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WO2000065011A1 - Detergents pour surfaces dures - Google Patents

Detergents pour surfaces dures Download PDF

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Publication number
WO2000065011A1
WO2000065011A1 PCT/EP2000/003309 EP0003309W WO0065011A1 WO 2000065011 A1 WO2000065011 A1 WO 2000065011A1 EP 0003309 W EP0003309 W EP 0003309W WO 0065011 A1 WO0065011 A1 WO 0065011A1
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WO
WIPO (PCT)
Prior art keywords
alkyl
alkenyl
carbon atoms
acid
alcohol
Prior art date
Application number
PCT/EP2000/003309
Other languages
German (de)
English (en)
Inventor
Jörg KAHRE
Michael Elsner
Bernhard Guckenbiehl
Anja Hanke
Ditmar Kischkel
Bernd Fabry
Original Assignee
Cognis Deutschland Gmbh
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
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Application filed by Cognis Deutschland Gmbh filed Critical Cognis Deutschland Gmbh
Publication of WO2000065011A1 publication Critical patent/WO2000065011A1/fr

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Classifications

    • 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
    • C11D1/88—Ampholytes; Electroneutral compounds
    • C11D1/94—Mixtures with anionic, cationic or 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
    • C11D1/83—Mixtures of non-ionic with anionic 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
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2003—Alcohols; Phenols
    • C11D3/2041—Dihydric alcohols
    • 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
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/146—Sulfuric acid esters
    • 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
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29—Sulfates of polyoxyalkylene ethers
    • 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
    • C11D1/662—Carbohydrates or derivatives
    • 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
    • C11D1/88—Ampholytes; Electroneutral compounds
    • C11D1/90—Betaines

Definitions

  • the invention is in the field of detergents and disinfectants and relates to preparations with a special surfactant combination and alkanediols and their use for the production of detergents.
  • toilet blocks As a cleaning agent for flush toilets, toilet blocks have been used for a long time in a fixed form, which are either hung in the cistern with the help of a device or fastened under the inner edge of the toilet.Their task is to clean the toilet surface during the flushing process and in particular by releasing it Fragrances to cover up unpleasant smells. Because of their task of releasing fragrances, cleaning agents for flushing toilets are also generally referred to in the literature as fragrance washers. Usually tensides, builder substances, inorganic salts and of course fragrances and colorants are used for their production. A large number of such formulations are known from the prior art.
  • EP 0265979 A1 (Akzo) relates to thickened aqueous cleaning agents which contain mixtures of cationic surfactants and amine oxides together with short-chain aryl sulfonates.
  • EP 0014979 A1 (Henkel) toilet blocks are known which contain alkylbenzenesulfonates and alkylsulfates as well as fatty alcohol or alkylphenol ethoxylates.
  • DE 4337032 C2 (Henkel) relates to toilet blocks containing alkyl sulfates, alkyl ether sulfates and alkyl glucosides.
  • EP 0268967 A1 (Henkel) discloses toilet blocks which contain sodium lauryl sulfate and fatty acid monoethanolamide.
  • the toilet blocks described are generally manufactured by casting, pressing, extruding or granulating processes, which require a high level of technical complexity and frequently suffer undesirable perfume losses due to the temperature load (casting / extruding process) that occurs. It also proves to be disadvantageous that the widespread refill units can only be used after the piece-like body has been completely used up. A desirable, arbitrary refill, for example for a stronger release of active ingredient or in particular for more intensive fragrance development, is not possible.
  • gel-shaped toilet cleaners with pseudoplastic properties are known, which considerably reduce the manufacturing effort and can be produced more cost-effectively due to simple technology.
  • the problem of individual refillability can also be solved by such pseudoplastic active ingredient preparations.
  • These gel-type toilet cleaners contain polysaccharides, in particular xanthan gum, to adjust the pseudoplastic properties, and as surfactants, alkyl polyglycosides and, if appropriate, anionic and / or nonionic co-surfactants.
  • these gel-form cleaning agents have to be manufactured with special precautions during gel formation, so that on the one hand no bubbles form and on the other hand the other ingredients can be incorporated evenly distributed in the gel.
  • the complex object of the present invention was therefore to provide new cleaning agents for hard surfaces, but preferably toilet cleaners, which have a viscosity which on the one hand enables easy application and on the other hand does not run too quickly on inclined surfaces in order to to ensure the longest possible exposure time.
  • the preparations should also have an improved cleaning ability, be bactericidal and maintain their advantageous viscosity without the use of typical thickeners.
  • the agents should have good initial foam behavior, allow the incorporation of a wide variety of perfume oils, even in large quantities, and also show a long service life, i.e. enable a high number of toilet flushes until the detergent is completely flushed (number of flushes).
  • the invention relates to cleaning agents for hard surfaces containing
  • the preparations according to the invention not only have excellent cleaning performance and bactericidal activity, but, compared to conventional agents, also have a significantly higher viscosity without the use of thickeners and have a pseudoplastic behavior.
  • the agents according to the invention are therefore distinguished not only due to easy application and excellent drainage behavior, they also have a high foaming capacity, allow the incorporation of larger quantities of different perfume substances and, due to their gel-like nature, can also be used primarily in water boxes in toilets ("toilet bowls”) dosing reliably over a longer period of time. It is also possible to dewater the aqueous preparations in whole or in part and to compress them into blocks (“toilet blocks”).
  • Alkyl and alkenyl oligoglycosides which form component (a) are known nonionic surfactants which follow the formula (I)
  • R 1 is an alkyl and / or alkenyl radical having 4 to 22 carbon atoms
  • G is a sugar radical having 5 or 6 carbon atoms
  • p is a number from 1 to 10. They can be obtained according to the relevant procedures in preparative organic chemistry.
  • the alkyl and / or alkenyl oligoglycosides can be derived from aldoses or ketoses with 5 or 6 carbon atoms, preferably glucose.
  • the preferred alkyl and / or alkenyl oligoglycosides are thus alkyl and / or alkenyl oligoglucosides.
  • alkyl and / or alkenyl oligoglycosides are preferred whose degree of oligomerization is less than 1.7 and is in particular between 1.2 and 1.4.
  • the alkyl or alkenyl radical R 1 can be derived from primary alcohols having 4 to 11, preferably 8 to 10, carbon atoms. Typical examples are butanol, capronalcohol, caprylic alcohol, capric alcohol and undecyl alcohol and their technical mixtures, such as are obtained, for example, in the hydrogenation of technical fatty acid methyl esters or in the course of the hydrogenation of aldehydes from Roelen's oxosynthesis.
  • the alkyl or alkenyl radical R 1 can also be derived from primary alcohols containing 12 to 22 preferably derive from 12 to 14 carbon atoms.
  • Typical examples are lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyla alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol, brassidyl alcohol and their technical mixtures, which can be obtained as well as their technical mixtures.
  • Alkyl oligoglucosides based on hardened C * i2 / i4 coconut alcohol with a DP of 1 to 3 are preferred.
  • Alkyl and / or alkenyl sulfates which are also frequently referred to as fatty alcohol or oxo alcohol sulfates and which form component (b1), are to be understood as meaning the sulfation products of primary alcohols which follow the formula (II)
  • R 2 represents a linear or branched, aliphatic alkyl and / or alkenyl radical having 6 to 22, preferably 12 to 18 carbon atoms and X represents an alkali and / or alkaline earth metal, ammonium, alkylammonium, alkanolammonium or glucammonium.
  • alkyl sulfates which can be used for the purposes of the invention are the sulfation products of capron alcohol, caprylic alcohol, capric alcohol, 2-ethylhexyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyla alcohol, aryl selyl alcohol, elaalyl alcohol and erucyl alcohol and their technical mixtures, which are obtained by high pressure hydrogenation of technical methyl ester fractions or aldehydes from Roelen's oxosynthesis.
  • the sulfation products can preferably be used in the form of their alkali salts, and in particular their sodium salts.
  • Alkyl sulfates based on Ci6 / ß ⁇ -tallow fatty alcohols or vegetable fatty alcohols of comparable carbon chain distribution in the form of their sodium salts are particularly preferred.
  • ether sulfates which form component (b2)
  • anionic surfactants which are produced on an industrial scale by SO 3 - or chlorosulfonic acid (CSA) sulfation of fatty alcohol or oxo alcohol polyglycol ethers and subsequent neutralization.
  • CSA chlorosulfonic acid
  • ether sulfates which follow the formula (III) are suitable
  • Typical examples are the sulfates of adducts of an average of 1 to 10 and in particular 2 to 5 moles of ethylene oxide with caprone alcohol, caprylic alcohol, 2-ethylhexyl alcohol, capric alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostyl alcohol, isostearyl alcohol Elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol and brassidyl alcohol and their technical mixtures, in the form of their sodium and / or magnesium salts.
  • the ether sulfates can have both a conventional and a narrow homolog distribution. It is particularly preferred to use ether sulfates based on adducts of on average 2 to 3 mol ethylene oxide with technical C12 / 14 or C 12/18 coconut oil alcohol fractions in the form of their sodium and / or magnesium salts.
  • Betaines which can be considered as component (b3) are known surfactants which are predominantly prepared by carboxyalkylation, preferably carboxymethylation, of amine compounds.
  • the starting materials are preferably condensed with halocarboxylic acids or their salts, in particular with sodium chloroacetate, one mol of salt being formed per mole of betaine.
  • unsaturated carboxylic acids such as acrylic acid is also possible.
  • betaines and "real" amphoteric surfactants reference is made to the contribution by U.PIoog in Seifen- ⁇ le-Fette-Wwachs, 198, 373 (1982). Further overviews on this topic can be found for example by A. O'Lennick et al.
  • betaines are the carboxyalkylation products of secondary and in particular tertiary amines which follow the formula (IV)
  • R 4 for alkyl and / or alkenyl radicals with 6 to 22 carbon atoms
  • R 5 for hydrogen or alkyl radicals with 1 to 4 carbon atoms
  • R 6 for alkyl radicals with 1 to 4 carbon atoms
  • m for numbers from 1 to 6 and Y. represents an alkali and / or alkaline earth metal or ammonium.
  • Typical examples are the carboxymethylation products of hexylmethylamine, hexyldimethylamine, octyldimethylamine, decyldi methylamine, dodecylmethylamine, dodecyldimethyiamine, dodecylethylmethylamine, Ci2 ⁇ coconut alkyldimethylamine, myristyldimethylamine, cetyldimethylamine, stearyldimethylamine, stearyiethylmethylamine, oleyldimethylamine, Ci6 / 18-tallow alkyldimethylamine and their technical grade. Also suitable are carboxyalkylation products of amidoamines which follow the formula (V)
  • R 7 CO for an aliphatic acyl radical with 6 to 22 carbon atoms and 0 or 1 to 3 double bonds
  • R 5 for hydrogen or alkyl radicals with 1 to 4 carbon atoms
  • R 6 for alkyl radicals with 1 to 4 carbon atoms
  • p and q independently of one another for Numbers from 1 to 6 and
  • Y represents an alkali and / or alkaline earth metal or ammonium.
  • Typical examples are reaction products of fatty acids with 6 to 22 carbon atoms, namely caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, ariaachostic acid, gadic acid acid, gadic acid acid, gadic acid acid, gadic acid acid - Acid and erucic acid and their technical mixtures, with N, N-dimethyiaminoethylamine, N, N-dimethylaminopropylamine, N, N-diethylaminoethylamine and N, N-diethylaminopropylamine, which are condensed with sodium chloroacetate. It is preferred to use a condensation product of C ⁇ / i ⁇ -coconut fatty acid-N, N-di
  • Alkanediols which are component (c) preferably follow the general formula (VI),
  • z stands for numbers from 5 to 12.
  • Typical examples are 1, 5-pentanediol, 1, 6-hexanediol, 1, 8-octanediol, 1, 10-decanediol and 1, 12-dodecanediol and mixtures thereof.
  • the preparations according to the invention can contain mineral acids, such as hydrochloric acid or phosphoric acid, or else organic acids, such as formic acid, adipic acid, tartaric acid or preferably citric acid.
  • mineral acids such as hydrochloric acid or phosphoric acid
  • organic acids such as formic acid, adipic acid, tartaric acid or preferably citric acid.
  • the amount used depends on the desired pH, which should be in the range of 1.5 to 3 in particular.
  • the agents contain
  • Another object of the present invention finally relates to the use of mixtures containing
  • the gel-form cleaning agents according to the invention can also contain co-surfactants, limescale dissolving agents, builders, perfumes, perfume solubilizers, solvents, germ-inhibiting agents, preservatives, dyes, pH regulators and the like.
  • Non-ionic, anionic, cationic and / or amphoteric or amphoteric surfactants can be present as co-surfactants, the proportion of which in the compositions is usually about 1 to 5% by weight and preferably 2 to 3% by weight.
  • anionic surfactants are soaps, alkylbenzenesulfonates, alkanesulfonates, olefin sulfonates, alkyl ether sulfonates, glycerin ether sulfonates, ⁇ -methyl ester sulfonates, sulfo fatty acids, glycerin ether sulfates, hydroxymixed ether sulfates, monoglyceride (amine) sulfate and sulfate mono- sulfate, fatty acid , mono- and dialkyl sulfosuccinamates, Sulfotriglyce- ride, amide soaps, ether carboxylic acids and salts thereof, fatty acid taurides, N-acylamino acids such as acyl lactylates, acyl tartrates, acyl glutamates and acyl aspartates, alkyl oligoglucoside sulf
  • anionic surfactants contain polyglycol ether chains, these can have a conventional, but preferably a narrow, homolog distribution.
  • Typical examples of nonionic surfactants are fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, fatty acid polyglycol esters, fatty acid amide polyglycol ethers, fatty amine polyglycol ethers, alkoxylated triglycerides, (hydroxy) mixed ethers or mixed formals, optionally partially oxidized glucoronic acid derivatives, fatty acid N-alkylglucamides, protein hydrolysates (especially vegetable polyols based on sorbic acid esters), especially vegetable polyols based on sorbic acid esters, especially vegetable polyols based on sorbate Polysorbates and amine oxides.
  • nonionic surfactants contain polyglycol ether chains, they can have a conventional, but preferably a narrow, homolog distribution.
  • Typical examples of cationic surfactants are esterquats and tetraalkylammonium compounds.
  • the surfactants mentioned are exclusively known compounds. With regard to the structure and manufacture of these substances, reference is made to relevant reviews, for example J.Falbe (ed.), "Surfactants in Consumer Products", Springer Verlag, Berlin, 1987, pp. 54-124 or J.Falbe (ed.), “Catalysts, Surfactants and mineral oil additives ", Thieme Verlag, Stuttgart, 1978, pp. 123-217. Alcohol ethoxylates, hydroxy mixed ethers, fatty acid methyl ester ethoxylates and / or amine oxides are preferably used as co-surfactants.
  • Descaling agents preferably include descaling acids such as citric acid, formic acid, acetic acid, lactic acid or their water-soluble salts, which can be used in an amount of 1 to 12, preferably 2 to 7,% by weight, based on the agent.
  • descaling acids such as citric acid, formic acid, acetic acid, lactic acid or their water-soluble salts, which can be used in an amount of 1 to 12, preferably 2 to 7,% by weight, based on the agent.
  • Suitable liquid, water-soluble builders are ethylenediaminetetraacetic acid, nitrilotriacetic acid, citric acid and inorganic phosphonic acids, such as, for example, the neutral sodium salts of 1-hydroxyethane-1, 1, -diphosphonate, which are present in amounts of 0.5 to 5, preferably 1 to 2,% by weight .-% may be present.
  • the solid or water-insoluble builder used is, in particular, finely crystalline, synthetic and bound water-containing zeolite such as zeolite NaA in detergent quality.
  • zeolite NaX and mixtures of NaA and NaX are also suitable.
  • the zeolite can be used as a spray-dried powder or as an undried stabilized suspension that is still moist from its manufacture.
  • the zeolite may contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C 12 -C 8 -fatty alcohols with 2 to 5 ethylene oxide groups or ethoxylated isotridecanoia.
  • Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22, in particular 20 to 22% by weight of bound water.
  • Suitable substitutes or partial substitutes for zeolites are crystalline, layered sodium silicates of the general formula NaMSi ⁇ 2x + ⁇ -yH2 ⁇ , where M is sodium or hydrogen, x is a number from 1, 9 to 4 and y is a number from 0 to 20 and preferred values for x is 2, 3 or 4.
  • Such crystalline layered silicates are described, for example, in European patent application EP 0164514 A1.
  • Preferred crystalline layered silicates are those in which M in the general formula represents sodium and x takes the values 2 or 3.
  • both ⁇ - and ⁇ -sodium disilicate Na ⁇ Si ⁇ Os'yH ⁇ O are preferred, wherein ⁇ -sodium disilicate can be obtained, for example, by the method described in international patent application WO 91/08171.
  • the preparations according to the invention can preferably contain 10 to 60% by weight of zeolite and / or crystalline layered silicates as solid builders, mixtures of zeolite and crystalline layered silicates in any ratio being particularly advantageous.
  • the agents contain 20 to 50% by weight of zeolite and / or crystalline layered silicates.
  • agents contain up to 40% by weight of zeolite and in particular up to 35% by weight of zeolite, in each case based on anhydrous active substance.
  • Other suitable ingredients of the agents are water-soluble amorphous silicates; they are preferably used in combination with zeolite and / or crystalline layered silicates.
  • Particularly preferred are agents which contain, above all, sodium silicate with a molar ratio (module) NaOO: S1O2 of 1: 1 to 1: 4.5, preferably of 1: 2 to 1: 3.5.
  • the content of amorphous sodium silicates in the agents is preferably up to 15% by weight and preferably between 2 and 8% by weight.
  • Phosphates such as tripolyphosphates, pyrophosphates and orthophosphates can also be present in small amounts in the compositions.
  • the content of the phosphates in the compositions is preferably up to 15% by weight, but in particular 0 to 10% by weight.
  • the agents can also contain layered silicates of natural and synthetic origin. Layered silicates of this type are known, for example, from patent applications DE 2334899 B1, EP 0026529 A1 and DE 3526405 A1. Their usability is not limited to a special composition or structural formula. However, smectites, in particular bentonites, are preferred here. Suitable layered silicates, which belong to the group of water-swellable smectites, are, for example, those of the general formulas
  • the layered silicates can also contain hydrogen, alkali, alkaline earth ions, in particular Na + and Ca 2+ .
  • the amount of water of hydration is usually in the range of 8 to 20% by weight and depends on the swelling condition or the type of processing.
  • Useful layer silicates are known, for example, from US 3,966,629, US 4,062,647, EP 0026529 A1 and EP 0028432 A1.
  • Layer silicates are preferably used which are largely free of calcium ions and strongly coloring iron ions due to an alkali treatment.
  • Usable organic builders are, for example, the polycarboxylic acids preferably used in the form of their sodium salts, such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided that such use is not objectionable for ecological reasons is, and mixtures of these.
  • Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these.
  • Suitable polymeric polycarboxylates are, for example, the sodium salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 800 to 150,000 (based on acid).
  • Suitable copolymeric polycarboxylates are, in particular, those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable.
  • Their relative molecular weight, based on free acids is generally 5,000 to 200,000, preferably 10,000 to 120,000 and in particular 50,000 to 100,000. The use of polymeric polycarboxylates is not absolutely necessary.
  • agents are preferred which are biodegradable polymers, for example terpolymers, the monomers acrylic acid and maleic acid or salts thereof, and vinyl alcohol or vinyl alcohol derivatives or the monomers acrylic acid and 2-alkylallylsulfonic acid or containing their salts and sugar derivatives.
  • terpolymers which are obtained according to the teaching of German patent applications DE 4221381 A1 and DE 4300772 A1 are particularly preferred.
  • Further suitable builder substances are polyacetals, which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups, for example as described in European patent application EP 0280223 A1.
  • Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and their mixtures and from polyolcarboxylic acids such as gluconic acid and / or glucoheptonic acid.
  • the group of citrates is particularly preferred.
  • the builders can be present in the compositions according to the invention in amounts of 0 to 5% by weight.
  • Suitable germ inhibitors are in particular isothiazoline mixtures, sodium benzoate and / or salicylic acid.
  • Other examples are substances with specific activity against gram-positive bacteria such as 2,4,4'-trichloro-2'-hydroxydiphenyl ether, chlorhexidine (1,6-di- (4-chlorophenyl-biguanido) hexane) or TCC (3 , 4,4'-trichlorocarbanilide).
  • Numerous fragrances and essential oils also have antimicrobial properties.
  • Typical examples are the active ingredients eugenol, menthol and thymol in clove, mint and thyme oil.
  • An interesting natural antiseptic agent is the terpene alcohol farnesol (3,7,11-trimethyl-2,6,10-dodecatrien-1-ol), which is present in the linden blossom oil and has a lily of the valley smell. Glycerol monolaurate has also proven itself as a bacteriostatic. The amount of these antimicrobial agents strongly depends on the effectiveness of the respective compound and can be up to 5% by weight.
  • the germ-inhibiting agents are preferably present in amounts between 0 and 10, preferably between 0.01 and 7% by weight.
  • the optional additional perfume substances are those that are common from the prior art.
  • Natural fragrances are extracts of flowers (lily, lavender, roses, jasmine, neroli, yla ⁇ g-ylang), stems and leaves (geranium, patchouli, petitgrain), fruits (anise, coriander, caraway, juniper), fruit peels (bergamot, lemon, Oranges), roots (mace, angeiica, celery, cardamom, costus, iris, calmus), woods (pine, sandal, guaiac, cedar, rosewood), herbs and grasses (tarragon, lemongrass, sage, thyme), Needles and twigs (spruce, fir, pine, mountain pine), resins and balms (galbanum, elemi, benzoin, myrrh, olibanum, opoponax).
  • Typical synthetic fragrance compounds are products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type. Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinylacetate, phenylethylacetate, linalylbenzoate, benzylformate, ethylmethylphenylglycinate, allylcyclohexylproalatlateylatylateylatylatepylatepylatepylatepylatepylatepylate.
  • the ethers include, for example, benzyl ethyl ether, the aldehydes, for example, the linear alkanals having 8 to 18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, lilial and bourgeonal, the ketones, for example, the ionones, ⁇ -
  • Sage oil family oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, lentil flower oil, juniper berry oil, vetiver oil, oliban oil, galbanum oil, labolanum oil and lavandin oil.
  • bergamot oil dihydromyrcenol, lilial, lyral, citronellol, phenylethyl alcohol, ⁇ - hexylcinnamaldehyde, geraniol, benzyl acetone, cyclamen aldehyde, linalool, Boisambrene Forte, Ambroxan, indole, hedione, Sandelice, lemon oil, mandarin oil, orange oil, allyl amyl glycolate, Cyclovertal, lavandin oil, muscatel Sage oil, ß-damascone, geranium oil bourbon, cyclohexyl salicylate, Vertofix Coeur, Iso
  • Perfume solubilizers which can be used in the agents according to the invention are polyol fatty acid esters, for example glycerol alkoxylated with 7 mol of ethylene oxide, which is esterified with coconut fatty acid (Cetiol HE®, Henkel KGaA) and / or hardened castor oil alkoxylated with 40 or 60 mol of ethylene oxide (Eumulgin® HRE 40 or . 60, Henkel KGaA) and / or 2-hydroxy fatty alcohol ethoxylates (Eumulgin® L, Henkel KGaA).
  • the amount of the perfume solubilizers in the agents according to the invention is generally between 0 and 10, preferably between 1 and 7% by weight.
  • alkanolamines in particular for dyes and perfume oils, alkanolamines, polyols such as ethylene glycol, propylene glycol, 1, 2 glycerol and other
  • n re mono- and polyhydric alcohols, and alkylbenzenesulfonates with 1 to 3 carbon atoms in the alkyl radical.
  • the content of the solvents depends on the type and amount of the constituents to be dissolved and is generally in the range from 0.5 to 5% by weight.
  • the preferably water-soluble dyes are contained either for the coloring of the agent or for the coloring of the liquid surrounding the container.
  • the content of water-soluble dyes is preferably below 1% by weight and serves to improve the appearance of the product. If an additional color signal is required during the flushing process, the content of water-soluble dyes can be up to 5% by weight.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)

Abstract

L'invention concerne des détergents pour surfaces dures, caractérisés en ce qu'ils renferment (a) un alkyl- et/ou alcényloligoglycoside, (b) un alkyl- et/ou alcényl(éther)sulfate et/ou une bétaïne, et (c) des alcanediols.
PCT/EP2000/003309 1999-04-22 2000-04-13 Detergents pour surfaces dures WO2000065011A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19918189.6 1999-04-22
DE1999118189 DE19918189A1 (de) 1999-04-22 1999-04-22 Reinigungsmittel für harte Oberflächen

Publications (1)

Publication Number Publication Date
WO2000065011A1 true WO2000065011A1 (fr) 2000-11-02

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PCT/EP2000/003309 WO2000065011A1 (fr) 1999-04-22 2000-04-13 Detergents pour surfaces dures

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DE (1) DE19918189A1 (fr)
WO (1) WO2000065011A1 (fr)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6786223B2 (en) 2001-10-11 2004-09-07 S. C. Johnson & Son, Inc. Hard surface cleaners which provide improved fragrance retention properties to hard surfaces
US20120201902A1 (en) * 2009-06-30 2012-08-09 The Trustees Of Columbia University In The City Of New York Antimicrobial/preservative compositions comprising botanicals
US9192559B2 (en) 2006-12-15 2015-11-24 Givaudan Sa Compositions
US9497975B2 (en) 2011-12-06 2016-11-22 The Trustees Of Columbia University In The City Of New York Broad spectrum natural preservative composition
US9511040B2 (en) 2007-06-20 2016-12-06 The Trustees Of Columbia University In The City Of New York Skin and surface disinfectant compositions containing botanicals
US9687429B2 (en) 2007-06-20 2017-06-27 The Trustees Of Columbia University In The City Of New York Antimicrobial compositions containing low concentrations of botanicals
US9968101B2 (en) 2011-11-03 2018-05-15 The Trustees Of Columbia University In The City Of New York Botanical antimicrobial compositions
US9981069B2 (en) 2007-06-20 2018-05-29 The Trustees Of Columbia University In The City Of New York Bio-film resistant surfaces
US10806144B2 (en) 2011-11-03 2020-10-20 The Trustees Of Columbia University In The City Of New York Composition with sustained antimicrobial activity

Families Citing this family (5)

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DE102005051860A1 (de) * 2005-10-25 2007-04-26 Beiersdorf Ag Langzeitstabile Gesichtswässer mit 1,2 Hexandiol
DE102005051866A1 (de) * 2005-10-25 2007-05-03 Beiersdorf Ag Verwendung von 1,2-Alkandiolen zur Verbesserung des Schaumverhaltens gelartiger, polyacrylatverdickter Reinigungszubereitungen
US8283304B2 (en) 2009-10-14 2012-10-09 S.C. Johnson & Son, Inc. Green compositions containing synergistic blends of surfactants and linkers
US8778860B2 (en) * 2009-10-14 2014-07-15 S.C. Johnson & Son, Inc. Green disinfection/sanitization compositions and processes of making thereof
US8541356B2 (en) * 2009-11-23 2013-09-24 S.C. Johnson & Son, Inc. Water-activated “green” multi-functional wipe

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DE4337032C1 (de) * 1993-10-29 1995-05-24 Henkel Kgaa Verwendung von Detergensgemischen zur Herstellung von Toilettensteinen
DE4420515A1 (de) * 1994-06-13 1995-12-14 Henkel Kgaa Milde wäßrige Rasierpräparate
WO1996030485A1 (fr) * 1995-03-24 1996-10-03 Warwick International Group Limited Detergent liquide isotrope alcalin avec du peroxyde
US5597407A (en) * 1993-11-02 1997-01-28 Henkel Corporation Method of thickening aqueous formulations
WO1998036041A1 (fr) * 1997-02-18 1998-08-20 Henkel Corporation Amelioration de l'activite de sulfate d'ether utilise dans des liquides de lavage delicat, au moyen d'alkylpolyglycoside
DE19715872A1 (de) * 1997-04-16 1998-10-22 Henkel Kgaa Gelförmiges Reinigungsmittel für Spültoiletten
US5834413A (en) * 1997-09-26 1998-11-10 Colgate-Palmolive Co. Liquid cleaning compositions
US5853743A (en) * 1997-08-05 1998-12-29 Colgate Palmolive Company Light duty liquid cleaning compositions
US5858955A (en) * 1997-12-16 1999-01-12 Colgate Palmolive Company Cleaning compositions containing amine oxide and formic acid

Patent Citations (9)

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Publication number Priority date Publication date Assignee Title
DE4337032C1 (de) * 1993-10-29 1995-05-24 Henkel Kgaa Verwendung von Detergensgemischen zur Herstellung von Toilettensteinen
US5597407A (en) * 1993-11-02 1997-01-28 Henkel Corporation Method of thickening aqueous formulations
DE4420515A1 (de) * 1994-06-13 1995-12-14 Henkel Kgaa Milde wäßrige Rasierpräparate
WO1996030485A1 (fr) * 1995-03-24 1996-10-03 Warwick International Group Limited Detergent liquide isotrope alcalin avec du peroxyde
WO1998036041A1 (fr) * 1997-02-18 1998-08-20 Henkel Corporation Amelioration de l'activite de sulfate d'ether utilise dans des liquides de lavage delicat, au moyen d'alkylpolyglycoside
DE19715872A1 (de) * 1997-04-16 1998-10-22 Henkel Kgaa Gelförmiges Reinigungsmittel für Spültoiletten
US5853743A (en) * 1997-08-05 1998-12-29 Colgate Palmolive Company Light duty liquid cleaning compositions
US5834413A (en) * 1997-09-26 1998-11-10 Colgate-Palmolive Co. Liquid cleaning compositions
US5858955A (en) * 1997-12-16 1999-01-12 Colgate Palmolive Company Cleaning compositions containing amine oxide and formic acid

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6786223B2 (en) 2001-10-11 2004-09-07 S. C. Johnson & Son, Inc. Hard surface cleaners which provide improved fragrance retention properties to hard surfaces
US9192559B2 (en) 2006-12-15 2015-11-24 Givaudan Sa Compositions
US9511040B2 (en) 2007-06-20 2016-12-06 The Trustees Of Columbia University In The City Of New York Skin and surface disinfectant compositions containing botanicals
US9687429B2 (en) 2007-06-20 2017-06-27 The Trustees Of Columbia University In The City Of New York Antimicrobial compositions containing low concentrations of botanicals
US9981069B2 (en) 2007-06-20 2018-05-29 The Trustees Of Columbia University In The City Of New York Bio-film resistant surfaces
US10542760B2 (en) 2007-06-20 2020-01-28 The Trustees Of Columbia University In The City Of New York Skin and surface disinfectant compositions containing botanicals
US20120201902A1 (en) * 2009-06-30 2012-08-09 The Trustees Of Columbia University In The City Of New York Antimicrobial/preservative compositions comprising botanicals
US9968101B2 (en) 2011-11-03 2018-05-15 The Trustees Of Columbia University In The City Of New York Botanical antimicrobial compositions
US10806144B2 (en) 2011-11-03 2020-10-20 The Trustees Of Columbia University In The City Of New York Composition with sustained antimicrobial activity
US9497975B2 (en) 2011-12-06 2016-11-22 The Trustees Of Columbia University In The City Of New York Broad spectrum natural preservative composition

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