of clays can be measured in several ways, including by electrodialysis, by exchange with ammonium ion followed by titration or by a methylene blue procedure, all as fully set forth in Grimshaw, "The Chemistry and Physics of Clays", pp. 264-265, Interscience (1971 ).
  • the cation exchange capacity of a clay mineral relates to such factors as the expandable properties of the clay, the charge of the clay, which, in turn, is determined at least in part by the lattice structure, and the like.
  • the ion exchange capacity of clays varies widely in the range from about 2 meq/100 g. for kaolinites to about 150 meq/100 g., and greater, for certain clays of the montmorillonite variety.
  • Illite clays have an ion exchange capacity somewhere in the lower portion of the range, i.e., around 26 meq/100 g. for an average illite clay.
  • Illite and kaolinite clays are preferably not used as the clay in the instant compositions. Indeed, such illite and kaolinite clays constitute a major component of clay soils and, as noted above, are removed from fabric surfaces by means of the instant compositions.
  • smectites such as nontonite, having an ion exchange capacity of around 70 meq/100 g.
  • montmorillonite which has an ion exchange capacity greater than 70 meq/100 g.
  • clay minerals useful herein can be characterised as expandable, three-layer smectite-type clays having an ion exchange capacity of at least about 50 meq/100 g.
  • the smectite clays used in the compositions herein are all commercially available. Such clays include, for example, montmorillonite, volchonskoite, nontronite, hectorite, saponite, sauconite, and vermiculite.
  • the clays herein are available under various tradenames, for example, Thixogel #1® and Gelwhite GP® from Georgia Kaolin Co., Elizabeth, New Jersey; Volclay BC® and Volclay #325®, from American Colloid Co., Skokie, Illinois; Black Hills Bentonite BH450®, from International Minerals and Chemicals; and Veegum Pro and Veegum F, from R.T. Vanderbilt. It is to be recognised that such smectite-type minerals obtained under the foregoing tradenames can comprise mixtures of the various discrete mineral entities. Such mixtures of the smectite minerals are suitable for use herein.
  • smectite-type clays having a cation exchange capacity of at least about 50 meq/100 g. are useful herein, certain clays are preferred.
  • Gelwhite GP® is an extremely white form of smectite clay and is therefore preferred when formulating white granular detergent compositions.
  • Volclay BC® which is a smectite-type clay mineral containing at least 3% of iron (expressed as Fe 2 O 3 ) in the crystal lattice, and which has a very high ion exchange capacity, is one of the most efficient and effective clays for use in laundry compositions and is preferred from the standpoint of product performance.
  • Appropriate clay minerals for use herein can be selected by virtue of the fact that smectites exhibit a true 14A x-ray diffraction pattern. This characteristic pattern, taken in combination with exchange capacity measurements performed in the manner noted above, provides a basis for selecting particular smectite-type minerals for use in the granular detergent compositions disclosed herein.
  • the clay is preferably mainly in the form of granules, with at least 50%, preferably at least 75%, and more preferable at least 90% being in the form of granules having a size of at least 0.1 mm up to 1.8 mm, preferably up to 1.18 mm, preferably from 0.15 mm to 0.85 mm.
  • the amount of clay in the granules is at least 50%, more preferably at least 70% and most preferably at least 90% by weight of the granules.
  • Smectite clays are disclosed in the US Patents No.s 3,862,058, 3,948,790, 3,954,632 and 4,062,647.
  • European Patents No.s EP-A-299,575 and EP-A- 313,146 in the name of the Procter and Gamble Company describe suitable organic polymeric clay flocculating agents.
  • Suitable softening ingredients are long chained polymers and copolymers derived from such monomers as ethylene oxide, acrylamide, acrylic acid, dimethylamino ethyl methacrylate, vinyl alcohol, vinyl pyrrolidone and ethylene imide.
  • Preferred are polymers of ethylene oxide, acrylamide and acrylic acid. These polymers preferably have average molecular weight in the range of from 100 000 to 10 million, more preferably from 150 000 to 5 million. Average molecular weight of a polymer can be easily measured using gel permeation chromatography, against standards of polyethylene oxide of narrow molecular weight distributions. The most preferred polymers are polyethylene oxides.
  • Suitable softening ingredients include cationic fabric softening agents can also be incorporated into compositions in accordance with the present invention which are suitable for use in methods of laundry washing.
  • Suitable cationic fabric softening agents include the water insoluble tertiary amines or dilong chain amide materials as disclosed in GB-A-1 514 276 and EP-B-0 011 340.
  • Enzymes Where present said enzymes are selected from the group consisting of cellulases, hemicellulases, peroxidases, proteases, gluco-amylases, amylases, xylanases, lipases, phospholipases, esterases, cutinases, pectinases, keratanases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases, malanases, ⁇ -glucanases, arabinosidases, hyaluronidase, chondroitinase, laccase or mixtures thereof.
  • Preferred enzymes include protease, amylase, lipase, peroxidases, cutinase and/or cellulase in conjunction with one or more plant cell wall degrading enzymes.
  • the cellulases usable in the present invention include both bacterial or fungal cellulase. Preferably, they will have a pH optimum of between.5 and 12 and an activity above 50 CEVU (Cellulose Viscosity Unit).
  • CEVU Cellulose Viscosity Unit
  • Suitable cellulases are disclosed in U.S. Patent 4,435,307, Barbesgoard et al, J61078384 and WO96/02653 which disclose fungal cellulases produced respectively from Humicola insolens, Trichoderma, Thielavia and Sporotrichum.
  • EP 739 982 describes cellulases isolated from novel Bacillus species. Suitable cellulases are also disclosed in GB-A-2.075.028; GB-A-2.095.275; DE-OS-2.247.832 and WO95/26398.
  • cellulases produced by a strain of Humicola insolens (Humicola grisea var. thermoidea), particularly the Humicola strain DSM
  • cellulases originated from Humicola insolens having a molecular weight of 50KDa, an isoelectric point of 5.5 and containing
  • DSM 1800 exhibiting cellulase activity
  • a preferred endoglucanase component has the amino acid sequence disclosed in PCT Patent Application No. WO
  • Suitable cellulases are the EGIII cellulases from Trichoderma longibrachiatum described in WO94/21801 , Genencor, published September 29,
  • cellulases having color care benefits.
  • cellulases examples include cellulases described in European patent application No. 91202879.2, filed November 6, 1991 (Novo). Carezyme and
  • Other suitable cellulases for fabric care and/or cleaning properties are described in WO96/34092, WO96/17994 and WO95/24471. Said cellulases are normally incorporated in the detergent composition at levels from 0.0001 % to 2% of active enzyme by weight of the detergent composition.
  • Peroxidase enzymes are used in combination with oxygen sources, e.g. percarbonate, perborate, persulfate, hydrogen peroxide, etc. They are used for "solution bleaching", i.e. to prevent transfer of dyes or pigments removed from substrates during wash operations to other substrates in the wash solution.
  • Peroxidase enzymes are known in the art, and include, for example, horseradish peroxidase, ligninase and haloperoxidase such as chloro- and bromo- peroxidase.
  • Peroxidase-containing detergent compositions are disclosed, for example, in PCT International Application WO 89/099813, WO89/09813 and in European Patent application EP No. 91202882.6, filed on November 6, 1991 and EP No. 96870013.8, filed February 20, 1996. Also suitable is the laccase enzyme.
  • Preferred enhancers are substitued phenthiazine and phenoxasine 10- Phenothiazinepropionicacid (PPT), 10-ethylphenothiazine-4-carboxylic acid (EPC), 10-phenoxazinepropionic acid (POP) and 10-methylphenoxazine (described in WO 94/12621) and substitued syringates (C3-C5 substitued alkyl syringates) and phenols.
  • Sodium percarbonate or perborate are preferred sources of hydrogen peroxide.
  • Said cellulases and/or peroxidases are normally incorporated in the detergent composition at levels from 0.0001 % to 2% of active enzyme by weight of the detergent composition.
  • Suitable lipase enzymes for detergent usage include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in British Patent 1 ,372,034.
  • Suitable lipases include those which show a positive immunological cross-reaction with the antibody of the lipase, produced by the microorganism Pseudomonas fluorescent IAM 1057. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipase P "Amano,” hereinafter referred to as "Amano-P".
  • lipases include Amano-CES, lipases ex Chromobacter viscosum, e.g. Chromobacter viscosum var. lipolyticum NRRLB 3673 from Toyo Jozo Co., Tagata, Japan; Chromobacter viscosum lipases from U.S. Biochemical Corp., U.S.A. and Disoynth Co., The Netherlands, and lipases ex Pseudomonas gladioli.
  • lipases such as M1 Lipase ⁇ ar, d LipomaxR (Gist-Brocades) and Lipolase ⁇ and Lipolase UltraR(Novo) which have found to be very effective when used in combination with the compositions of the present invention.
  • lipolytic enzymes described in EP 258 068, WO 92/05249 and WO 95/22615 by Novo Nordisk and in WO 94/03578, WO 95/35381 and WO 96/00292 by Unilever.
  • cutinases [EC 3.1.1.50] which can be considered as a special kind of lipase, namely lipases which do not require interfacial activation. Addition of cutinases to detergent compositions have been described in e.g. WO-A- 88/09367 (Genencor); WO 90/09446 (Plant Genetic System) and WO 94/14963 and WO 94/14964 (Unilever).
  • the lipases and/or cutinases are normally incorporated in the detergent composition at levels from 0.0001 % to 2% of active enzyme by weight of the detergent composition.
  • Suitable proteases are the subtilisins which are obtained from particular strains of S. subtilis and B. licheniformis (subtilisin BPN and BPN').
  • One suitable protease is obtained from a strain of Bacillus, having maximum activity throughout the pH range of 8-12, developed and sold as ESPERASE® by Novo Industries A S of Denmark, hereinafter "Novo". The preparation of this enzyme and analogous enzymes is described in GB 1 ,243,784 to Novo.
  • Other suitable proteases include ALCALASE®, DURAZYM® and SAVINASE® from Novo and MAXATASE®, MAXACAL®, PROPERASE® and MAXAPEM® (protein engineered Maxacal) from Gist-Brocades.
  • Proteolytic enzymes also encompass modified bacterial serine proteases, such as those described in European Patent Application Serial Number 87 303761.8, filed April 28, 1987 (particularly pages 17, 24 and 98), and which is called herein "Protease B", and in European Patent Application 199,404, Venegas, published October 29, 1986, which refers to a modified bacterial serine protealytic enzyme which is called "Protease A” herein.
  • Protease C is a variant of an alkaline serine protease from Bacillus in which lysine replaced arginine at position 27, tyrosine replaced valine at position 104, serine replaced asparagine at position 123, and alanine replaced threonine at position 274.
  • Protease C is described in EP 90915958:4, corresponding to WO 91/06637, Published May 16, 1991. Genetically modified variants, particularly of Protease C, are also included herein.
  • a preferred protease referred to as "Protease D” is a carbonyl hydrolase variant having an amino acid sequence not found in nature, which is derived from a precursor carbonyl hydrolase by substituting a different amino acid for a plurality of amino acid residues at a position in said carbonyl hydrolase equivalent to position +76, preferably also in combination with one or more amino acid residue positions equivalent to those selected from the group consisting of +99, +101 , +103, +104, +107, +123, +27, +105, +109, +126, +128, +135, +156, +166, +195, +197, +204, +206, +210, +216, +217, +218, +222, +260, +265, and/or +274 according to the numbering of Bacillus amyloliquefaciens subtilisin, as described in WO95/10591 and in the patent application of C. Ghosh, et al, "Bleaching Compositions Comprising Protease Enzy
  • proteases described in patent applications EP 251 446 and WO 91/06637, protease BLAP® described in WO91/02792 and their variants described in WO 95/23221.
  • protease from Bacillus sp. NCIMB 40338 described in WO 93/18140 A to Novo.
  • Enzymatic detergents comprising protease, one or more other enzymes, and a reversible protease inhibitor are described in WO 92/03529 A to Novo.
  • a protease having decreased adsorption and increased hydrolysis is available as described in WO 95/07791 to Procter & Gamble.
  • a recombinant trypsin-like protease for detergents suitable herein is described in WO 94/25583 to Novo.
  • Other suitable proteases are described in EP 516200 by Unilever.
  • protease enzymes which are a carbonyl hydrolase variant having an amino acid sequence not found in nature, which is derived by replacement of a plurality of amino acid residues of a precursor carbonyl hydrolase with different amino acids, wherein said plurality of amino acid residues replaced in the precursor enzyme correspond to position +210 in combination with one or more of the following residues: +33, +62, +67, +76, +100, +101 , +103, +104, +107, +128, +129, +130, +132, +135, +156, +158, +164, +166, +167, +170, +209, +215, +217, +218 and +222, where the numbered positions correspond to naturally-occurring subtilisin from Bacillus amyloliouefaciens or to equivalent amino acid residues in other carbonyl hydrolases or subtilisins (such as Bacillus lentus subtilisin).
  • Preferred enzymes of this type include those having position changes +
  • the proteolytic enzymes are incorporated in the detergent compositions of the present invention a level of from 0.0001 % to 2%, preferably from 0.001 % to 0.2%, more preferably from 0.005% to 0.1% pure enzyme by weight of the composition.
  • Amylases ( ⁇ and/or ⁇ ) can be included for removal of carbohydrate-based stains.
  • WO94/02597 Novo Nordisk A/S published February 03, 1994, describes cleaning compositions which incorporate mutant amylases. See also WO95/10603, Novo Nordisk A/S, published April 20, 1995.
  • Other amylases known for use in cleaning compositions include both ⁇ - and ⁇ -amylases.
  • - Amylases are known in the art and include those disclosed in US Pat. no. 5,003,257; EP 252,666; WO/91/00353; FR 2,676,456; EP 285,123; EP 525,610; EP 368,341 ; and British Patent specification no. 1 ,296,839 (Novo).
  • amylases are stability-enhanced amylases described in WO94/18314, published August 18, 1994 and WO96/05295, Genencor, published February 22, 1996 and amylase variants having additional modification in the immediate parent available from Novo Nordisk A/S, disclosed in WO 95/10603, published April 95. Also suitable are amylases described in EP 277 216, WO95/26397 and WO96/23873 (all by Novo Nordisk).
  • ⁇ -amylases examples are Purafect Ox Am® from Genencor and Termamyl®, Ban® ,Fungamyl® and Duramyl®, Natalase ® all available from Novo Nordisk A/S Denmark.
  • WO95/26397 describes other suitable amylases : ⁇ -amylases characterised by having a specific activity at least 25% higher than the specific activity of Termamyl® at a temperature range of 25°C to 55°C and at a pH value in the range of 8 to 10, measured by the Phadebas® ⁇ -amylase activity assay. Suitable are variants of the above enzymes, described in WO96/23873 (Novo Nordisk). Other amylolytic enzymes with improved properties with respect to the activity level and the combination of thermostability and a higher activity level are described in WO95/35382.
  • Preferred amylase enzymes include those described in WO95/26397 and in co- pending application by Novo Nordisk PCT/DK96/00056.
  • amylolytic enzymes are incorporated in the detergent compositions of the present invention a level of from 0.0001 % to 2%, preferably from 0.00018% to 0.06%, more preferably from 0.00024% to 0.048% pure enzyme by weight of the composition
  • compositions of the present invention comprise amylase enzymes, particularly those described in WO95/26397 and co-pending application by Novo Nordisk PCT/DK96/00056 in combination with a complementary amylase.
  • complementary it is meant the addition of one or more amylase suitable for detergency purposes.
  • Examples of complementary amylases ( ⁇ and/or ⁇ ) are described below.
  • WO94/02597 and WO95/10603, Novo Nordisk A/S describe cleaning compositions which incorporate mutant amylases.
  • Other amylases known for use in cleaning compositions include both ⁇ - and ⁇ -amylases.
  • ⁇ - Amylases are known in the art and include those disclosed in US Pat. no. 5,003,257; EP 252,666; WO/91 /00353; FR 2,676,456; EP 285,123; EP 525,610; EP 368,341 ; and British Patent specification no. 1 ,296,839 (Novo).
  • amylases are stability-enhanced amylases described in WO94/18314, and WO96/05295, Genencor and amylase variants having additional modification in the immediate parent available from Novo Nordisk A/S, disclosed in WO 95/10603. Also suitable are amylases described in EP 277 216 (Novo Nordisk). Examples of commercial ⁇ -amylases products are Purafect Ox Am® from Genencor and Termamyl®, Ban® ,Fungamyl® and Duramyl®, all available from Novo Nordisk A/S Denmark.
  • WO95/26397 describes other suitable amylases : ⁇ -amylases characterised by having a specific activity at least 25% higher than the specific activity of Termamyl® at a temperature range of 25°C to 55°C and at a pH value in the range of 8 to 10, measured by the Phadebas® ⁇ - amylase activity assay. Suitable are variants of the above enzymes, described in WO96/23873 (Novo Nordisk). Other amylolytic enzymes with improved properties with respect to the activity level and the combination of thermostability and a higher activity level are described in WO95/35382.
  • Preferred complementary amylases for the present invention are the amylases sold under the tradename Purafect Ox Am R described in WO 94/18314, WO96/05295 sold by Genencor; Termamyl®, Fungamyl®, Ban® Natalase ® and Duramyl®, all available from Novo Nordisk A/S and Maxamyl® by Gist-Brocades.
  • Said complementary amylase is generally incorporated in the detergent compositions of the present invention a level of from 0.0001 % to 2%, preferably from 0.00018% to 0.06%, more preferably from 0.00024% to 0.048% pure enzyme by weight of the composition.
  • a weight of pure enzyme ratio of specific amylase to the complementary amylase is comprised between 9:1 to 1:9, more preferably between 4:1 to 1 :4, and most preferably between 2:1 and 1 :2.
  • the above-mentioned enzymes may be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin. Origin can further be mesophilic or extremophilic (psychrophilic, psychrotrophic, thermophilic, barophilic, alkalophilic, acidophilic, halophilic, etc.). Purified or non-purified forms of these enzymes may be used. Also included by definition, are mutants of native enzymes. Mutants can be obtained e.g. by protein and/or genetic engineering, chemical and/or physical modifications of native enzymes. Common practice as well is the expression of the enzyme via host organisms in which the genetic material responsible for the production of the enzyme has been cloned.
  • Said enzymes are normally incorporated in the detergent composition at levels from 0.0001 % to 2% of active enzyme by weight of the detergent composition.
  • the enzymes can be added as separate single ingredients (prills, granulates, stabilized liquids, etc... containing one enzyme ) or as mixtures of two or more enzymes ( e.g. cogranulates ).
  • enzyme oxidation scavengers which are described in Copending European Patent application 92870018.6 filed on January 31 , 1992.
  • enzyme oxidation scavengers are ethoxylated tetraethylene polyamines.
  • a range of enzyme materials and means for their incorporation into synthetic detergent compositions is also disclosed in WO 9307263 A and WO 9307260 A to Genencor International, WO 8908694 A to Novo, and U.S. 3,553,139, January 5, 1971 to McCarty et al. Enzymes are further disclosed in U.S. 4,101 ,457, Place et al, July 18, 1978, and in U.S. 4,507,219, Hughes, March 26, 1985. Enzyme materials useful for liquid detergent formulations, and their incorporation into such formulations, are disclosed in U.S. 4,261 ,868, Hora et al, April 14, 1981. Enzymes for use in detergents can be stabilised by various techniques.
  • Enzyme stabilisation techniques are disclosed and exemplified in U.S. 3,600,319, August 17, 1971 , Gedge et al, EP 199,405 and EP 200,586, October 29, 1986, Venegas. Enzyme stabilisation systems are also described, for example, in U.S. 3,519,570. A useful Bacillus, sp. AC13 giving proteases, xylanases and cellulases, is described in WO 9401532 A to Novo.
  • Suitable bleaching agents include chlorine and oxygen-releasing bleaching agents, preferably oxygen-releasing bleaching agent containing a hydrogen peroxide source and an organic peroxyacid bleach precursor compound.
  • the production of the organic peroxyacid occurs by an in situ reaction of the precursor with a source of hydrogen peroxide.
  • Preferred sources of hydrogen peroxide include inorganic perhydrate bleaches.
  • a preformed organic peroxyacid is incorporated into the composition in a liquid matrix as a suspended particulate as described above. Compositions containing mixtures of a hydrogen peroxide source and organic peroxyacid precursor in combination with a preformed organic peroxyacid are also envisaged.
  • Particulate compositions preferably include a hydrogen peroxide source, as an oxygen-releasing bleach.
  • Suitable hydrogen peroxide sources include the inorganic perhydrate salts.
  • the inorganic perhydrate salts are normally incorporated in the form of the sodium salt at a level of from 1 % to 40% by weight, more preferably from 2% to 30% by weight and most preferably from 5% to 25% by weight of the compositions.
  • inorganic perhydrate salts include perborate, percarbonate, perphosphate, persulfate and persilicate salts.
  • the inorganic perhydrate salts are normally the alkali metal salts.
  • the inorganic perhydrate salt may be included as the crystalline solid without additional protection.
  • the preferred executions of such granular compositions utilize a coated form of the material which provides better storage stability for the perhydrate salt in the granular product.
  • Sodium perborate can be in the form of the monohydrate of nominal formula NaB ⁇ 2H2 ⁇ 2 or the tetrahydrate NaB ⁇ 2H2 ⁇ 2-3H2 ⁇ .
  • Alkali metal percarbonates, particularly sodium percarbonate are preferred perhydrates for inclusion in compositions in accordance with the invention.
  • Sodium percarbonate is an addition compound having a formula corresponding to 2Na2CO3.3H2O2, and is available commercially as a crystalline solid.
  • Sodium percarbonate being a hydrogen peroxide addition compound tends on dissolution to release the hydrogen peroxide quite rapidly which can increase the tendency for localised high bleach concentrations to arise.
  • the percarbonate is most preferably incorporated into such compositions in a coated form which provides in-product stability.
  • a suitable coating material providing in product stability comprises mixed salt of a water soluble alkali metal sulphate and carbonate.
  • mixed salt of a water soluble alkali metal sulphate and carbonate.
  • the weight ratio of the mixed salt coating material to percarbonate lies in the range from 1 : 200 to 1 : 4, more preferably from 1 : 99 to 1 : 9, and most preferably from 1 : 49 to 1 : 19.
  • the mixed salt is of sodium sulphate and sodium carbonate which has the general formula Na2S ⁇ 4.n.Na2C ⁇ 3 wherein n is from 0.1 to 3, preferably n is from 0.3 to
  • n is from 0.2 to 0.5.
  • Another suitable coating material providing in product stability comprises sodium silicate of Si ⁇ 2 : Na2 ⁇ ratio from 1.8 : 1 to 3.0 : 1 , preferably 1.8:1 to 2.4:1 , and/or sodium metasilicate, preferably applied at a level of from 2% to 10%, (normally from 3% to 5%) of Si ⁇ 2 by weight of the inorganic perhydrate salt.
  • Magnesium silicate can also be included in the coating. Coatings that contain silicate and borate salts or boric acids or other inorganics are also suitable.
  • Peroxyacid bleach precursors are compounds which react with hydrogen peroxide in a perhydrolysis reaction to produce a peroxyacid.
  • peroxyacid bleach precursors may be represented as
  • L is a leaving group and X is essentially any functionality, such that on perhydrolysis the structure of the peroxyacid produced is
  • Peroxyacid bleach precursor compounds are preferably incorporated at a level of from 0.5% to 20% by weight, more preferably from 1 % to 10% by weight, most preferably from 1.5% to 5% by weight of the compositions.
  • Suitable peroxyacid bleach precursor compounds typically contain one or more N- or O-acyl groups, which precursors can be selected from a wide range of classes.
  • Suitable classes include anhydrides, esters, imides, lactams and acylated derivatives of imidazoles and oximes. Examples of useful materials within these classes are disclosed in GB-A-1586789.
  • Suitable esters are disclosed in GB-A-836988, 864798, 1147871 , 2143231 and EP-A-0170386.
  • L group The leaving group, hereinafter L group, must be sufficiently reactive for the perhydrolysis reaction to occur within the optimum time frame (e.g., a wash cycle). However, if L is too reactive, this activator will be difficult to stabilise for use in a bleaching composition.
  • Preferred L groups are selected from the group consisting of:
  • R is an alkyl, aryl, or alkaryl group containing
  • R is an alkyl chain containing from 1 to 8 carbon
  • R is H or R
  • R° is an alkenyl chain containing from 1 to 8 carbon atoms
  • R 1 3 4 and Y is H or a solubilizing group.
  • Any of R , R and R may be substituted by essentially any functional group including, for example alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl, amide and ammonium or alkyl ammonium groups.
  • the preferred solubilizing groups are -SO 3 " M + , -CO 2 " M + , -SO 4 " M + , -N + (R ) 4 X “ and O ⁇ -N(R ) 3 and most preferably -SO 3 " M and -CO 2 M wherein R is an alkyl chain containing from 1 to 4 carbon atoms, M is a cation which provides solubility to the bleach activator and X is an anion which provides solubility to the bleach activator.
  • M is an alkali metal, ammonium or substituted ammonium cation, with sodium and potassium being most preferred, and X is a halide, hydroxide, methylsulfate or acetate anion.
  • Perbenzoic acid precursor compounds provide perbenzoic acid on perhydrolysis.
  • Suitable O-acylated perbenzoic acid precursor compounds include the substituted and unsubstituted benzoyl oxybenzene sulfonates, including for example benzoyl oxybenzene sulfonate:
  • benzoylation products of sorbitol, glucose, and all saccharides with benzoylating agents including for example:
  • Perbenzoic acid precursor compounds of the imide type include N-benzoyl succinimide, tetrabenzoyl ethylene diamine and the N-benzoyl substituted ureas.
  • Suitable imidazole type perbenzoic acid precursors include N-benzoyl imidazole and N-benzoyl benzimidazole and other useful N-acyl group-containing perbenzoic acid precursors include N-benzoyl pyrrolidone, dibenzoyl taurine and benzoyl pyroglutamic acid.
  • perbenzoic acid precursors include the benzoyl diacyl peroxides, the benzoyl tetraacyl peroxides, and the compound having the formula:
  • Phthalic anhydride is another suitable perbenzoic acid precursor compound herein:
  • Suitable N-acylated lactam perbenzoic acid precursors have the formula:
  • n is from 0 to 8, preferably from 0 to 2
  • R is a benzoyl group.
  • Perbenzoic acid derivative precursors provide substituted perbenzoic acids on perhydrolysis.
  • Suitable substituted perbenzoic acid derivative precursors include any of the herein disclosed perbenzoic precursors in which the benzoyl group is substituted by essentially any non-positively charged (i.e.; non-cationic) functional group including, for example alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl and amide groups.
  • a preferred class of substituted perbenzoic acid precursor compounds are the amide substituted compounds of the following general formulae:
  • R1 is an aryl or alkaryl group with from 1 to 14 carbon atoms
  • R 2 is an arylene, or alkarylene group containing from 1 to 14 carbon atoms
  • R ⁇ is H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms and L can be essentially any leaving group.
  • R1 preferably contains from 6 to 12 carbon atoms.
  • R 2 preferably contains from 4 to 8 carbon atoms.
  • R ⁇ may be aryl, substituted aryl or alkylaryl containing branching, substitution, or both and may be sourced from either synthetic sources or natural sources including for example, tallow fat. Analogous structural variations are permissible for R 2 .
  • substitution can include alkyl, aryl, halogen, nitrogen, sulphur and other typical substituent groups or organic compounds.
  • R ⁇ is preferably H or methyl.
  • R1 and R5 should not contain more than 18 carbon atoms in total. Amide substituted bleach activator compounds of this type are described in EP-A- 0170386.
  • Cationic peroxyacid precursor compounds produce cationic peroxyacids on perhydrolysis.
  • cationic peroxyacid precursors are formed by substituting the peroxyacid part of a suitable peroxyacid precursor compound with a positively charged functional group, such as an ammonium or alkyl ammonium group, preferably an ethyl or methyl ammonium group.
  • Cationic peroxyacid precursors are typically present in the compositions as a salt with a suitable anion, such as for example a halide ion or a methylsulfate ion.
  • the peroxyacid precursor compound to be so cationically substituted may be a perbenzoic acid, or substituted derivative thereof, precursor compound as described hereinbefore.
  • the peroxyacid precursor compound may be an alkyl percarboxylic acid precursor compound or an amide substituted alkyl peroxyacid precursor as described hereinafter
  • Cationic peroxyacid precursors are described in U.S. Patents 4,904,406; 4,751 ,015; 4,988,451; 4,397,757; 5,269,962; 5,127,852; 5,093,022; 5,106,528; U.K. 1 ,382,594; EP 475,512, 458,396 and 284,292; and in JP 87-318,332.
  • Suitable cationic peroxyacid precursors include any of the ammonium or alkyl ammonium substituted alkyl or benzoyl oxybenzene sulfonates, N-acylated caprolactams, and monobenzoyltetraacetyl glucose benzoyl peroxides.
  • a preferred cationically substituted benzoyl oxybenzene sulfonate is the 4- (trimethyl ammonium) methyl derivative of benzoyl oxybenzene sulfonate:
  • a preferred cationically substituted alkyl oxybenzene sulfonate has the formula:
  • Preferred cationic peroxyacid precursors of the N-acylated caprolactam class include the trialkyl ammonium methylene benzoyl caprolactams, particularly trimethyl ammonium methylene benzoyl caprolactam:
  • N-acylated caprolactam class examples include the trialkyl ammonium methylene alkyl caprolactams:
  • n is from 0 to 12, particularly from 1 to 5.
  • Another preferred cationic peroxyacid precursor is 2-(N,N,N-trimethyl ammonium) ethyl sodium 4-sulphophenyl carbonate chloride.
  • Alkyl percarboxylic acid bleach precursors form percarboxylic acids on perhydrolysis.
  • Preferred precursors of this type provide peracetic acid on perhydrolysis.
  • Preferred alkyl percarboxylic precursor compounds of the imide type include the N-,N,N ⁇ N ⁇ tetra acetylated alkylene diamines wherein the alkylene group contains from 1 to 6 carbon atoms, particularly those compounds in which the alkylene group contains 1 , 2 and 6 carbon atoms. Tetraacetyl ethylene diamine (TAED) is particularly preferred.
  • TAED Tetraacetyl ethylene diamine
  • alkyl percarboxylic acid precursors include sodium 3,5,5-tri- methyl hexanoyloxybenzene sulfonate (iso-NOBS), sodium nonanoyloxybenzene sulfonate (NOB ' S), sodium acetoxybenzene sulfonate (ABS) and penta acetyl glucose.
  • Amide substituted alkyl peroxyacid precursors are also suitable, including those of the following general formulae:
  • R ⁇ is an alkyl group with from 1 to 14 carbon atoms
  • R 2 is an alkylene group containing from 1 to 14 carbon atoms
  • R ⁇ is H or an alkyl group containing 1 to 10 carbon atoms and L can be essentially any leaving group.
  • R ⁇ preferably contains from 6 to 12 carbon atoms.
  • R 2 preferably contains from 4 to 8 carbon atoms.
  • R ⁇ may be straight chain or branched alkyl containing branching, substitution, or both and may be sourced from either synthetic sources or natural sources including for example, tallow fat. Analogous structural variations are permissible for R 2 .
  • the substitution can include alkyl, halogen, nitrogen, sulphur and other typical substituent groups or organic compounds.
  • R ⁇ is preferably H or methyl.
  • R ⁇ and R ⁇ should not contain more than 18 carbon atoms in total. Amide substituted bleach activator compounds of this type are described in EP-A-0170386.
  • precursor compounds of the benzoxazin-type as disclosed for example in EP-A-332,294 and EP-A-482,807, particularly those having the formula:
  • R.. is H, alkyl, alkaryl, aryl, arylalkyl, and wherein R 2 , Ro, R 4 , and Re may be the same or different substituents selected from H, halogen, alkyl, alkenyl, aryl, hydroxyl, alkoxyl, amino, alkyl amino, COORg (wherein R Q is H or an alkyl group) and carbonyl functions.
  • An especially preferred precursor of the benzoxazin-type is:
  • the organic peroxyacid bleaching system may contain, in addition to, or as an alternative to, an organic peroxyacid bleach precursor compound, a preformed organic peroxyacid , typically at a level of from 0.5% to 25% by weight, more preferably from 1 % to 10% by weight of the composition.
  • a preferred class of organic peroxyacid compounds are the amide substituted compounds of the following general formulae:
  • R ⁇ is an alkyl, aryl or alkaryl group with from 1 to 14 carbon atoms
  • R 2 is an alkylene, arylene, and alkarylene group containing from 1 to 14 carbon atoms
  • R 5 is H or an alkyl, aryl, or alkaryl group containing 1 to 10 carbon atoms.
  • R1 preferably contains from 6 to 12 carbon atoms.
  • R 2 preferably contains from 4 to 8 carbon atoms.
  • R1 may be straight chain or branched alkyl, substituted aryl or alkylaryl containing branching, substitution, or both and may be sourced from either synthetic sources or natural sources including for example, tallow fat. Analogous structural variations are permissible for R 2 .
  • substitution can include alkyl, aryl, halogen, nitrogen, sulphur and other typical substituent groups or organic compounds.
  • R 5 is preferably H or methyl.
  • R1 and R ⁇ should not contain more than 18 carbon atoms in total. Amide substituted organic peroxyacid compounds of this type are described in EP-A- 0170386.
  • organic peroxyacids include diacyl and tetraacylperoxides, especially diperoxydodecanedioc acid, diperoxytetradecanedioc acid, and diperoxyhexadecanedioc acid.
  • Dibenzoyl peroxide is a preferred organic peroxyacid herein.
  • Mono- and diperazelaic acid, mono- and diperbrassylic acid are also suitable herein.
  • peracid Pre-formed monoperoxycarboxylic acids (hereafter referred to as peracid) suitable for use herein are mono peracids, meaning that the peracid contains one peroxygen group.
  • the peracid is in solid form.
  • R is a linear or branched alkyl chain having at least 1 carbon atom and X is hydrogen or a substituent group selected from the group consisting of alkyl, especially alkyl chains of from 1 to 24 carbon atoms, aryl, halogen, ester, ether, amine, amide, substituted phthalic amino, imide, hydroxide, sulphide, sulphate, sulphonate, carboxylic, heterocyclic, nitrate, aldehyde, phosphonate, phosphonic or mixtures thereof.
  • the R group preferably comprises up to 24 carbon atoms.
  • the R group may be a branched alkyl chain comprising one or more side chains which comprise substituent groups selected from the group consisting of aryl, halogen, ester, ether, amine, amide, substituted phthalic amino, imide, hydroxide, sulphide, sulphate, sulphonate, carboxylic, heterocyclic, nitrate, aldehyde, ketone or mixtures thereof.
  • X group is a phthalimido group.
  • particularly preferred peracids are those having general formula:
  • R is C1-20 and where A, B, C and D are independently either hydrogen or substituent groups individually selected from the group consisting of alkyl, hydroxyl, nitro, halogen, amine, ammonium, cyanide, carboxylic, sulphate, sulphonate, aldehydes or mixtures thereof.
  • R is an alkyl group having from 3 to 12 carbon atoms, more preferably from 5 to 9 carbon atoms.
  • Preferred substituent groups A, B, C and D are linear or branched alkyl groups having from 1 to 5 carbon atoms, but more preferably hydrogen.
  • Preferred peracids are selected from the group consisting of phthaloyl amido peroxy hexanoic acid, phthaloyl amido peroxy heptanoic acid, phthaloyl amido peroxy octanoic acid, phthaloyl amido peroxy nonanoic acid, phthaloyl amido peroxy decanoic acid and mixtures thereof.
  • the peracid has the formula such that R is CsH 10 i.e. phthaloyl amido peroxy hexanoic acid or PAP.
  • This peracid is preferably used as a substantially water-insoluble solid or wetcake and is available from Ausimont under the trade name Euroco.
  • the peracid is preferably used at a level of from 0.1 % to 30%, more preferably from 0.5% to 18% and most preferably 1 % to 12% by weight of the composition.
  • compositions described herein which contain bleach as detergent component may additionally contain as a preferred component, a metal containing bleach catalyst.
  • a metal containing bleach catalyst is a transition metal containing bleach catalyst, more preferably a manganese or cobalt-containing bleach catalyst.
  • compositions of the present invention may comprise an effective amount of a bleach catalyst.
  • an effective amount is defined as "an amount of the transition-metal bleach catalyst present in the present invention compositions, or during use according to the present invention methods, that is sufficient, under whatever comparative or use conditions are employed, to result in at least partial oxidation of the material sought to be oxidized by the composition or method.”
  • compositions of the present invention comprise from 1 ppb (0.0000001 %), more preferably from 100 ppb (0.00001 %), yet more preferably from 500 ppb (0.00005%), still more preferably from 1 ppm (0.0001 %) to 99.9%, more preferably to 50%, yet more preferably to 5%, still more preferably to 500 ppm (0.05%) by weight of the composition, of a metal bleach catalyst as described herein below.
  • a suitable type of bleach catalyst is a catalyst comprising a heavy metal cation of defined bleach catalytic activity, such as copper, iron cations, an auxiliary metal cation having little or no bleach catalytic activity, such as zinc or aluminium cations, and a sequestrant having defined stability constants for the catalytic and auxiliary metal cations, particularly ethylenediaminetetraacetic acid, ethylenediaminetetra(methylenephosphonic acid) and water-soluble salts thereof.
  • a heavy metal cation of defined bleach catalytic activity such as copper, iron cations
  • an auxiliary metal cation having little or no bleach catalytic activity such as zinc or aluminium cations
  • a sequestrant having defined stability constants for the catalytic and auxiliary metal cations, particularly ethylenediaminetetraacetic acid, ethylenediaminetetra(methylenephosphonic acid) and water-soluble salts thereof.
  • Preferred types of bleach catalysts include the manganese-based complexes disclosed in U.S. Pat. 5,246,621 and U.S. Pat. 5,244,594. Preferred examples of these catalysts include Mn'V2(u-O)3(1 ,4,7-trimethyl-1 ,4,7-triazacyclononane)2- (PF ⁇ )2. Mn'"2(u-O)-j (u-OAc)2(1 ,4,7-trimethyl-1 ,4,7-triazacyclononane)2-
  • ligands suitable for use herein include 1 ,5,9-trimethyl-1 ,5,9- triazacyclododecane, 2-methyl-1 ,4,7-triazacyclononane, . 2-methyl-1 ,4,7- triazacyclononane, 1 ,2,4,7-tetramethyl-1 ,4,7- triazacyclononane, and mixtures thereof.
  • the bleach catalysts useful in the compositions herein may also be selected as apprdpriate for the present invention.
  • suitable bleach catalysts see U.S. Pat. 4,246,612 and U.S. Pat. 5,227,084. See also U.S. Pat. 5,194,416 which teaches mononuclear manganese (IV) complexes such as Mn(1,4,7- trimethyl-1 ,4,7-triazacyclononane)(OCH3)3_(PF6).
  • Still another type of bleach catalyst is a water-soluble complex of manganese (III), and/or (IV) with a ligand which is a non-carboxylate polyhydroxy compound having at least three consecutive C-OH groups.
  • Preferred ligands include sorbitol, iditol, dulsitol, mannitol, xylithol, arabitol, adonitol, meso-erythritol, meso-inositol, lactose, and mixtures thereof.
  • U.S. Pat. 5,114,611 teaches a bleach catalyst comprising a complex of transition metals, including Mn, Co, Fe, or Cu, with an non-(macro)-cyclic ligand. Said ligands are of the formula:
  • Preferred ligands include pyridine, pyridazine, pyrimidine, pyrazine, imidazole, pyrazole, and triazole rings.
  • said rings may be substituted with substituents such as alkyl, aryl, alkoxy, halide, and nitro.
  • Particularly preferred is the ligand 2,2'-bispyridylamine.
  • Preferred bleach catalysts include Co, Cu, Mn, Fe,- bispyridylmethane and -bispyridylamine complexes.
  • Highly preferred catalysts include Co(2,2'-bispyridylamine)Cl2, Di(isothiocyanato)bispyridylamine-cobalt (II), trisdipyridylamine-cobalt(ll) perchlorate, Co(2,2-bispyridylamine)2 ⁇ 2Cl ⁇ 4,
  • Bis-(2,2'-bispyridylamine) copper(ll) perchlorate tris(di-2-pyridylamine) iron(ll) perchlorate, and mixtures thereof.
  • Preferred examples include binuclear Mn complexes with tetra-N-dentate and bi- N-dentate ligands, including N4Mn l "(u-O)2Mn lv N4) + and [Bipy2Mn lll (u-
  • the bleach-catalyzing manganese complexes of the present invention have not been elucidated, it may be speculated that they comprise chelates or other hydrated coordination complexes which result from the interaction of the carboxyl and nitrogen atoms of the ligand with the manganese cation.
  • the oxidation state of the manganese cation during the catalytic process is not known with certainty, and may be the (+11), (+111), (+IV) or (+V) valence state. Due to the ligands' possible six points of attachment to the manganese cation, it may be reasonably speculated that multi-nuclear species and/or "cage" structures may exist in the aqueous bleaching media. Whatever the form of the active Mn- ligand species which actually exists, it functions in an apparently catalytic manner to provide improved bleaching performances on stubborn stains such as tea, ketchup, coffee, wine, juice, and the like.
  • bleach catalysts are described, for example, in European patent application, publication no. 408,131 (cobalt complex catalysts), European patent applications, publication nos. 384,503, and 306,089 (metallo-porphyrin catalysts), U.S. 4,728,455 (manganese/multidentate ligand catalyst), U.S. 4,711 ,748 and European patent application, publication no. 224,952, (absorbed manganese on aluminosilicate catalyst), U.S. 4,601 ,845 (aluminosilicate support with manganese and zinc or magnesium salt), U.S. 4,626,373 (manganese/ligand catalyst), U.S. 4,119,557 (ferric complex catalyst), German Pat.
  • cobalt (111) catalysts having the formula:
  • Preferred cobalt catalysts of this type have the formula:
  • the preferred cobalt catalyst of this type useful herein are cobalt pentaamine chloride salts having the formula [Co(NH3)5CI] Yy, and especially
  • Preferred T are selected from the group consisting of chloride, iodide, I3-, formate, nitrate, nitrite, sulfate, sulfite, citrate, acetate, carbonate, bromide, PF ⁇ " ,
  • T can be protonated if more than one anionic group exists in T, e.g., HPO4 2 ", HCO3-, H2PO4", etc.
  • T may be selected from the group consisting of non-traditional inorganic anions such as anionic surfactants (e.g., linear alkylbenzene sulfonates (LAS), alkyl sulfates (AS), alkylethoxysulfonates (AES), etc.) and/or anionic polymers (e.g., polyacrylates, polymethacrylates, etc.).
  • anionic surfactants e.g., linear alkylbenzene sulfonates (LAS), alkyl sulfates (AS), alkylethoxysulfonates (AES), etc.
  • anionic polymers e.g., polyacrylates, polymethacrylates, etc.
  • the M moieties include, but are not limited to, for example, F", SO4 "2 , NCS " ,
  • M can be protonated if more than one anionic group exists in M (e.g.,
  • Preferred M moieties are substituted and unsubstituted C1-C30 carboxylic acids having the formulas:
  • R is preferably selected from the group consisting of hydrogen and C «
  • Such substituted R therefore include the moieties -(CH2)n ⁇ and -(CH2)nNR'4 + , wherein n is an integer from 1 to 16, preferably from 2 to 10, and most preferably from 2 to 5.
  • M are carboxylic acids having the formula above wherein R is selected from the group consisting of hydrogen, methyl, ethyl, propyl, straight or branched C4-C12 Qlkyl, and benzyl. Most preferred R is methyl.
  • Preferred carboxylic acid M moieties include formic, benzoic, octanoic, nonanoic, decanoic, dodecanoic, malonic, maleic, succinic, adipic, phthalic, 2- ethylhexanoic, naphthenoic, oleic, palmitic, triflate, tartrate, stearic, butyric, citric, acrylic, aspartic, fumaric, lauric, linoleic, lactic, malic, and especially acetic acid.
  • the B moieties include carbonate, di- and higher carboxylates (e.g., oxalate, malonate, malic, succinate, maleate), picolinic acid, and alpha and beta amino acids (e.g., glycine, alanine, beta-alanine, phenylalanine).
  • carboxylates e.g., oxalate, malonate, malic, succinate, maleate
  • picolinic acid e.g., glycine, alanine, beta-alanine, phenylalanine.
  • Cobalt bleach catalysts useful herein are known, being described for example along with their base hydrolysis rates, in M. L. Tobe, "Base Hydrolysis of Transition-Metal Complexes", Adv. Inorg. Bioinorg. Mech.. (1983), 2, pages 1-94.
  • cobalt pentaamine acetate salts having the formula [Co(NH3)5OAc] Ty, wherein OAc represents an acetate moiety, and especially cobalt pentaamine acetate chloride, [Co(NH 3 ) 5 OAc]CI 2 ; as well as [Co(NH 3 ) 5 OAc](OAc)2; [Co(NH3) 5 OAc](PF 6 ) 2 ; [Co(NH 3 ) 5 OAc](SO 4 ); [Co(NH3) 5 OAc](BF 4 )2; and [Co(NH3) 5 OAc](NO 3 )2 (herein "PAC").
  • PAC cobalt pentaamine acetate salts having the formula [Co(NH3)5OAc] Ty, wherein OAc represents an acetate moiety, and especially cobalt pentaamine acetate chloride, [Co(NH 3 ) 5 OAc]CI 2 ; as well as [Co(NH 3 ) 5 OA
  • Cobalt catalysts suitable for incorporation into the detergent compositions of the present invention may be produced according to the synthetic routes disclosed in U.S. Patent Nos. 5,559,261 , 5,581 ,005, and 5,597,936, the disclosures of which are herein incorporated by reference.
  • bleach catalysts include transition-metal bleach catalyst comprising :
  • a transition metal selected from the group consisting of Mn(ll), Mn(lll), Mn(IV), Mn(V), Fe(ll), Fe(lll), Fe(IV), Co(l), Co(ll), Co(lll), Ni(l), Ni(ll), Ni(lll), Cu(l), Cu(ll), Cu(ll), Cr(ll), Cr(lll), Cr(IV), Cr(V), Cr(VI), V(lll), V(IV), V(V), Mo(IV), Mo(V), Mo(VI), W(IV), W(V), W(VI), Pd(ll), Ru(ll), Ru(lll), and Ru(IV), preferably Mn(ll), Mn(lll), Mn(IV), Fe(ll), Fe(lll), Fe(IV), Cr(ll), Cr(IV), Cr(V), Cr(VI), and mixtures thereof;
  • a cross-bridged macropolycyclic ligand being coordinated by four or five donor atoms to the same transition metal, said ligand comprising:
  • an organic macrocycle ring containing four or more donor atoms (preferably at least 3, more preferably at least 4, of these donor atoms are N) separated from each other by covalent linkages of 2 or 3 non- donor atoms, two to five (preferably three to four, more preferably four) of these donor atoms being coordinated to the same transition metal atom in the complex; b) a cross-bridged chain which covalently connects at least 2 non- adjacent donor atoms of the organic macrocycle ring, said covalently connected non-adjacent donor atoms being bridgehead donor atoms which are coordinated to the same transition metal in the complex, and wherein said cross-bridged chain comprises from 2 to about 10 atoms (preferably the cross-bridged chain is selected from 2, 3 or 4 non-donor atoms, and 4-6 non-donor atoms with a further donor atom); and
  • non-macropolycyclic ligands preferably selected from the group consisting of H2O, ROH, NR3, RCN, OH “ , OOH “ , RS “ ,
  • SO4 , SO3 , PO4 organic phosphates, organic phosphonates, organic sulfates, organic sulfonates, and aromatic N donors such as pyridines, pyrazines, pyrazoles, imidazoles, benzimidazoles, pyrimidines, triazoles and thiazoles with R being H, optionally substituted alkyl, optionally substituted aryl.
  • the preferred cross-bridged macropolycyclic ligands are is selected from the group consisting of:
  • X is selected from the group consisting of oxygen, sulfur, -NR- phosphorous, or X represents a covalent bond wherein E has the formula:
  • each E units the sum of a + a' is independently selected from 1 to 5; each G unit is a moiety (CR n ) b ; each R unit is independently selected from H, alkyl, alkenyl, alkynyl, aryl, alkylaryl, and heteroaryl, or two or more R units are covalently bonded to form an aromatic, heteroaromatic, cycloalkyl, or heterocycloalkyl ring; each D unit is a donor atom independently selected from the group consisting of nitrogen, oxygen, sulfur, and phosphorous, and at least two atoms which comprise D units are bridgehead donor atoms coordinated to the transition metal; B units are a carbon atom, a D unit, or a cycloalkyl or heterocyclic ring; each n is an integer independently selected from 1 and 2, completing the valence of the carbon atoms to which the R units are covalently bonded; each
  • a preferred ligand for the purposes of the present invention 5,12-dimethyl-1 ,5,8,12 ⁇ tetraaza- bicyclo[6.6.2]hexadecane, has the IUPAC name 4,11-dimethyl-1 ,4,8,11-tetraaza- bicyclo[6.6.2]hexadecane.
  • a further preferred ligand is 5,12-diethyl-1 ,5,8,12- tetraaza-bicyclo[6.6.2]hexadecane.
  • Metal bleach catalysts useful in the invention compositions can in general include known compounds where they conform with the invention definition, as well as, more preferably, any of a large number of novel compounds expressly designed for the present laundry use.
  • Suitable bleach catalysts for use in the compositions herein further include for example:
  • suitable complexes useful as transition-metal bleach catalysts further include not only monometallic, mononuclear kinds such as those illustrated hereinabove but also bimetallic, trimetallic or cluster kinds. Monometallic, mononuclear complexes are preferred. As defined herein, a monometallic transition-metal bleach catalyst contains only one transition metal atom per mole of complex. A monometallic, mononuclear complex is one in which any donor atoms of the essential macrocyclic ligand are bonded to the same transition metal atom, that is, the essential ligand does not "bridge" across two or more transition-metal atoms.
  • manganese transition metal complexes are the manganese(lll) and manganese(IV) complexes having the general formula:
  • X is independently a coordinating or bridging species non- limiting examples of which are H 2 O, O 2 2" , O 2" , “ OH, HO 2 " , SH “ , S 2' , >SO, Cl “ , SCN “ , N 3 “ , N 3” , RSO 3 “ , RCOO “ , NH 2 " , and NR 3 , wherein R is H alkyl, aryl, each of which is optionally substituted, and R 1 COO, wherein R 1 is an alkyl, aryl unit, each of which may be optionally substituted;
  • L is a ligand which is an organic molecule containing a number of nitrogen atoms which co-ordinate via all or some of said nitrogen atoms to the manganese centers; z denotes the charge of the complex and is an integer which can have a positive or negative value;
  • Y is a monovalent or multivalent counter-ion, which provides charge neutrality, which dependent upon the charge z of the complex; and q is z/Y.
  • manganese complexes are those wherein said coordinating or bridging group X is either C ⁇ COO " , O 2" , and mixtures thereof, preferably when said manganese atom is in the (IV) oxidation state and X is O 2" .
  • Ligands which are preferred are those which contain at least three nitrogen atoms and which coordinate via three nitrogen atoms to one of the manganese centers and are preferably of a macrocyclic nature.
  • Preferred ligands have the formula:
  • preferred ligands are 1 ,4,7-trimethyl-1 ,4,7- triazacyclononane (Me 3 -TACN), and 1 ,2,4,7-tetramethyl-1 ,4,7-triazacyclononane (Me 4 -TACN).
  • the selection of the counter ion Y for establishing charge neutrality is not critical for the activity of the complex.
  • Non-limiting examples of said counter ions are chloride, sulphate, nitrate, methylsulphate, surfactant-ions, such as long chain alkylsulphates, alkylsulphonates, alkylbenzenesulphonates, tosylate, trifluoromethylsulphonate, perchlorate, BPh " , PF 6 " , and mixtures thereof.
  • manganese complexes of this type include: i) [(Me 3 -TACN)Mn l (m-O) 3 Mn l (Me 3 -TACN)] 2+ (PF 6 -) 2 ; ii) [(Me 4 -TACN)Mn l (m-O) 3 Mn l (Me 4 -TACN)] 2+ (PF 6 " )2; iii) [(Me3-TACN)Mn l "(m-O)(m-OAc)2Mn l "(Me3-TACN)] 2+ (PF 6 " )2; iv) [(Me 4 -TACN)Mn lll (m-O)(m-OAc) 2 Mn" l (Me 4 -TACN)] 2+ (PF 6 " )2;
  • manganese complex catalysts are the mononuclear complexes having the formula:
  • R is C1-C20 radical selected from the group consisting of alkyl, cycloalkyl, aryl, benzyl, and radical combinations thereof; at least two R radicals may also be connected to one another so as to form a bridging unit between two oxygens that coordinate with the manganese;
  • L is a ligand selected from a C 3 -C 6 o radical having at least 3 nitrogen atoms coordinating with the manganese; and
  • Y is an oxidatively-stable counterion dependent upon the charge of the complex.
  • Non-limiting examples of preferred complexes are those wherein L is 1,4,7- trimethyl-1 ,4,7-triazacyclononane, and 2 methyl-1 ,4,7-trimethyl-1 ,4,7- triazacyclononane, and R is Ci alkyl.
  • mononuclear manganese complex catalysts which are capable of bleaching in the absence of a source of hydrogen peroxide or other peroxygen bleaching agent include those having the formula:
  • t is 2; s is 3; R 1 , R 2 and R 3 are each independently selected from hydrogen, C ⁇ -C 6 alkyl, aryl, each of which can be optionally substituted.
  • a particularly useful metal bleach catalyst is [Mn(Bcyclam)CI2]:
  • the bleach catalysts herein may be co-processed with adjunct materials so as to reduce the colour impact if desired for the aesthetics of the product, or to be included in enzyme-containing particles as exemplified hereinafter, or the compositions may be manufactured to contain catalyst "speckles".
  • Organic polymeric compounds may be added as preferred components of the compositions in accord with the invention.
  • organic polymeric compound it is meant essentially any polymeric organic compound commonly found in detergent compositions having dispersant, anti-redeposition, soil release agents or other detergency properties.
  • Organic polymeric compound is typically incorporated in the detergent compositions of the invention at a level of from 0.1 % to 30%, preferably from 0.5%o to 15%, most preferably from 1% to 10% by weight of the compositions.
  • organic polymeric compounds include the water soluble organic homo- or co-polymeric polycarboxylic acids, modified polycarboxylates or their salts in which the polycarboxylic acid comprises at least two carboxyl radicals separated from each other by not more than two carbon atoms. Polymers of the latter type are disclosed in GB-A-1 ,596,756.
  • salts are polyacrylates of molecular weight 2000-10000 and their copolymers with any suitable other monomer units including modified acrylic, fumaric, maleic, itaconic, aconitic, mesaconic, citraconic and methylenemalonic acid or their salts, maleic anhydride, acrylamide, alkylene, vinylmethyl ether, styrene and any mixtures thereof.
  • Preferred are the copolymers of acrylic acid and maleic anhydride having a molecular weight of from 5000 to 100 000, more preferably from 20,000 to 100,000.
  • Preferred commercially available acrylic acid containing polymers having a molecular weight below 15,000 include those sold under the tradename Sokalan PA30, PA20, PA15, PA10 and Sokalan CP10 by BASF GmbH, and those sold under the tradename Acusol 45N, 480N, 460N by Rohm and Haas.
  • Preferred acrylic acid containing copolymers include those which contain as monomer units: a) from 90% to 10%, preferably from 80% to 20% by weight acrylic acid or its salts and b) from 10% to 90%, preferably from 20% to 80% by weight of a substituted acrylic monomer or its salts having the general formula - [CR2-CR1 (CO-O-R3)]- wherein at least one of the substituents R ⁇
  • , R2 or R3 preferably R ⁇
  • or R2 can be a hydrogen
  • R3 can be a hydrogen or alkali metal salt.
  • Most preferred is a substituted acrylic monomer wherein Ri is methyl, R2 is hydrogen (
  • polyamine and modified polyamine compounds are useful herein including those derived from aspartic acid such as those disclosed in EP-A-305282, EP-A- 305283 and EP-A-351629.
  • Other optional polymers may polyvinyl alcohols and acetates both modified and non-modified, cellulosics and modified cellulosics, polyoxyethylenes, polyoxypropylenes, and copolymers thereof, both modified and non-modified, terephthalate esters of ethylene or propylene glycol or mixtures thereof with polyoxyalkylene units.
  • Suitable polymeric soil release agents include those soil release agents having:
  • nonionic hydrophile components consisting essentially of (i) polyoxyethylene segments with a degree of polymerization of at least 2, or (ii) oxypropylene or polyoxypropylene segments with a degree of polymerization of from 2 to 10, wherein said hydrophile segment does not encompass any oxypropylene unit unless it is bonded to adjacent moieties at each end by ether linkages, or (iii) a mixture of oxyalkylene units comprising oxyethylene and from
  • hydrophile segments preferably comprising at least 25% oxyethylene units and more preferably, especially for such components having 20 to 30 oxypropylene units, at least 50% oxyethylene units; or (b) one or more hydrophobe components comprising (i) C3 oxyalkylene terephthalate segments, wherein, if said hydrophobe components also comprise oxyethylene terephthalate, the ratio of oxyethylene terephthalate: C3 oxyalkylene terephthalate units is 2:1 or lower, (ii) C4-C6 alkylene or oxy C4-C6 alkylene segments, or mixtures therein, (iii) poly (vinyl ester) segments, preferably polyvinyl acetate, having a degree of polymerization of at least 2, or (iv) C1-C4 alkyl ether or C4 hydroxyalkyl ether substituents, or mixtures therein, wherein said substituents are present in the form of C1-C4
  • the polyoxyethylene segments of (a)(i) will have a degree of polymerization of from 200, although higher levels can be used, preferably from 3 to 150, more preferably from 6 to 100.
  • Suitable oxy C4-C6 alkylene hydrophobe segments include, but are not limited to, end-caps of polymeric soil release agents such as M ⁇ 3S(CH2) n OCH2CH2 ⁇ -, where M is sodium and n is an integer from 4-6, as disclosed in U.S. Patent 4,721 ,580, issued January 26, 1988 to Gosselink.
  • Polymeric soil release agents useful herein also include cellulosic derivatives such as hydroxyether cellulosic polymers, copolymeric blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate, and the like. Such agents are commercially available and include hydroxyethers of cellulose such as METHOCEL (Dow).
  • Cellulosic soil release agents for use herein also include those selected from the group consisting of C1-C4 alkyl and C4 hydroxyalkyl cellulose; see U.S. Patent
  • Soil release agents characterized by poly(vinyl ester) hydrophobe segments include graft copolymers of poly(vinyl ester), e.g., C-i-C ⁇ vinyl esters, preferably poly(vinyl acetate) grafted onto polyalkylene oxide backbones, such as polyethylene oxide backbones.
  • poly(vinyl ester) e.g., C-i-C ⁇ vinyl esters
  • poly(vinyl acetate) grafted onto polyalkylene oxide backbones such as polyethylene oxide backbones.
  • Another suitable soil release agent is a copolymer having random blocks of ethylene terephthalate and polyethylene oxide (PEO) terephthalate.
  • the molecular weight of this polymeric soil release agent is in the range of from 25,000 to 55,000. See U.S. Patent 3,959,230 to Hays, issued May 25, 1976 and U.S. Patent 3,893,929 to Basadur issued July 8, 1975.
  • Another suitable polymeric soil release agent is a polyester with repeat units of ethylene terephthalate units contains 10-15% by weight of ethylene terephthalate units together with 90-80% by weight of polyoxyethylene terephthalate units, derived from a polyoxyethylene glycol of average molecular weight 300-5,000.
  • Another suitable polymeric soil release agent is a sulfonated product of a substantially linear ester oligomer comprised of an oligomeric ester backbone of terephthaloyl and oxyalkyleneoxy repeat units and terminal moieties covalently attached to the backbone.
  • These soil release agents are described fully in U.S. Patent 4,968,451 , issued November 6, 1990 to J.J. Scheibel and E.P. Gosselink.
  • Other suitable polymeric soil release agents include the terephthalate polyesters of U.S. Patent 4,711 ,730, issued December 8, 1987 to Gosselink et al, the anionic end-capped oligomeric esters of U.S.
  • Patent 4,721 ,580 issued January 26, 1988 to Gosselink
  • block polyester oligomeric compounds of U.S. Patent 4,702,857 issued October 27, 1987 to Gosselink.
  • Other polymeric soil release agents also include the soil release agents of U.S. Patent 4,877,896, issued October 31, 1989 to Maldonado et al, which discloses anionic, especially sulfoarolyl, end-capped terephthalate esters.
  • Another soil release agent is an oligomer with repeat units of terephthaloyl units, sulfoisoterephthaloyl units, oxyethyleneoxy and oxy-1 ,2-propylene units.
  • the repeat units form the backbone of the oligomer. and are preferably terminated with modified isethionate end-caps.
  • a particularly preferred soil release agent of this type comprises one sulfoisophthaloyl unit, 5 terephthaloyl units, oxyethyleneoxy and oxy-1 ,2-propyleneoxy units in a ratio of from 1.7 to 1.8, and two end-cap units of sodium 2-(2-hydroxyethoxy)-ethanesulfonate.
  • compositions of the invention may contain as an optional component a heavy metal ion sequestrant.
  • heavy metal ion sequestrant it is meant herein components which act to sequester (chelate) heavy metal ions. These components may also have calcium and magnesium chelation capacity, but preferentially they show selectivity to binding heavy metal ions such as iron, manganese and copper.
  • Heavy metal ion sequestrants are generally present at a level of from 0.005% to 20%, preferably from 0.1 % to 10%, more preferably from 0.25% to 7.5% and most preferably from 0.5% to 5% by weight of the compositions.
  • Heavy metal ion sequestrants which are acidic in nature, having for example phosphonic acid or carboxylic acid functionalities, may be present either in their acid form or as a complex/salt with a suitable counter cation such as an alkali or alkaline metal ion, ammonium, or substituted ammonium ion, or any mixtures thereof.
  • a suitable counter cation such as an alkali or alkaline metal ion, ammonium, or substituted ammonium ion, or any mixtures thereof.
  • any salts/complexes are water soluble.
  • the molar ratio of said counter cation to the heavy metal ion sequestrant is preferably at least 1 :1.
  • Suitable heavy metal ion sequestrants for use herein include organic phosphonates, such as the amino alkylene poly (alkylene phosphonates), alkali metal ethane 1-hydroxy disphosphonates and nitrilo trimethylene phosphonates.
  • organic phosphonates such as the amino alkylene poly (alkylene phosphonates), alkali metal ethane 1-hydroxy disphosphonates and nitrilo trimethylene phosphonates.
  • Preferred among the above species are diethylene triamine penta (methylene phosphonate), ethylene diamine tri (methylene phosphonate) hexamethylene diamine tetra (methylene phosphonate) and hydroxy-ethylene 1 ,1 diphosphonate.
  • Suitable heavy metal ion sequestrant for use herein include nitrilotriacetic acid and polyaminocarboxylic acids such as ethylenediaminotetracetic acid, ethylenetriamine pentacetic acid, ethylenediamine disuccinic acid, ethylenediamine diglutaric acid, 2-hydroxypropylenediamine disuccinic acid or any salts thereof.
  • Preferred EDDS compounds are the free acid form and the sodium or magnesium salt or complex thereof.
  • Organo diphosphonic acid which does not contain nitrogen as part of its chemical structure. This definition therefore excludes the organo aminophosphonates, which however may be included in compositions of the invention as heavy metal ion sequestrant components.
  • the organo diphosphonic acid is preferably a C1-C4 diphosphonic acid, more preferably a C2 diphosphonic acid, such as ethylene diphosphonic acid, or most preferably ethane 1 -hydroxy-1 , 1 -diphosphonic acid (HEDP) and may be present in partially or fully ionized form, particularly as a salt or complex.
  • HEDP ethane 1 -hydroxy-1 , 1 -diphosphonic acid
  • compositions optionally contains a water-soluble sulfate salt.
  • the water-soluble sulfate salt is at the level of from 0.1 % to 40%, more preferably from 1 % to 30%, most preferably from 5% to 25% by weight of the compositions.
  • the water-soluble sulfate salt may be essentially any salt of sulfate with any counter cation.
  • Preferred salts are selected from the sulfates of the alkali and alkaline earth metals, particularly sodium sulfate.
  • An alkali metal silicate is a preferred component of the compositions of the present invention.
  • a preferred alkali metal silicate is sodium silicate having an SiO2:Na2O ratio of from 1.8 to 3.0, preferably from 1.8 to 2.4, most preferably
  • Sodium silicate is preferably present at a level of less than 20%, preferably from 1 % to 15%, most preferably from 3% to 12% by weight of Si ⁇ 2-
  • the alkali metal silicate may be in the form of either the anhydrous salt or a hydrated salt.
  • Alkali metal silicate may also be present as a component of an alkalinity system.
  • the alkalinity system also preferably contains sodium metasilicate, present at a level of at least 0.4% Si ⁇ 2 by weight.
  • Sodium metasilicate has a nominal Si ⁇ 2 :
  • the weight ratio of said sodium silicate to said sodium metasilicate, measured as Si ⁇ 2, is preferably from 50:1 to 5:4, more preferably from 15:1 to 2:1 , most preferably from 10:1 to 5:2.
  • colourant means any substance that absorbs specific wavelengths of light from the visible light spectrum. Such colourants when added to a detergent composition have the effect of changing the visible colour and thus the appearance of the detergent composition.
  • Colourants may be for example either dyes or pigments.
  • the colourants are stable in composition in which they are to be incorported. Thus in a composition of high pH the colourant is preferably alkali stable and in a composition of low pH the colourant is preferably acid stable.
  • the first and/or second and/or subsequent compositions may contain a colourant, a mixture of colourants, coloured particles or mixture of coloured particles such that the various phases have different visual appearances.
  • a colourant Preferably one of either the first or the second phases comprises a colourant.
  • both the first and second and/or subsequent phases comprise a colourant it is preferred that the colourants have a different visual appearance.
  • Preferred enzyme-containing compositions herein may comprise from 0.001% to 10%, preferably from 0.005% to 8%, most preferably from 0.01 % to 6%, by weight of an enzyme stabilizing system.
  • the enzyme stabilizing system can be any stabilizing system which is compatible with the detersive enzyme.
  • Such stabilizing systems can comprise calcium ion, boric acid, propylene glycol, short chain carboxylic acid, boronic acid, chlorine bleach scavengers and mixtures thereof.
  • Such stabilizing systems can also comprise reversible enzyme inhibitors, such as reversible protease inhibitors.
  • the detergent tblets of the present invention when formulated for use in machine washing compositions, preferably comprise a suds suppressing system present at a level of from 0.01 % to 15%, preferably from 0.05% to 10%, most preferably from 0.1 % to 5% by weight of the composition.
  • Suitable suds suppressing systems for use herein may comprise essentially any known antifoam compound, including, for example silicone antifoam compounds, 2-alkyl and alcanol antifoam compounds.
  • Preferred suds suppressing systems and antifoam compounds are disclosed in PCT Application No. WO93/08876 and EP-A-705 324.
  • compositions herein may also comprise from 0.01 % to 10 %, preferably from 0.05% to 0.5% by weight of polymeric dye transfer inhibiting agents.
  • the polymeric dye transfer inhibiting agents are preferably selected from polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N- vinylimidazole, polyvinylpyrrolidonepolymers or combinations thereof.
  • compositions suitable for use in laundry washing methods as described herein also optionally contain from 0.005% to 5% by weight of certain types of hydrophilic optical brighteners.
  • Hydrophilic optical brighteners useful herein include those having the structural formula:
  • is selected from anilino, N-2-bis-hydroxyethyl and NH-2- hydroxyethyl
  • R2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N- methylamino, morphilino, chloro and amino
  • M is a salt-forming cation such as sodium or potassium.
  • is anilino
  • R2 is N-2-bis-hydroxyethyl and M is a cation such as sodium
  • the brightener is 4,4',-bis[(4-anilino-6-(N-2-bis- hydroxyethyl)-s-triazine-2-yl)amino]-2,2'-stilbenedisulfonic acid and disodium salt.
  • This particular brightener species is commercially marketed under the tradename Tinopal-UNPA-GX by Ciba-Geigy Corporation. Tinopal-UNPA-GX is the preferred hydrophilic optical brightener useful in the detergent compositions herein.
  • R-) is anilino
  • R2 is N-2-hydroxyethyl-N-2- methylamino
  • M is a cation such as sodium
  • the brightener is 4,4'-bis[(4- anilino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazine-2-yl)amino]2,2'- stilbenedisulfonic acid disodium salt.
  • This particular brightener species is commercially marketed under the tradename Tinopal 5BM-GX by Ciba-Geigy Corporation.
  • the brightener is 4,4'-bis[(4-anilino-6-morphilino-s-triazine-2- yl)amino]2,2'-stilbenedisulfonic acid, sodium salt.
  • This particular brightener species is commercially marketed under the tradename Tinopal AMS-GX by Ciba Geigy Corporation.
  • Brightener 49 available from Ciba-Geigy.
  • compositions of the invention include perfumes and filler salts, with sodium sulfate being a preferred filler salt.
  • compositions of the present invention are preferably not formulated to have an unduly high pH, in preference having a pH measured as a 1 % solution in distilled water of from 7.0 to 12.5, more preferably from 7.5 to 11.8, most preferably from 8.0 to 11.5.
  • the present example is representative of the laundry additive sachets as described herein and are not meant to be limiting.
  • Compartment 2 Liquid (15 g) Isoparaffin 55% CLASS* 5% PAP 25% NOBS 15%
  • CLASS crystalline linear alkyl benzene sulphonate (LAS) structure

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Textile Engineering (AREA)
  • Detergent Compositions (AREA)
  • Bag Frames (AREA)
  • Packages (AREA)
  • Wrappers (AREA)

Abstract

La présente invention concerne des sachets d'additifs de blanchisserie. Ces sachets comportent au moins deux compartiments et peut en comporter d'autres. Au moins un des compartiments renferme une composition d'additifs liquides de blanchisserie.
PCT/US2001/004694 2000-02-17 2001-02-13 Sachet d'additifs de blanchisserie WO2001061099A1 (fr)

Priority Applications (7)

Application Number Priority Date Filing Date Title
US10/204,259 US7351683B2 (en) 2000-02-17 2001-02-13 Laundry additive sachet
MXPA02008067A MXPA02008067A (es) 2000-02-17 2001-02-13 Saco de aditivo para lavanderia.
EP01910655A EP1255887A2 (fr) 2000-02-17 2001-02-13 Sachet d'additifs de blanchisserie
JP2001559930A JP5000060B2 (ja) 2000-02-17 2001-02-13 洗濯添加剤用小袋
AU2001238240A AU2001238240A1 (en) 2000-02-17 2001-02-13 Laundry additive sachet
BR0108441-0A BR0108441A (pt) 2000-02-17 2001-02-13 Saché aditivo de lavanderia
CA002396931A CA2396931A1 (fr) 2000-02-17 2001-02-13 Sachet d'additifs de blanchisserie

Applications Claiming Priority (8)

Application Number Priority Date Filing Date Title
EP00870023.9 2000-02-17
EP00870023 2000-02-17
EP00870124.5 2000-06-09
EP00870124A EP1126070B1 (fr) 2000-02-17 2000-06-09 Sachet avec additives pour le linge
USPCT/US00/19619 2000-07-19
PCT/US2000/019619 WO2002008370A2 (fr) 2000-07-19 2000-07-19 Composition de nettoyage
USPCT/US00/20255 2000-07-25
PCT/US2000/020255 WO2002008371A2 (fr) 2000-02-17 2000-07-25 Composition de lavage

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US10/903,230 Continuation US7615524B2 (en) 2000-02-17 2004-07-30 Laundry additive sachet

Publications (2)

Publication Number Publication Date
WO2001061099A1 true WO2001061099A1 (fr) 2001-08-23
WO2001061099A8 WO2001061099A8 (fr) 2002-05-16

Family

ID=56290042

Family Applications (3)

Application Number Title Priority Date Filing Date
PCT/US2000/020255 WO2002008371A2 (fr) 2000-02-17 2000-07-25 Composition de lavage
PCT/US2000/032533 WO2001060966A1 (fr) 2000-02-17 2000-11-29 Produit detergent
PCT/US2001/004694 WO2001061099A1 (fr) 2000-02-17 2001-02-13 Sachet d'additifs de blanchisserie

Family Applications Before (2)

Application Number Title Priority Date Filing Date
PCT/US2000/020255 WO2002008371A2 (fr) 2000-02-17 2000-07-25 Composition de lavage
PCT/US2000/032533 WO2001060966A1 (fr) 2000-02-17 2000-11-29 Produit detergent

Country Status (12)

Country Link
EP (2) EP1255807B1 (fr)
JP (3) JP2005507432A (fr)
CN (2) CN1225537C (fr)
AR (2) AR028508A1 (fr)
AT (1) ATE369417T1 (fr)
AU (2) AU2001218076A1 (fr)
BR (2) BR0017112B1 (fr)
CA (2) CA2397241C (fr)
DE (1) DE60035902T2 (fr)
ES (1) ES2290059T3 (fr)
MX (2) MXPA02008065A (fr)
WO (3) WO2002008371A2 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2387598A (en) * 2002-04-20 2003-10-22 Reckitt Benckiser Nv Water-soluble container and a process for its preparation
EP2746381A1 (fr) * 2012-12-21 2014-06-25 The Procter & Gamble Company Kit de nettoyage
EP2857486A1 (fr) 2013-10-07 2015-04-08 WeylChem Switzerland AG Poche à compartiments multiples comprenant des compositions de nettoyage, processus de lavage et utilisation de produits de lavage et de nettoyage de textiles et plats

Families Citing this family (54)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6557732B2 (en) 2000-07-19 2003-05-06 The Procter & Gamble Company Detergent pack
EP1479756B1 (fr) * 2000-11-27 2005-09-07 The Procter & Gamble Company Procédé pour laver la vaisselle
US8658585B2 (en) 2000-11-27 2014-02-25 Tanguy Marie Louise Alexandre Catlin Detergent products, methods and manufacture
JP4707933B2 (ja) 2000-11-27 2011-06-22 ザ プロクター アンド ギャンブル カンパニー 食器洗浄方法
US7125828B2 (en) 2000-11-27 2006-10-24 The Procter & Gamble Company Detergent products, methods and manufacture
US6492312B1 (en) * 2001-03-16 2002-12-10 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Water soluble sachet with a dishwashing enhancing particle
CA2443113C (fr) 2001-05-14 2009-12-01 The Procter & Gamble Company Produit de nettoyage comprenant trois zones distinctes
US6521581B1 (en) 2001-12-14 2003-02-18 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Water-soluble package with multiple distinctly colored layers of liquid laundry detergent
EP1601753B1 (fr) * 2003-03-11 2007-07-25 Reckitt Benckiser N.V. Emballage contenant une composition detergente
DE102004019138A1 (de) * 2004-04-16 2005-11-10 Henkel Kgaa Bleichmittelhaltiges Wasch- oder Reinigungsmittel in wasserlöslicher oder wasserdispergierbarer Portionsverpackung
GB2417250A (en) * 2004-08-20 2006-02-22 Reckitt Benckiser Nv Multi-chamber bottle containg a liquid detergent composition
US8431517B2 (en) * 2004-09-28 2013-04-30 The Procter & Gamble Company Surface corrosion protection detergent compositions containing polyvalent metal compounds and high levels of low foaming, nonionic surfactants
DE602005015532D1 (de) † 2004-11-22 2009-09-03 Procter & Gamble Wasserlöslicher Beutel gefüllt mit einer Flüssigkeit
US7534759B2 (en) 2005-02-17 2009-05-19 The Procter & Gamble Company Fabric care composition
US8814861B2 (en) 2005-05-12 2014-08-26 Innovatech, Llc Electrosurgical electrode and method of manufacturing same
KR100681815B1 (ko) * 2005-12-02 2007-02-12 한국생명공학연구원 리컴비네이즈 매개 선택표지 유전자 발현유도에 의한 목표유전자 간편 클로닝 및 목표 단백질 신속 발현 방법.
US20090233830A1 (en) * 2008-03-14 2009-09-17 Penny Sue Dirr Automatic detergent dishwashing composition
GB0811399D0 (en) 2008-06-20 2008-07-30 Edwards David B Cushion Pack
EP2210520A1 (fr) * 2009-01-22 2010-07-28 The Procter & Gamble Company Paquet comprenant un matériau adhésif de fourniture de parfum
EP2443222B1 (fr) * 2009-06-15 2018-03-14 Ecolab USA Inc. Procédés d'utilisation pour le nettoyage de salissures à base de matière grasse à teneur nulle en matière grasse trans
US8188027B2 (en) 2009-07-20 2012-05-29 The Procter & Gamble Company Liquid fabric enhancer composition comprising a di-hydrocarbyl complex
US20110240510A1 (en) * 2010-04-06 2011-10-06 Johan Maurice Theo De Poortere Optimized release of bleaching systems in laundry detergents
PL218313B1 (pl) 2010-10-28 2014-11-28 Inst Immunologii I Terapii Doświadczalnej Pan Kompetytywna metoda otrzymywania preparatów bakteriofagowych
JP5883294B2 (ja) * 2011-11-22 2016-03-09 菱江化学株式会社 漂白剤、洗浄漂白剤及び殺菌剤
US9487735B2 (en) 2012-05-14 2016-11-08 Ecolab Usa Inc. Label removal solution for low temperature and low alkaline conditions
EP2850167B1 (fr) * 2012-05-14 2018-10-31 Ecolab USA Inc. Solution de retrait d'étiquette pour des bouteilles de boisson consignées
DE102013200358A1 (de) * 2013-01-14 2014-07-17 Henkel Ag & Co. Kgaa Wasserarme bis wasserfreie flüssige Reinigungsmittel
DE102013004428A1 (de) 2013-03-15 2014-09-18 Clariant International Ltd. Verfahren zum Waschen und Reinigen von Textilien
CN103408119A (zh) * 2013-08-05 2013-11-27 东华大学 一种用于印染废水的快速无机絮凝脱色剂及其制备方法和应用
CN103408118A (zh) * 2013-08-05 2013-11-27 东华大学 一种絮凝氧化处理印染废水的方法
EP2857485A1 (fr) 2013-10-07 2015-04-08 WeylChem Switzerland AG Poche à compartiments multiples comprenant des compositions de nettoyage sans alkanolamine, processus de lavage et utilisation de produits de lavage et de nettoyage de textiles et plats
EP2857487A1 (fr) 2013-10-07 2015-04-08 WeylChem Switzerland AG Poche à compartiments multiples comprenant des compositions de nettoyage, processus de lavage et utilisation de produits de lavage et de nettoyage de textiles et plats
EP2940116B1 (fr) * 2014-04-30 2018-10-17 The Procter and Gamble Company Composition détergente
CN106795465B (zh) * 2014-10-17 2020-10-16 巴斯夫欧洲公司 包含含mgda的洗涤剂组合物的容器
US10480113B2 (en) * 2014-12-23 2019-11-19 Electrolux Appliances Aktiebolag Method for operating a laundry washing machine using a unit dose package and laundry washing machine
CN107384654B (zh) * 2016-05-17 2021-04-27 北京绿伞化学股份有限公司 一种除垢去污防护产品
US10982373B2 (en) 2016-06-09 2021-04-20 Conopco, Inc. Laundry liquid mixing apparatus
EP3469130A1 (fr) * 2016-06-09 2019-04-17 Unilever PLC Produits de blanchisserie
DE102016115927A1 (de) 2016-08-26 2018-03-01 Brauns-Heitmann GmbH & Co Kommanditgesellschaft Färbesystem für textile Materialien
EP3526389A1 (fr) * 2016-10-11 2019-08-21 Unilever PLC Dispositif de dosage de lessive
EP3342846B1 (fr) * 2016-12-31 2020-04-08 Grupa Inco S.A. Capsule auto-dissoluble pour la préparation de solutions de lavage
CN107495917A (zh) * 2017-09-11 2017-12-22 广州烁炫日用品有限公司 一种不伤手无防腐剂环保的餐具清洁球
EP3692133A1 (fr) 2017-10-05 2020-08-12 Unilever PLC Procédés et dispositifs pour la lessive individualisée
GB2571336A (en) 2018-02-26 2019-08-28 Unilever Plc Methods and system for monitoring and replenishing one or more laundry components
DE102019126124A1 (de) * 2019-09-27 2021-04-01 Henkel Ag & Co. Kgaa Verfahren zur Herstellung Tensid enthaltender Zusammensetzungen in einem sequenziellen Verfahren
WO2021083678A1 (fr) 2019-11-01 2021-05-06 Unilever Ip Holdings B.V. Récipient à dosage automatique recyclable
EP4263779A1 (fr) * 2020-12-21 2023-10-25 Unilever IP Holdings B.V. Composition de traitement de linge
EP4279571A1 (fr) * 2022-05-19 2023-11-22 The Procter & Gamble Company Composition de lavage comprenant des spores
WO2024166841A1 (fr) * 2023-02-06 2024-08-15 花王株式会社 Article de produit de nettoyage
US20240409858A1 (en) * 2023-06-07 2024-12-12 The Procter & Gamble Company Automatic dishwashing detergent water-soluble pouch comprising solvent
EP4474455A1 (fr) * 2023-06-07 2024-12-11 The Procter & Gamble Company Sachet soluble dans l'eau de détergent pour lave-vaisselle automatique comprenant une amylase
EP4474459A1 (fr) * 2023-06-07 2024-12-11 The Procter & Gamble Company Sachet soluble dans l'eau de détergent pour lave-vaisselle automatique comprenant une protéase
EP4474461A1 (fr) * 2023-06-07 2024-12-11 The Procter & Gamble Company Procédé de traitement de vaisselle dans un lave-vaisselle domestique automatique
US20240409852A1 (en) * 2023-06-07 2024-12-12 The Procter & Gamble Company Automatic dishwashing detergent water-soluble pouch

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4410441A (en) * 1982-04-26 1983-10-18 Lever Brothers Company Product for treating fabrics in a washing machine
EP0132726A2 (fr) * 1983-07-21 1985-02-13 Henkel Kommanditgesellschaft auf Aktien Emballage pour produit de lavage, de rinçage ou de nettoyage
EP0284191A2 (fr) * 1987-03-24 1988-09-28 The Clorox Company Pellicule polymère libérant des additifs de lavage pendant le rinçage
US4776455A (en) * 1986-03-07 1988-10-11 Lever Brothers Company Compartmented product for dispensing treatment agents in a washing or dishwashing machine
EP0414462A2 (fr) * 1989-08-23 1991-02-27 Unilever Plc Produit de traitement pour le linge

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL266614A (fr) * 1960-07-07
DE1945038A1 (de) * 1969-09-05 1971-03-11 Miele & Cie Verfahren zum Reinigen von wasserunloeslichen Verschmutzungen in Geschirrspuelmaschinen
US4743394A (en) * 1984-03-23 1988-05-10 Kaufmann Edward J Concentrated non-phosphate detergent paste compositions
US5102573A (en) * 1987-04-10 1992-04-07 Colgate Palmolive Co. Detergent composition
US4973416A (en) * 1988-10-14 1990-11-27 The Procter & Gamble Company Liquid laundry detergent in water-soluble package
DE4009532A1 (de) * 1990-03-24 1991-09-26 Henkel Kgaa Waschmittel-formkoerper
AU637902B2 (en) * 1990-05-07 1993-06-10 Colgate-Palmolive Company, The Nonaqueous liquid automatic dishwasher detergent composition
US5750487A (en) * 1993-04-12 1998-05-12 Colgate-Palmolive Co. Tricritical point compositions
DE69425142T2 (de) * 1993-06-01 2001-03-22 Ecolab Inc., St. Paul Verdickte reiniger fuer harte oberflaechen
AU7563094A (en) * 1993-08-27 1995-03-21 Colgate-Palmolive Company, The Nonaqueous liquid microemulsion compositions
EP0752466A1 (fr) * 1995-07-05 1997-01-08 The Procter & Gamble Company Compositions détergentes non-aqueuses contenant un système effervescent
EP0912714A1 (fr) * 1996-06-28 1999-05-06 The Procter & Gamble Company Compositions nettoyantes liquides non aqueuses contenant des particules enrobees
JP4015727B2 (ja) * 1997-10-21 2007-11-28 ディバーシー・アイピー・インターナショナル・ビー・ヴイ 洗浄助剤組成物
CA2220312C (fr) * 1997-11-10 1999-11-09 Murugesu Nandhakumaran Recepteur radio et reemetteur
JPH11302693A (ja) * 1998-04-16 1999-11-02 Minnesota Mining & Mfg Co <3M> 濃縮された洗浄剤組成物

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4410441A (en) * 1982-04-26 1983-10-18 Lever Brothers Company Product for treating fabrics in a washing machine
EP0132726A2 (fr) * 1983-07-21 1985-02-13 Henkel Kommanditgesellschaft auf Aktien Emballage pour produit de lavage, de rinçage ou de nettoyage
US4776455A (en) * 1986-03-07 1988-10-11 Lever Brothers Company Compartmented product for dispensing treatment agents in a washing or dishwashing machine
EP0284191A2 (fr) * 1987-03-24 1988-09-28 The Clorox Company Pellicule polymère libérant des additifs de lavage pendant le rinçage
EP0414462A2 (fr) * 1989-08-23 1991-02-27 Unilever Plc Produit de traitement pour le linge

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2387598A (en) * 2002-04-20 2003-10-22 Reckitt Benckiser Nv Water-soluble container and a process for its preparation
WO2003089329A1 (fr) 2002-04-20 2003-10-30 Reckitt Benckiser N.V. Contenants solubles dans l'eau
EP2746381A1 (fr) * 2012-12-21 2014-06-25 The Procter & Gamble Company Kit de nettoyage
WO2014099854A1 (fr) * 2012-12-21 2014-06-26 The Procter & Gamble Company Système de nettoyage
EP2857486A1 (fr) 2013-10-07 2015-04-08 WeylChem Switzerland AG Poche à compartiments multiples comprenant des compositions de nettoyage, processus de lavage et utilisation de produits de lavage et de nettoyage de textiles et plats

Also Published As

Publication number Publication date
CN1401030A (zh) 2003-03-05
CA2396931A1 (fr) 2001-08-23
JP2004500460A (ja) 2004-01-08
MXPA02008065A (es) 2003-02-27
CA2397241A1 (fr) 2001-08-23
WO2001060966A8 (fr) 2003-01-03
JP2013067802A (ja) 2013-04-18
WO2002008371A3 (fr) 2008-05-15
AU2001218076A1 (en) 2001-08-27
WO2001060966A1 (fr) 2001-08-23
EP1255807B1 (fr) 2007-08-08
BR0017112B1 (pt) 2011-06-14
ES2290059T3 (es) 2008-02-16
ATE369417T1 (de) 2007-08-15
DE60035902D1 (de) 2007-09-20
EP1255807A1 (fr) 2002-11-13
AR035167A1 (es) 2004-05-05
DE60035902T2 (de) 2008-04-17
WO2001061099A8 (fr) 2002-05-16
AR028508A1 (es) 2003-05-14
CA2397241C (fr) 2008-12-30
CN1225537C (zh) 2005-11-02
AU2001238240A1 (en) 2001-08-27
BR0108441A (pt) 2002-12-17
WO2002008371A2 (fr) 2002-01-31
JP2005507432A (ja) 2005-03-17
EP1255887A2 (fr) 2002-11-13
CN1434857A (zh) 2003-08-06
BR0017112A (pt) 2003-01-14
JP5000060B2 (ja) 2012-08-15
MXPA02008067A (es) 2003-02-27

Similar Documents

Publication Publication Date Title
EP1126070B1 (fr) Sachet avec additives pour le linge
WO2001061099A1 (fr) Sachet d&#39;additifs de blanchisserie
US7351683B2 (en) Laundry additive sachet
US6599871B2 (en) Detergent tablet
WO1999006521A1 (fr) Pastille detergente
IES990570A2 (en) Detergent tablet
WO1999027067A1 (fr) Pastille de detergent
CA2314484A1 (fr) Comprime detergent
US20020028757A1 (en) Process of treating fabrics with a detergent tablet comprising an ion exchange resin
EP1103596B1 (fr) Comprimés détergents et leur production
EP1097191A2 (fr) Pastille detergente
US7615524B2 (en) Laundry additive sachet
AU4968699A (en) Detergent tablet
EP1097192A2 (fr) Pastille detergente
WO2000066687A1 (fr) Procede de traitement de tissus au moyen d&#39;un comprime d&#39;additif detergent a lessive
GB2327948A (en) Dish-washer detergent composition containing a high cloud point surfactant
MXPA01000629A (en) Detergent tablet
MXPA00005230A (en) Detergent tablet
MXPA00005225A (en) Detergent tablet

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AT AU AZ BA BB BG BR BY BZ CA CH CN CR CU CZ CZ DE DE DK DK DM DZ EE EE ES FI FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NO NZ PL PT RO RU SD SE SG SI SK SK SL TJ TM TR TT TZ UA UG US UZ VN YU ZA ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE TR BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
AK Designated states

Kind code of ref document: C1

Designated state(s): AE AG AL AM AT AT AU AZ BA BB BG BR BY BZ CA CH CN CR CU CZ CZ DE DE DK DK DM DZ EE EE ES FI FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NO NZ PL PT RO RU SD SE SG SI SK SK SL TJ TM TR TT TZ UA UG US UZ VN YU ZA ZW

AL Designated countries for regional patents

Kind code of ref document: C1

Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE TR BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG

WR Later publication of a revised version of an international search report
WWE Wipo information: entry into national phase

Ref document number: 2396931

Country of ref document: CA

WWE Wipo information: entry into national phase

Ref document number: 018051650

Country of ref document: CN

ENP Entry into the national phase

Ref country code: JP

Ref document number: 2001 559930

Kind code of ref document: A

Format of ref document f/p: F

WWE Wipo information: entry into national phase

Ref document number: PA/a/2002/008067

Country of ref document: MX

WWE Wipo information: entry into national phase

Ref document number: 2001910655

Country of ref document: EP

WWW Wipo information: withdrawn in national office

Ref document number: 2001910655

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 10204259

Country of ref document: US

WWP Wipo information: published in national office

Ref document number: 2001910655

Country of ref document: EP

REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

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