[go: up one dir, main page]

WO1996016150A1 - Detergent anti-salissures ayant une association de tensioactifs determinee - Google Patents

Detergent anti-salissures ayant une association de tensioactifs determinee Download PDF

Info

Publication number
WO1996016150A1
WO1996016150A1 PCT/EP1995/004398 EP9504398W WO9616150A1 WO 1996016150 A1 WO1996016150 A1 WO 1996016150A1 EP 9504398 W EP9504398 W EP 9504398W WO 9616150 A1 WO9616150 A1 WO 9616150A1
Authority
WO
WIPO (PCT)
Prior art keywords
weight
acid
alkyl
nonionic surfactant
water
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/EP1995/004398
Other languages
German (de)
English (en)
Inventor
Fred Schambil
Peter Krings
Georg Meine
Eduard Smulders
Horst Upadek
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of WO1996016150A1 publication Critical patent/WO1996016150A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3715—Polyesters or polycarbonates
    • 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
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0036—Soil deposition preventing compositions; Antiredeposition agents
    • 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
    • C11D1/72—Ethers of polyoxyalkylene glycols

Definitions

  • the invention relates to detergents and cleaning agents which contain dirt-repellent polymer and a combination of certain anionic surfactant of the ether sulfate type and certain nonionic surfactant of the alkyl polyethoxylate type.
  • detergents In addition to the ingredients that are indispensable for the washing process, such as surfactants and builder materials, detergents generally contain further constituents, which can be summarized under the term washing auxiliaries and which contain different active ingredient groups such as foam regulators, graying inhibitors, bleaching agents, bleach activators and color transfer inhibitors include.
  • Such auxiliary substances also include substances which impart dirt-repellent properties to the laundry fiber and which, if present during the washing process, support the dirt-removing ability of the other detergent components. The same applies analogously to cleaning agents for hard surfaces.
  • Such dirt-releasing substances are often referred to as “soil release” active ingredients or because of their ability to make the treated surface, for example the fiber, dirt-repellent, “soil repellents”.
  • copolyesters which contain dicarboxylic acid units, alkylene glycol units and polyalkylene glycol units. Soil-removing copolyesters of the type mentioned and their use in detergents have been known for a long time.
  • German Offenlegungsschrift DT 16 17 14 describes a washing process using polyethylene terephthalate-polyoxyethylene glycol copolymers.
  • the German Offenlegungsschrift DT 22 00911 relates to detergents which contain nonionic surfactant and a copolymer of polyoxyethylene glycol and polyethylene terephthalate.
  • German laid-open specification DT 22 53063 mentions acidic textile finishing agents which contain a copolymer of a dibasic carboxylic acid and an alkylene or cycloalkylene polyglycol and optionally an alkylene or cycloalkylene glycol.
  • Polymers with a molecular weight of 15,000 to 50,000 made of ethylene terephthalate and polyethylene oxide terephthalate, the polyethylene glycol units having molecular weights of 1,000 to 10,000 and since the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate is 2: to 6: 1 can, according to the German patent application DE 3324258 in Detergents are used.
  • European patent EP 066944 relates to textile treatment agents which contain a copolyester of ethylene glycol, polyethylene glycol, aromatic dicarboxylic acid and sulphonated aromatic dicarboxylic acid in certain molar ratios.
  • European patent EP 185427 discloses methyl or ethyl end-capped polyesters with ethylene and / or propylene terephthalate and polyethylene oxide terephthalate units and detergents containing such soil-release poly.
  • European patent EP 241 984 relates to a polyester which, in addition to oxyethylene groups and terephthalic acid units, also contains substituted ethylene units and glycerol units.
  • polyesters which contain, in addition to oxyethylene groups and terephthalic acid units, 1,2-propylene, 1,2-butylene and / or 3-methoxy-1,2-propylene groups and glycerol units C ⁇ - to C4 ⁇ alkyl groups are end groups closed.
  • the European patent EP 253 567 relates to soil release polymers with a molecular weight of 900 to 9000 made of ethylene terephthalate and polyethylene oxide terephthalate, the polyethylene glycol units having molecular weights of 300 to 3000 and the molar ratio of ethylene terephthalate to polyethylene oxide -terephthalate is 0.6 to 0.95.
  • European patent application EP 272033 discloses at least a proportion of polyesters with poly-propylene terephthalate and polyoxyethylene terephthalate units which are end-capped by C4-alkyl or acyl radicals.
  • European patent EP 274907 describes Sulphoethyl end-capped terephthalate-containing soil release polyesters.
  • European patent application EP 357280 sulfonation of unsaturated end groups produces soil-release polyesters with terephthalate, alkylene glycol and poly-C2-4-glycol units.
  • This object was essentially achieved by the presence of a surfactant combination of ether sulfates with low average degrees of ethoxylation and alkyl oligoethoxylates with average degrees of ethoxylation in the range from 6.5 to 8.5.
  • the invention accordingly relates to a washing or cleaning agent which contains a combination of active ingredients comprising dirt-releasing polyester, anionic surfactant of the ether sulfate type according to the general formula
  • R 1 is an alkyl or alkenyl radical having 10 to 22, in particular 12 to 18, carbon atoms
  • X is an alkali, ammonium or alkyl or hydroxyalkyl-substituted ammonium ion and n is a number from 0.5 to 3, in particular of 1 to 2 mean and nonionic surfactant according to the general formula
  • R2 is an alkyl or alkenyl radical having 10 to 22, in particular 1 to 18, carbon atoms and m is a number from 6.5 to 8.5, in particular from 6.8 to 7.5.
  • Another object of the invention is the use of such a combination of active ingredients of dirt-releasing polyester, ether sulfate according to formula I and nonionic surfactant according to formula II in detergents and cleaning agents, in particular to increase their cleaning performance compared to greasy soiling.
  • the weight ratio of dirt-releasing polyester to ether sulfate according to formula I is preferably 1:25 to 1: 3, in particular 1:20 to 1: 5.
  • the weight ratio of ether sulfate according to formula I to nonionic surfactant according to formula II is preferably 3: 1 to 1: 2, in particular 2: 1 to 1: 1.5.
  • Suitable dirt-releasing polyesters are known from the documents cited above and are commercially available, for example, under the names Sokalan (R) HC 9798X from BASF or Velvetol (R) 251C from Rhone-Poulenc.
  • the preferred dirt-releasing polyesters include those compounds which are formally accessible by esterification of two monomer parts, the first monomer being a dicarboxylic acid HOOC-Ph-COOH and the second monomer being a diol H0- (CHR 3 -) a 0H, which is also known as polymeric diol H- (0- (CHR3-) a ) [ j OH may be present.
  • Ph represents an o-, m- or p-phenylene radical, which can carry 1 to 4 substituents selected from alkyl radicals having 1 to 22 carbon atoms, sulfonic acid groups, carboxyl groups and mixtures thereof
  • R3 is hydrogen, an alkyl radical having 1 to 22 carbon atoms and their mixtures
  • a is a number from 2 to 6
  • b is a number from 1 to 300.
  • both monodiol units -0- (CHR3-) a 0- and poly er are in the polyesters which can be prepared from these - diol units - (0- (CHR3-) a ) D 0- before.
  • the molar ratio of monomer diol units to poly erdiol units is preferably 100: 1 to 1: 100, in particular 10: 1 to 1:10.
  • the degree of polymerization b in the polymer diol units is preferably in the range from 4 to 200, in particular from 12 to 140.
  • the molecular weight or the average molecular weight or the maximum of the molecular weight distribution of preferred dirt-releasing polyesters is preferably in the range from 250 to 100,000, in particular from 500 to 50,000.
  • the acid underlying the rest of Ph is preferably selected from terephthalic acid, isophthalic acid, phthalic acid, trimellitic acid, mellitic acid, the isomers of sulfophthalic acid, sulfoisophthalic acid and sulfoterephthalic acid and mixtures thereof. If their acid groups are not part of the ester bonds in the polymer, they are preferably in salt form, in particular as an alkali or ammonium salt. Among these, the sodium and potassium salts are particularly preferred.
  • small amounts, in particular not more than 10 mol%, based on the amount of Ph with the meaning given above, of other acids which have at least two carboxyl groups can be present in the dirt-releasing polyester.
  • these include, for example, alkylene and alkenylene dicarboxylic acids such as malonic acid, succinic acid, fumaric acid, maleic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid.
  • the preferred diols H0- (CHR3-) a 0H include those in which R3 is hydrogen and a is a number from 2 to 6, and those in which a is 2 and R3 is hydrogen and the alkyl radicals having 1 to 10 , in particular 1 to 3 carbon atoms is selected.
  • R3 is hydrogen and a is a number from 2 to 6
  • R3 is hydrogen and the alkyl radicals having 1 to 10 , in particular 1 to 3 carbon atoms is selected.
  • those of the formula H0-CH2-CHR3-0H, in which R3 has the abovementioned meaning are particularly preferred.
  • diol components are ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octahediol, 1,2-decanediol diol, 1,2-dodecanediol and neopentyl glycol.
  • Particularly preferred among the polymeric diols is polyethylene glycol with an average molecular weight in the range from 1000 to 6000.
  • the polyesters composed as described above can also be end group-closed, alkyl groups having 1 to 22 carbon atoms and esters of monocarboxylic acids being suitable as end groups.
  • the end groups bonded via ester bonds can be based on alkyl, alkenyl and aryl monocarboxylic acids having 5 to 32 carbon atoms, in particular 5 to 18 carbon atoms.
  • alkyl, alkenyl and aryl monocarboxylic acids having 5 to 32 carbon atoms, in particular 5 to 18 carbon atoms.
  • These include valeric acid, caproic acid, oenanthic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, undecenoic acid, lauric acid, lauroleic acid, tridecanoic acid, myristic acid, myristoleic acid, pentadecanoic acid, palmitic acid, stearic acid, petroselinic acid, linoleic acid, linoleic acid, oleic linaidic acid, oleic acid, linoleic acid, oleic acid, linoleic acid, oleic acid
  • the end groups can also be based on hydroxymonocarboxylic acids having 5 to 22 carbon atoms, which include, for example, hydroxyvaleric acid, hydroxycaproic acid, ricinoleic acid, their hydrogenation product hydroxystearic acid and o-, - and p-hydroxybenzoic acid.
  • the hydroxymonocarboxylic acids can in turn be connected to one another via their hydroxyl group and their carboxyl group and can therefore be present several times in an end group.
  • the number of hydroxymonocarboxylic acid units per end group is preferably in the range from 1 to 50, in particular from 1 to 10.
  • Detergents or cleaning agents which contain the active ingredient combination according to the invention can contain all the usual other constituents of such agents which do not interact undesirably with the soil-release polymer or the surfactants.
  • the active ingredient combination according to the invention is preferably used in amounts of 5% by weight to 50% by weight, in particular 8% to 25% by weight incorporated into washing or cleaning agents.
  • such an agent contains, in addition to the nonionic surfactant according to formula II introduced with the active ingredient combination according to the invention, further nonionic surfactant selected from fatty alkyl polyglycosides, fatty alkyl polyalkoxylates, in particular ethoxylates and / or propoxylates, fatty acid polyhydroxyamides and / or ethoxylation and / or or propoxylation products of fatty alkyl amines, vicinal diols, fatty acid alkyl esters and / or fatty acid amides and mixtures thereof, in particular in an amount in the range from 2% by weight to 25% by weight.
  • further nonionic surfactant selected from fatty alkyl polyglycosides, fatty alkyl polyalkoxylates, in particular ethoxylates and / or propoxylates, fatty acid polyhydroxyamides and / or ethoxylation and / or or propoxylation products of fatty alkyl amines, vicinal
  • a further embodiment of such agents comprises the presence of additional synthetic anionic surfactants of the sulfate and / or sulfonate type, in particular fatty alkyl sulfate, fatty alkyl ether sulfate, which does not correspond to formula I, sulfofatty acid esters and / or sulfofatty acid disalts, in particular in an amount in the range from 2% by weight. % to 25% by weight.
  • the anionic surfactant is preferably selected from the alkyl or alkenyl sulfates and / or the alkyl or alkenyl ether sulfates in which the alkyl or alkenyl group has 8 to 22, in particular 12 to 18, carbon atoms.
  • the nonionic surfactants in question include the alkoxylates, in particular the ethoxylates and / or propoxylates of saturated or mono- to polyunsaturated linear or branched chain alcohols having 10 to 22 carbon atoms, preferably 12 to 18 carbon atoms.
  • the degree of alkoxylation of the alcohols is generally between 1 and 6 or between 9 and 20, preferably between 3 and 6.
  • the nonionic surfactant of the formula II contained in the active compound combination according to the invention they can be prepared in a known manner by reacting the corresponding alcohols can be prepared with the corresponding alkylene oxides.
  • the derivatives of fatty alcohols are particularly suitable, although their branched chain isomers, in particular so-called oxo alcohols, can also be used to prepare alkoxylates which can be used.
  • the alkoxylates in particular the ethoxylates, of primary alcohols with linear, in particular dodecyl, tetradecyl, hexadecyl or ocadecyl radicals, and mixtures thereof, can be used.
  • 1 to 20 times, in particular 3 to 10 times, alkoxylation products of alkylamines, vicinal diols and carboxamides, which correspond to the alcohols mentioned with regard to the alkyl part, can be used.
  • ethylene oxide and / or propylene oxide insertion products of fatty acid alkyl esters such as can be prepared in accordance with the process specified in international patent application WO 90/13533, and fatty acid polyhydroxyamides, as are used, for example, in accordance with the processes of the US Pat US 1 985424, US 2016962 and US 2 703 798 and the international patent application WO 92/06984 can be produced.
  • alkyl polyglycosides suitable for incorporation into the agents according to the invention are compounds of the general formula (G) n-OR ⁇ in which R ⁇ is an alkyl or alkenyl radical having 8 to 22 C atoms, G is a glycose unit and p is a number between 1 and 10 mean.
  • R ⁇ is an alkyl or alkenyl radical having 8 to 22 C atoms
  • G is a glycose unit
  • p is a number between 1 and 10 mean.
  • the glycoside component (G) p is oligomers or polymers from naturally occurring aldose or ketose monomers, in particular glucose, mannose, fructose, galactose, talose, gulose, altrose, allos, idose, ribose , Arabinose, xylose and lyxose.
  • the oligomers consisting of such glycosidically linked monomers are characterized not only by the type of sugar they contain, but also by their number, the so-called degree of olergization.
  • the degree of oligomerization p generally takes broken numerical values as the quantity to be determined analytically; it is between 1 and 10, for the glycosides preferably used below 1.5, in particular between 1.2 and 1.4.
  • the preferred monomer building block is glucose because of its good availability.
  • the alkyl or alkenyl part R 4 of the glycosides preferably also originates from easily accessible derivatives of renewable raw materials, in particular from fatty alcohols, although their branched chain isomers, in particular so-called oxo alcohols, can also be used to produce usable glycosides. Accordingly, the primary alcohols with linear octyl, decyl, dodecyl, tetradecyl, hexadecyl or octadecyl radicals and mixtures thereof are particularly useful.
  • Additional nonionic surfactant is in agents which contain the combination of active ingredients on which the invention is based, preferably in amounts of up to 30% by weight, in particular of 1% by weight to 25% by weight, in each case based on the total agent , contain.
  • Agents according to the invention can instead or in addition further surfactants, preferably synthetic anionic surfactants of the sulfate or sulfonate type, in amounts of preferably not more than 20% by weight, in particular from 0.1% by weight to 18% by weight, in each case based on the total mean.
  • synthetic anionic surfactants which are particularly suitable for use in agents of this type are the alkyl and / or alkenyl sulfates with 8 to 22 carbon atoms which carry an alkali metal, ammonium or alkyl or hydroxyalkyl substituted ammonium ion as countercation .
  • the derivatives of fatty alcohols with in particular 12 to 18 carbon atoms and their branched chain analogs, the so-called oxo alcohols, are preferred.
  • the alkyl and alkenyl sulfates can be prepared in a known manner by reacting the corresponding alcohol component with a conventional sulfating reagent, in particular sulfur trioxide or chlorosulfonic acid, and then neutralizing with alkali metal, ammonium or alkyl or hydroxyalkyl substituted ammonium bases can be produced.
  • a conventional sulfating reagent in particular sulfur trioxide or chlorosulfonic acid
  • Such alkyl and / or alkenyl sulfates are preferably present in amounts from 0.1% by weight to 20% by weight, in particular from 0.5% by weight to 18% by weight.
  • Suitable anionic surfactants of the sulfonate type include the .alpha.-sulfoesters obtainable by reacting fatty acid esters with sulfur trioxide and subsequent neutralization, in particular those derived from fatty acids having 8 to 22 carbon atoms, preferably 12 to 18 carbon atoms, and linear alcohols with 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, derived sulfonation products, as well as the sulfofatty acids resulting from these by formal saponification.
  • Soaps are considered as further optional surfactant ingredients, whereby saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid or stearic acid, as well as soaps derived from natural fatty acid mixtures, for example coconut, palm kernel or tallow fatty acids, are suitable.
  • those soap mixtures are preferred which are composed of 50% by weight to 100% by weight of saturated Ci2-Ci8 fatty acid soaps and up to 50% by weight of oleic acid soap.
  • Soap is preferably contained in amounts of 0.1% by weight to 5% by weight. However, in particular in liquid agents according to the invention, higher amounts of soap of generally up to 20% by weight can also be present.
  • an agent according to the invention contains water-soluble and / or water-insoluble builders, in particular selected from alkali alumosilicate, crystalline alkali silicate with a modulus above 1, monomeric polycarboxylate, polymeric polycarboxylate and mixtures thereof, in particular in amounts in the range from 2.5% by weight. % to 60% by weight.
  • An agent which has the active ingredient combination on which the invention is based preferably contains 20% by weight to 55% by weight of water-soluble and / or water-insoluble, organic and / or inorganic builders.
  • the water-soluble organic builder substances include, in particular, those from the class of the polycarboxylic acids, in particular citric acid and sugar acids, and the polymeric (poly) carboxylic acids, in particular the polycarboxylates of the international patent application WO 93/16110, which are accessible by oxidation of polysaccharides Acrylic acids, methacrylic acids, maleic acids and copolymers of these, which may also contain small amounts of polymerizable substances without carboxylic acid functionality in copolymerized form.
  • the relative molecular mass of the homopolymers of unsaturated carboxylic acids is generally between 5000 and 200000, that of the copolymers between 2000 and 200000, preferably 50,000 to 120,000, based on free acid.
  • a particularly preferred acrylic acid-maleic acid copolymer has a relative molecular weight of 50,000 to 100,000.
  • Suitable, albeit less preferred, compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinyl ethyl ethers, vinyl esters, ethylene, propylene and styrene, in which the proportion of the acid is at least 50% by weight.
  • Terpolymers can also be used as water-soluble organic builder substances which contain two unsaturated acids and / or their salts as monomers and vinyl alcohol and / or a vinyl alcohol derivative or a carbohydrate as the third monomer.
  • the first acidic monomer or its salt is derived from a monoethylenically unsaturated C 1 -C 6 -carboxylic acid and preferably from a C3-C4 monocarboxylic acid, in particular from (meth) acrylic acid.
  • the second acidic monomer or its salt can be a derivative of a C4-C8 dicarboxylic acid, preferably a C4-C8 dicarboxylic acid, maleic acid being particularly preferred.
  • the third monomeric unit is formed from vinyl alcohol and / or preferably an esterified vinyl alcohol.
  • vinyl alcohol derivatives are preferred which are an ester of short-chain carboxylic acids, for example C 1 -C 4 -carboxylic acids, with vinyl alcohol.
  • Preferred terpolymers contain 60% by weight to 95% by weight, in particular 70% by weight to 90% by weight of (meth) acrylic acid or (meth) acrylate, particularly preferably acrylic acid or acrylate, and maleic acid or Maleate and 5 wt .-% to 40 wt .-%, preferably 10 wt .-% to 30 wt .-% vinyl alcohol and / or vinyl acetate.
  • the second acidic monomer or its salt can also be a derivative of an allylsulfonic acid which is in the 2-position with an alkyl radical, is preferably substituted with a C 1 -C 4 -alkyl radical, or an aromatic radical, which is preferably derived from benzene or benzene derivatives.
  • Preferred terpolymers contain 40% by weight to 60% by weight, in particular 45 to 55% by weight of (meth) acrylic acid or (meth) acrylate, particularly preferably acrylic acid or acrylate, 10% by weight to 30% by weight .-%, preferably 15% by weight to 25% by weight of methylailsulfonic acid or methylailsulfonate and as the third monomer 15% by weight to 40% by weight, preferably 20% by weight to 40% by weight of a carbohydrate.
  • This carbohydrate can be, for example, a mono-, di-, oligo- or polysaccharide, mono-, di- or oligosaccharides being preferred, sucrose being particularly preferred.
  • the use of the third monomer presumably creates predetermined breaking points in the polymer, which are responsible for the good biodegradability of the polymer.
  • These terpolymers can be produced in particular by processes which are described in German patent DE 4221 381 and German patent application DE 43 00 772 and generally have a relative molecular weight between 1000 and 200000, preferably between 200 and 50,000 and in particular between 3,000 and 10,000. They can be used, in particular for the preparation of liquid compositions, in the form of aqueous solutions, preferably in the form of 30 to 50 percent by weight aqueous solutions. All of the polycarboxylic acids mentioned are generally used in the form of their water-soluble salts, in particular their alkali metal salts.
  • Such organic builder substances are preferably present in amounts of up to 40% by weight, in particular up to 25% by weight and particularly preferably from 1% by weight to 5% by weight. Amounts close to the upper limit mentioned are preferably used in paste-like or liquid, in particular water-containing, agents which contain the active ingredient combination on which the invention is based.
  • the water-insoluble, water-dispersible inorganic builder materials used are, in particular, crystalline or amorphous alkali alumosilicates, in amounts of up to 50% by weight, preferably not more than 40% by weight and in liquid compositions, in particular from 1% by weight to 5% .-%, used.
  • the crystalline aluminum silicates in detergent quality in particular zeolite A, zeolite P and optionally zeolite X, are preferred.
  • Quantities close to the upper limit mentioned are preferably used in solid, particulate compositions.
  • Suitable aluminosilicates in particular have no particles with a grain size above 30 ⁇ m and preferably consist of at least 80% by weight of particles with a size below 10 ⁇ m.
  • Suitable substitutes or partial substitutes for the aluminosilicate mentioned are crystalline or amorphous alkali silicates, which can be present alone or as a mixture with one another.
  • the alkali silicates which can be used as builders in the agents according to the invention preferably have a molar ratio of alkali oxide to SiO 2 below 0.95, in particular from 1: 1.1 to 1:12, and can be amorphous or crystalline.
  • Preferred alkali silicates are the sodium silicates, in particular the amorphous sodium silicates, with a Na 2 O: Si O 2 molar ratio of 1: 2 to 1: 2.8.
  • Such amorphous alkali silicates are commercially available, for example, under the name Portil ( R ).
  • Portil ( R ) Those with a molar Na2 ⁇ : Si ⁇ 2 ratio of 1: 1.9 to 1: 2.8 can be produced by the process of European patent application EP 0425427. In the course of production, they are preferably added as a solid, not in the form of a solution.
  • the crystalline silicates used are preferably crystalline sheet silicates of the general formula a2Si x ⁇ 2 ⁇ + i'.yH2 ⁇ in which x, the so-called modulus, is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4.
  • Crystalline layered silicates which fall under this general formula are described, for example, in European patent application EP 0 164 514.
  • Preferred crystalline layered silicates are those in which x assumes the values 2 or 3 in the general formula mentioned.
  • both ⁇ - and J-sodium disilicate are preferred, whereby ⁇ -sodium disilicate can be obtained, for example, by the method described in international patent application WO 91/08171.
  • fr sodium silicates with a modulus between 1.9 and 3.2 can be produced according to Japanese patent applications JP 04/238809 or JP 04/260610.
  • anhydrous crystalline alkali silicates of the above general formula, in which x denotes a number from 1.9 to 2.1, can be prepared from amorphous alkali silicates, as in European patent applications EP 0548599, EP 0502325 and EP 0425428 can be used in agents according to the invention.
  • a crystalline layered sodium silicate with a modulus of 2 to 3 is used, as can be produced from sand and soda by the process of European patent application EP 0436835.
  • Crystalline sodium silicates with a modulus in the range from 1.9 to 3.5 are used in a further preferred embodiment of the washing or ripening according to the invention detergent used.
  • the content of alkali silicates which can be used as a builder is preferably 1% by weight to 50% by weight and in particular 5% by weight to 35% by weight, based on the anhydrous active substance.
  • alkali alumosilicate in particular zeolite
  • the alkali silicate content is preferably 1% by weight to 15% by weight and in particular 2% by weight to 8% by weight, based on anhydrous active substance .
  • the weight ratio of aluminosilicate to silicate, based in each case on anhydrous active substances, is then preferably 4: 1 to 10: 1.
  • the weight ratio of amorphous alkali silicate to crystalline alkali silicate is preferably 1: 2 to 2: 1 and in particular 1: 1 to 2: 1.
  • alkali carbonates, alkali hydrogen carbonates and alkali sulfates and mixtures thereof are suitable.
  • additional inorganic material can be present in amounts up to 70% by weight, but is preferably absent entirely.
  • the agents can contain further constituents customary in washing and cleaning agents.
  • These optional components include, in particular, enzymes, enzyme stabilizers, bleaching agents, bleach activators, complexing agents for heavy metals, for example aminopolycarboxylic acids, aminohydroxypolycarboxylic acids, polyphosphonic acids and / or aminopolyphosphonic acids, graying inhibitors, for example cellulose ethers, color transfer or vinyl inhibitors, for example polyvinyl pyrrolidone, vinylpyrdin-N-oxide, foam inhibitors, for example organopolysiloxanes or paraffins, solvents and optical brighteners, for example stilbene disulfonic acid derivatives.
  • enzymes enzyme stabilizers
  • bleaching agents for bleach activators
  • complexing agents for heavy metals for example aminopolycarboxylic acids, aminohydroxypolycarboxylic acids, polyphosphonic acids and / or aminopolyphosphonic acids
  • graying inhibitors for example cellulose ethers
  • color transfer or vinyl inhibitors for example polyviny
  • optical brighteners in particular compounds from the class of the substituted 4,4'-bis- (2, 4,6-triamino-s-triazinyl) -stilbene-2,2'-disulfonic acids, up to 5% by weight, in particular 0.1% by weight to 2% by weight, of complexing agents for heavy metals, in particular aminoalkylenephosphonic acids and their salts, up to 3% by weight, in particular 0.5% by weight to 2% by weight, of graying inhibitors and up to 2% by weight, in particular 0.1% by weight to 1% by weight Contain foam inhibitors, the weight percentages each referring to the entire average.
  • solvents which are used in particular in the case of liquid agents according to the invention are preferably those which are water-miscible. These include the lower alcohols, for example ethanol, propanol, iso-propanol, and the isomeric butanols, glycerol, lower glycols, for example ethylene and propylene glycol, and the ethers which can be derived from the classes of compounds mentioned.
  • the dirt-releasing polyesters are usually dissolved or in suspended form.
  • Any enzyme present is preferably selected from the group comprising protease, amylase, lipase, cellulase, hemicellulase, oxidase, peroxidase or mixtures of these.
  • Protease obtained from microorganisms, such as bacteria or fungi is primarily suitable. It can be obtained in a known manner by fermentation processes from suitable microorganisms, which are described, for example, in German patent applications DE 1940488, DE 2044 161, DE 2201 803 and DE 21 21 397, the US patents US 3632957 and US 4264 738, European patent application EP 006638 and international patent application WO 91/02792.
  • Proteases are commercially available, for example, under the names BLAP ( R ), Savinase ( R ), Esperase ( R ), Maxatase ( R ), 0ptimase ( R ), Alcalase ( R ), Durazym ( R ) or Maxapem ( R ) .
  • the lipase that can be used can be obtained from Humicola lanuginosa, for example in European patent applications EP 258068 and EP 305216 and EP 341 947, from Bacillus species, as described for example in international patent application WO 91/16422 or European patent application EP 384717, from Pseudomonas species, as for example in European patent applications EP 468102, EP 385401, EP 375102, EP 334462, EP 331 376, EP 330641, EP 214761, EP 218272 or EP 204284 or the international patent application WO 90/10695, from Fusariu species, as described for example in the European patent application EP 130064, from Rhizopus species, as described for example in European patent application EP 117 553, or from Aspergillus species, as described for example in European patent application EP 167 309.
  • Suitable lipases are, for example, under the names Lipolase ( R ), Lipozym ( R ), Lipoma ⁇ (), Amano ( R ) Lipase, Toyo-Jozo ( R ) Lipase, Meito ( R ) Lipase and Diosynth ( R ) lipase commercially available.
  • Suitable amylases are commercially available, for example, under the names Maxamyl ( R ) and Termamyl ( R ).
  • the cellulase which can be used can be an enzyme which can be obtained from bacteria or fungi and which has a pH optimum, preferably in the weakly acidic to weakly alkaline range from 6 to 9.5.
  • Such cellulases are known, for example, from German laid-open publications DE 31 17250, DE 3207825, DE 3207847, DE 3322950 or European patent applications EP 265832, EP 269977, EP 270974, EP 273 125 and EP 339550.
  • customary enzyme stabilizers which are optionally present, in particular in liquid agents according to the invention, include amino alcohols, for example mono-, di-, triethanol- and -propanolamine and their mixtures, lower carboxylic acids, for example from European patent applications EP 376705 and EP 378261 known, boric acid or alkali borates, boric acid-carboxylic acid combinations, such as from.
  • European patent application EP 451 921 known boric acid esters, as known for example from international patent application WO 93/11215 or European patent application EP 511 456, boronic acid derivatives, as known for example from European patent application EP 583536, calcium salts, for example those from European Patent EP 28865 known Ca-formic acid combination, magnesium salts, such as from the European patent application EP 378262 known, and / or sulfur-containing reducing agents, such as known from European patent applications EP 080 748 or EP 080223.
  • Suitable foam inhibitors include long-chain soaps, in particular beef soap, fatty acid amides, paraffins, waxes, microcrystalline waxes, organopolysiloxanes and mixtures thereof, which can also contain microfine, optionally silanized or otherwise hydrophobized silica.
  • foam inhibitors are preferably bound to granular, water-soluble carrier substances, as described, for example, in German patent application DE 34 36 194, European patent applications EP 262 588, EP 301 414, EP 309931 or European patent EP 150386.
  • an agent according to the invention can contain graying inhibitors.
  • Graying inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing graying of the fibers.
  • Water-soluble colloids of mostly organic nature are suitable for this purpose, for example the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
  • Water-soluble polyamides containing acidic groups are also suitable for this purpose.
  • Soluble starch preparations and starch products other than those mentioned above can also be used, for example partially hydrolyzed starch. Na carboxymethyl cellulose, methyl cellulose, methyl hydroxyethyl cellulose and mixtures thereof are preferably used.
  • a further embodiment of an agent according to the invention contains bleaching agents based on peroxygen, in particular in amounts in the range from 5% by weight to 70% by weight, and optionally bleach activator, in particular in amounts in the range from 2% by weight to 10% by weight.
  • bleaches that come into consideration are the per compounds generally used in detergents, such as hydrogen peroxide, perborate, which can be present as tetra- or monohydrate, percarbonate, perpyrophosphate and persilicate, which are generally present as alkali metal salts, in particular as sodium salts
  • Such bleaching agents are found in detergents which Contain polymer according to the invention, preferably in amounts up to 25 wt .-%, in particular up to 15 wt .-% and particularly preferably of
  • the optional component of the bleach activators comprises the N- or O-acyl compounds normally used, for example polyacylated alkylenediamines, in particular tetraacetylethylenediamine, acylated glycolurils, in particular tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, urazipamides, sulfikurylamides, sulfikuryls, dikuricoles Cyanurates, moreover carboxylic acid anhydrides, in particular phthalic anhydride, carboxylic acid esters, in particular sodium isononanoyl-phenolsulfonate, and acylated sugar derivatives, in particular pentaacetyl glucose.
  • N- or O-acyl compounds normally used for example polyacylated alkylenediamines, in particular tetraacetylethylenediamine, acylated glycolurils, in particular tetraace
  • the bleach activators can be coated or granulated with Hü11 substances in a known manner, with tetraacetylethylenediamine granulated with average grain sizes of 0.01 mm to 0.8 mm using carboxyethyl cellulose.
  • Such bleach activators are preferably contained in detergents in amounts of up to 8% by weight, in particular from 2% by weight to 6% by weight, in each case based on the total agent.
  • an agent according to the invention is particulate and, in addition to the active ingredient combination according to the invention, contains 20% by weight to 55% by weight of inorganic builders, up to 15% by weight, in particular 2% by weight to 12% by weight.
  • % water-soluble organic builder 2.5% by weight to 20% by weight of synthetic anionic surfactant, 0.5% by weight to 20% by weight of nonionic surfactant, up to 25% by weight, in particular 1% by weight up to 15% by weight of bleach, up to 8% by weight, in particular 0.5% by weight of
  • such a powdery composition in particular for use as a mild detergent, contains 20% by weight to 55% by weight of inorganic builder, up to 15% by weight, in particular 2% by weight to 12% by weight of water-soluble organic builder, 4% by weight to 24% by weight of nonionic surfactant, up to 15% by weight, in particular 1% by weight to 10% by weight of synthetic anionic surfactant, to 65% by weight, in particular 1% by weight to 30% by weight, of inorganic salts, in particular alkali carbonate and / or sulfate, and neither bleaching agent nor bleach activator.
  • a further preferred embodiment comprises a liquid agent containing 5% by weight to 35% by weight of water-soluble organic builder, up to 15% by weight, in particular 0.1% by weight to 5% by weight of water-insoluble inorganic builder, up to 15% by weight, in particular 0.5% by weight to 10% by weight of synthetic anionic surfactant, 1% by weight to 25% by weight of nonionic surfactant, up to 15% by weight %, in particular 4% by weight to 12% by weight of soap and up to 30% by weight, in particular 1% by weight to 25% by weight of water and / or water-miscible solvent.
  • Powdery detergents of the composition given in Table 2 below were tested for their washing performance against greasy soiling.
  • the standardized test soils on cotton listed in Table 2 were washed in a Miele ( R ) W 933 washing machine in a 1-cycle process together with 3.5 kg of normally soiled household laundry at 40 ° C or 60 ° C (water hardness 16 ° dH , Detergent dosage 98 g).
  • the test fabrics were then dried and their cleanliness was determined by reflectance measurement (at 460 nm). The reflectance values are also shown in Table 2. It can be seen that agents with the active ingredient combination according to the invention (agents M1 and M2) have significantly better soil release properties than agents which lack a component of the active ingredient combination.
  • Table 1 Composition [% by weight]
  • Nonionic surfactant c 5 5 - 5
  • Soiling A dust / wool fat; 40 degree wash

Landscapes

  • 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)
  • Detergent Compositions (AREA)

Abstract

L'invention vise à améliorer le pouvoir détersif de détergents et de nettoyants contenant des polymères qui dissolvent les salissures et de tensioactifs de type sulfate d'éther. On utilise à cet effet une association de principes actifs comprenant un polyester anti-salissure, un tensioactif de type sulfate d'éther d'après la formule générale R1-(OCH2CH2)n-O-SO3X, dans laquelle R1 désigne un reste alkyle ou un reste alkényle ayant entre 10 et 22 atomes de C, X désigne un ion alcalin, ammonium ou alkyle ou un ion ammonium substitué par hydroxyalkyle et n vaut entre 0,5 et 3, ainsi qu'un tensioactif non ionique d'après la formule générale R2-(OCH2CH2)m-OH, dans laquelle R2 désigne un reste alkyle ou un reste alkényle ayant entre 10 et 22 atomes de C, et m vaut entre 6,5 et 8,5.
PCT/EP1995/004398 1994-11-17 1995-11-08 Detergent anti-salissures ayant une association de tensioactifs determinee Ceased WO1996016150A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19944440956 DE4440956A1 (de) 1994-11-17 1994-11-17 Schmutzabweisendes Waschmittel mit bestimmter Tensidkombination
DEP4440956.7 1994-11-17

Publications (1)

Publication Number Publication Date
WO1996016150A1 true WO1996016150A1 (fr) 1996-05-30

Family

ID=6533486

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1995/004398 Ceased WO1996016150A1 (fr) 1994-11-17 1995-11-08 Detergent anti-salissures ayant une association de tensioactifs determinee

Country Status (2)

Country Link
DE (1) DE4440956A1 (fr)
WO (1) WO1996016150A1 (fr)

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6514927B2 (en) 1997-06-17 2003-02-04 Clariant Gmbh Detergent and cleaner containing soil release polymer and alkanesulfonate and/or α-olefinsulfonate
WO2011120799A1 (fr) 2010-04-01 2011-10-06 Unilever Plc Procédé de structuration de liquides détergents à l'aide d'huile de ricin hydrogénée
EP2476743A1 (fr) 2011-04-04 2012-07-18 Unilever Plc, A Company Registered In England And Wales under company no. 41424 of Unilever House Procédé de lavage du linge
EP2495300A1 (fr) 2011-03-04 2012-09-05 Unilever Plc, A Company Registered In England And Wales under company no. 41424 of Unilever House Structuration de liquides détergents avec de l'huile de ricin hydrogénée
DE102012204270A1 (de) 2012-03-19 2013-09-19 Henkel Ag & Co. Kgaa Flüssiges Waschmittel mit erhöhter Reinigungsleistung
WO2013139702A1 (fr) 2012-03-21 2013-09-26 Unilever Plc Particules de détergent à lessive
WO2016155993A1 (fr) 2015-04-02 2016-10-06 Unilever Plc Composition
WO2017133879A1 (fr) 2016-02-04 2017-08-10 Unilever Plc Liquide détergent
WO2017211700A1 (fr) 2016-06-09 2017-12-14 Unilever Plc Produits de blanchisserie
WO2017211697A1 (fr) 2016-06-09 2017-12-14 Unilever Plc Produits de lessive
WO2018127390A1 (fr) 2017-01-06 2018-07-12 Unilever N.V. Composition d'élimination de taches
WO2018224379A1 (fr) 2017-06-09 2018-12-13 Unilever Plc Système de distribution de lessive liquide
WO2019038187A1 (fr) 2017-08-24 2019-02-28 Unilever Plc Perfectionnements se rapportant au nettoyage de tissus
WO2019038186A1 (fr) 2017-08-24 2019-02-28 Unilever Plc Perfectionnements se rapportant au nettoyage de tissus
WO2019063402A1 (fr) 2017-09-29 2019-04-04 Unilever Plc Produits de lessive
WO2019068473A1 (fr) 2017-10-05 2019-04-11 Unilever Plc Produits de lessive

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AR010265A1 (es) * 1996-11-01 2000-06-07 Procter & Gamble Composiciones detergentes para el lavado a mano que comprende una combinacion de surfactantes y polimero de liberacion de suciedad

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0199403A2 (fr) * 1985-04-15 1986-10-29 The Procter & Gamble Company Compositions détergentes liquides stables
US4721580A (en) * 1987-01-07 1988-01-26 The Procter & Gamble Company Anionic end-capped oligomeric esters as soil release agents in detergent compositions
EP0272033A2 (fr) * 1986-12-15 1988-06-22 The Procter & Gamble Company Copolymères et ester téréphthalique et leur utilisation dans les compositions de nettoyage du linge
EP0442101A1 (fr) * 1990-01-19 1991-08-21 BASF Aktiengesellschaft Polyesters contenant des surfactants non ioniques sous forme condensée, leur préparation et leur utilisation dans les détergents
WO1992004433A1 (fr) * 1990-09-07 1992-03-19 The Procter & Gamble Company Agents anti-salissure ameliores pour produits de lessive granulaires
WO1994024242A1 (fr) * 1993-04-08 1994-10-27 The Procter & Gamble Company Tensioactifs de (2,3) sulfates d'alkyle secondaires se trouvant dans des particules de tensioactifs melanges

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0199403A2 (fr) * 1985-04-15 1986-10-29 The Procter & Gamble Company Compositions détergentes liquides stables
EP0272033A2 (fr) * 1986-12-15 1988-06-22 The Procter & Gamble Company Copolymères et ester téréphthalique et leur utilisation dans les compositions de nettoyage du linge
US4721580A (en) * 1987-01-07 1988-01-26 The Procter & Gamble Company Anionic end-capped oligomeric esters as soil release agents in detergent compositions
EP0442101A1 (fr) * 1990-01-19 1991-08-21 BASF Aktiengesellschaft Polyesters contenant des surfactants non ioniques sous forme condensée, leur préparation et leur utilisation dans les détergents
WO1992004433A1 (fr) * 1990-09-07 1992-03-19 The Procter & Gamble Company Agents anti-salissure ameliores pour produits de lessive granulaires
WO1994024242A1 (fr) * 1993-04-08 1994-10-27 The Procter & Gamble Company Tensioactifs de (2,3) sulfates d'alkyle secondaires se trouvant dans des particules de tensioactifs melanges

Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6514927B2 (en) 1997-06-17 2003-02-04 Clariant Gmbh Detergent and cleaner containing soil release polymer and alkanesulfonate and/or α-olefinsulfonate
WO2011120799A1 (fr) 2010-04-01 2011-10-06 Unilever Plc Procédé de structuration de liquides détergents à l'aide d'huile de ricin hydrogénée
EP2495300A1 (fr) 2011-03-04 2012-09-05 Unilever Plc, A Company Registered In England And Wales under company no. 41424 of Unilever House Structuration de liquides détergents avec de l'huile de ricin hydrogénée
EP2476743A1 (fr) 2011-04-04 2012-07-18 Unilever Plc, A Company Registered In England And Wales under company no. 41424 of Unilever House Procédé de lavage du linge
WO2012136427A1 (fr) 2011-04-04 2012-10-11 Unilever Plc Procédé de lavage d'un tissu
DE102012204270A1 (de) 2012-03-19 2013-09-19 Henkel Ag & Co. Kgaa Flüssiges Waschmittel mit erhöhter Reinigungsleistung
WO2013139726A1 (fr) 2012-03-19 2013-09-26 Henkel Ag & Co. Kgaa Détergent liquide présentant une puissance de nettoyage augmentée
US9422509B2 (en) 2012-03-19 2016-08-23 Henkel Ag & Co. Kgaa Liquid detergent with increased cleaning performance
WO2013139702A1 (fr) 2012-03-21 2013-09-26 Unilever Plc Particules de détergent à lessive
WO2016155993A1 (fr) 2015-04-02 2016-10-06 Unilever Plc Composition
WO2017133879A1 (fr) 2016-02-04 2017-08-10 Unilever Plc Liquide détergent
WO2017211700A1 (fr) 2016-06-09 2017-12-14 Unilever Plc Produits de blanchisserie
WO2017211697A1 (fr) 2016-06-09 2017-12-14 Unilever Plc Produits de lessive
WO2018127390A1 (fr) 2017-01-06 2018-07-12 Unilever N.V. Composition d'élimination de taches
WO2018224379A1 (fr) 2017-06-09 2018-12-13 Unilever Plc Système de distribution de lessive liquide
WO2019038187A1 (fr) 2017-08-24 2019-02-28 Unilever Plc Perfectionnements se rapportant au nettoyage de tissus
WO2019038186A1 (fr) 2017-08-24 2019-02-28 Unilever Plc Perfectionnements se rapportant au nettoyage de tissus
WO2019063402A1 (fr) 2017-09-29 2019-04-04 Unilever Plc Produits de lessive
WO2019068473A1 (fr) 2017-10-05 2019-04-11 Unilever Plc Produits de lessive
DE212018000292U1 (de) 2017-10-05 2020-04-15 Unilever N.V. Waschmittelprodukte

Also Published As

Publication number Publication date
DE4440956A1 (de) 1996-05-23

Similar Documents

Publication Publication Date Title
EP0991743B1 (fr) Detergent et produit de nettoyage
EP0759947B1 (fr) Polyesters facilitant le lavage
EP3049508B1 (fr) Carbamates de cellulose utilisés comme principes actifs ayant la capacité de dissoudre les saletés
EP2836580B1 (fr) Cellulose microfibrillaire en tant que substance active à pouvoir détachant
WO1996016150A1 (fr) Detergent anti-salissures ayant une association de tensioactifs determinee
EP1592766B1 (fr) Procede pour renforcer la puissance de nettoyage de produits de lavage au moyen d'une combinaison de derives de cellulose
EP1888733B1 (fr) Renforcement de l'activite nettoyante de lessives par l'intermediaire de polymeres
EP1592765B1 (fr) Augmentation de la puissance de nettoyage de produits de lavage a l'aide d'un derive cellulosique et d'un polymere hygroscopique
WO2001007551A1 (fr) Utilisation d'alcools polyvinyliques comme additifs de detergent capables de detacher les salissures
EP3083918B1 (fr) Copolymères comprenant des groupes siloxane, utilisés comme agents antisalissures
EP1888732B1 (fr) Renforcement du pouvoir detersif de detergents par l'intermediaire d'un polymere
EP0944701A1 (fr) Polymeres facilitant le lavage, agissant sur le coton
DE4417686A1 (de) Endgruppenmodifizierte schmutzablösevermögende Polyester
EP0808357B1 (fr) Detergent fortement alcalin contenant un polymere detachant
DE102022200882A1 (de) Polymere schmutzablösevermögende Wirkstoffe
EP2917319B1 (fr) Polymères comportant des groupes polaires, servant de substances actives à pouvoir détachant
DE102004063766A1 (de) Verwendung von polyglykolether-modifiziertem Polysaccharid als schmutzablösevermögender Waschmittelzusatz
DE19502181A1 (de) Endgruppenmodifizierte schmutzablösevermögende Polyester
DE10351322A1 (de) Bleichmittelhaltiges Waschmittel mit baumwollaktivem schmutzablösevermögendem Cellulosederivat
DE102020200175A1 (de) Carboxymethylierte Poly(2-Vinylpyridine) als schmutzablösevermögende Wirkstoffe
DE19934983A1 (de) Verwendung von Polyvinylalkoholen als schmutzablösevermögende Waschmittelzusätze

Legal Events

Date Code Title Description
AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB GR IE IT LU MC NL PT SE

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
122 Ep: pct application non-entry in european phase