WO1998023714A1 - Polymeres facilitant le lavage, agissant sur le coton - Google Patents

Polymeres facilitant le lavage, agissant sur le coton Download PDF

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Publication number
WO1998023714A1
WO1998023714A1 PCT/EP1997/006448 EP9706448W WO9823714A1 WO 1998023714 A1 WO1998023714 A1 WO 1998023714A1 EP 9706448 W EP9706448 W EP 9706448W WO 9823714 A1 WO9823714 A1 WO 9823714A1
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acid
weight
carbon atoms
polymer
groups
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PCT/EP1997/006448
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German (de)
English (en)
Inventor
Georg Meine
Thomas Möller
Fred Schambil
Ludwig Schieferstein
Paul Birnbrich
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Henkel Kommanditgesellschaft Auf Aktien
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Priority to EP97951237A priority Critical patent/EP0944701A1/fr
Publication of WO1998023714A1 publication Critical patent/WO1998023714A1/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
    • 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
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines

Definitions

  • the present invention relates to the use of certain dirt-releasing polymers for enhancing the cleaning performance of detergents when washing textiles, in particular those which consist of cotton or contain cotton, and detergents which contain such dirt-releasing polymers.
  • detergents In addition to the ingredients that are indispensable for the washing process, such as surfactants and builder materials, detergents generally contain other ingredients, which can be summarized under the term washing aids and which include such different active ingredient groups as foam regulators, graying inhibitors, bleaching agents, bleach activators and color transfer inhibitors.
  • 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.
  • soil release agents are often referred to as "soil release” actives or because of their ability to make the treated surface, for example the fiber, dirt repellent, "soil repellents".
  • German Offenlegungsschrift DT 16 17 141 describes a washing process using polyethylene terephthalate-polyoxyethylene glycol copolymers.
  • German laid-open specification DT 22 00 911 relates to detergents which contain nonionic surfactant and a copolymer of polyoxyethylene glycol and polyethylene terephthalate.
  • acidic textile finishing agents are mentioned, which are a copolymer of a dibasic carboxylic acid and an alkylene or Contain cycloalkylene polyglycol and optionally an alkylene or cycloalkylene glycol. Polymers made from ethylene terephthalate and polyethylene oxide terephthalate.
  • polyethylene glycol units have molecular weights of 750 to 5000 and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate is 50:50 to 90:10, and their use in detergents are described in German patent DE 28 57292.
  • 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 1000 to 10,000 and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate being 2: 1 to 6: 1, can be according to the German published patent application DE 33 24258 can be used in detergents.
  • European patent EP 066 944 relates to textile treatment agents which contain a copolyester of ethylene glycol, polyethylene glycol, aromatic dicarboxylic acid and sulfonated aromatic dicarboxylic acid in certain molar ratios.
  • European or European patent EP 185 427 discloses methyl or ethyl end-capped polyesters with ethylene and / or propylene terephthalate and polyethylene oxide terephthalate units and detergents which contain such a soil release polymer.
  • 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, in addition to oxyethylene groups and terephthalic acid units, contain 1,2-propylene, 1,2-butylene and / or 3-methoxy-1,2-propylene groups and glycerol units and with Cp to C 4 alkyl groups are end group capped.
  • 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 0.6 to Is 0.95.
  • European patent application EP 272 033 discloses polyesters with poly-propylene terephthalate and polyoxyethylene terephthalate units which are end group capped by d- 4 -alkyl or acyl radicals.
  • European patent EP 274 907 describes sulfoethyl end group-capped terephthalate-containing soil release polyesters.
  • European patent application EP 357 280 soil-release polyesters with terephthalate, alkylene glycol and poly-C 1 -glycol units are produced by sulfonation of unsaturated end groups.
  • the polymers known from this extensive state of the art have the disadvantage that they have no or only inadequate effectiveness in textiles which do not consist, or at least not predominantly, of polyester.
  • a large part of today's textiles consists of cotton or cotton-polyester blended fabrics, so that there is a need for polymers which are more effective at removing soiling from such textiles in the case of greasy soiling.
  • the invention relates to the use of water-soluble nitrogen-containing dirt-releasing polymers to enhance the cleaning performance of detergents when washing textiles which consist of cotton or contain cotton.
  • Another object of the invention is the use of a combination of such a cotton-active nitrogen-containing dirt-releasing polymer with a polyester-active dirt-releasing polymer made of a dicarboxylic acid and an optionally polymeric diol for enhancing the cleaning performance of detergents when washing textiles.
  • water-soluble is to be understood as meaning a solubility of at least 0.001 g, preferably at least 0.01 g, of the polymer per liter of water at room temperature and pH 7. However, under these conditions, preferably used polymers have a solubility of at least 1 g per liter, in particular at least 10 g per liter.
  • Nitrogen-containing, dirt-releasing polymers can be either neutral or cationically charged, the cationic polymers in particular being preferably used to enhance the cleaning performance when washing textiles made of cotton.
  • the positive charge is introduced into the polymer by quaternization of the nitrogen.
  • Corresponding charge-balancing anions are, for example, chloride, bromide, sulfate, hydrogen sulfate, carbonate and hydrogen carbonate. At least partial charge balancing can be brought about by carboxylate groups present in the polymer.
  • Suitable nitrogen-containing dirt-releasing polymers include, in particular, those which essentially consist of one another
  • R'-CH CR 2 -CO-Z- (C n H 2n ) -NR 3 R 4 (I)
  • R 1 -CH CR 2 -CO-Z- (C n H 2n ) -N + R 3 R 4 R 5 A " (II) in which R 1 and R 2 independently of one another represent hydrogen or a methyl group, R 3 , R 4 and R 5 independently of one another are alkyl groups with 1 to 4 carbon atoms, Z for an NH group or an oxygen atom, n for an integer from 2 to 5 and A " for the anion of an organic or inorganic acid, and (ß) monomeric carboxylic acid (derivatives) n of the general formulas (III) or
  • R 6 -CH CR 7 -CONH 2 (IV) in which R 6 and R 7 independently of one another for hydrogen or methyl groups and R 8 for hydrogen, an alkali metal, alkaline earth metal, aluminum or ammonium ion or an alkyl group with 1 to 4 Carbon atoms are there.
  • the monomers ( ⁇ ) include, for example, dimethyl aminoethyl acrylamide, dimethylaminoethyl methacrylamide, dimethylaminopropylacrylamide, dimethylaminopropyl methacrylamide and diethylaminoethyl acrylamide if Z is an NH group, or dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate and diethylaminoethyl acrylate.
  • Monomers of the formula (I) or (II) which are derivatives of acrylamide or methacrylamide are advantageously used. Those are also preferred Monomers of the formula (I) or (II) in which R and R 4 or R 3 , R 4 and R 5 are methyl groups.
  • Dimethylaminoethyl methacrylate is a very particularly preferred monomer of formula (I).
  • the monomeric carboxylic acids or carboxylic acid derivatives (ß) include acrylic acid, methacrylic acid, crotonic acid and 2-methyl-crotonic acid as well as their amides and C ⁇ - 4 alkyl esters.
  • acrylic or methacrylic acid, in particular acrylic acid, and their amides or esters are preferably used.
  • the particularly preferred esters include those of methanol, ethanol, propanol, butanol and in particular isobutanol.
  • Preferred salts of the carboxylic acids mentioned are the lithium, sodium, potassium, magnesium, calcium and aluminum salts. The sodium salt is particularly preferred.
  • ammonium salts of carboxylic acids can be used, in which the ammonium ion can carry one to three alkyl groups with 1-4 carbon atoms or hydroxyalkyl groups with 2-4 carbon atoms .
  • the salts those with unsubstituted ammonium ions and triethanolammonium ions are preferred.
  • Reaction products of monomeric dicarboxylic acids with 2 to 22 C atoms, in particular 4 to 8 C atoms, with aliphatic or cycloaliphatic secondary amines of the general formula (V) are also useful as nitrogen-containing dirt-releasing polymers in the context of the invention.
  • polyester-active dirt-releasing polymers which can be used in addition to the nitrogen-containing polymers include copolyesters of dicarboxylic acids, for example adipic acid, phthalic acid or terephthalic acid, diols, for example ethylene glycol or propylene glycol, and polydiols, for example polyethylene lenglycol or polypropylene glycol.
  • dicarboxylic acids for example adipic acid, phthalic acid or terephthalic acid
  • diols for example ethylene glycol or propylene glycol
  • polydiols for example polyethylene lenglycol or polypropylene glycol.
  • 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 HO- (CHR ⁇ -) a OH, which is also used as a polymer Diol H- (O- (CHRn-) a ) b OH may be present.
  • Ph means 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.
  • R 11 is hydrogen, an alkyl radical with 1 to 22 C atoms and mixtures thereof, a is a number from 2 to 6 and b is a number from 1 to 300.
  • Both monomer diol units -O- (CHR ⁇ -) are preferably present in the polyesters obtainable from these. a O- as well as polymer diol units - (O- (CHR ⁇ -) a ) b O-.
  • the molar ratio of monomer diol units to polymer diol 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 in the range from 250 to 100,000, in particular from 500 to 50,000
  • the acid on which the radical Ph is based 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 them, 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 HO- (CHR n -) a OH include those in which R 11 is hydrogen and a is a number from 2 to 6, and those in which a is 2 and R 11 is hydrogen and the alkyl radicals 1 to 10, in particular 1 to 3 carbon atoms is selected.
  • diols those of the formula HO-CH 2 -CHR "-OH, in which R 11 has the abovementioned meaning, are particularly preferred.
  • Examples of diol components are ethylene glycol.
  • 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 C atoms, in particular 5 to 18 C atoms.
  • valeric acid caproic acid, enanthic 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, petroselagenic acid.
  • Gadoleic acid arachidonic acid, behenic 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-, m- and p-hydroxybenzoic acid.
  • the hydroxy monocarboxylic acids can in turn be linked 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.
  • the use according to the invention can take place in the course of a washing process in such a way that the nitrogen-containing polymer is added separately to a detergent-containing liquor, or the polymer is introduced into the liquor as part of the detergent.
  • Another object of the invention is therefore a detergent which contains a nitrogen-containing polymer described above.
  • Detergents which contain a nitrogen-containing polymer to be used according to the invention can contain all the usual other constituents of such compositions which do not interact undesirably with the soil-release polymer.
  • the nitrogen-containing polymer is preferably incorporated into detergent in amounts of 0.1% by weight to 5% by weight, in particular 0.5% by weight to 2.5% by weight.
  • such an agent contains nonionic surfactant selected from fatty alkyl polyglycosides, fatty alkyl polyalkoxylates, in particular ethoxylates and / or propoxylates, fatty acid polyhydroxyamides and / or ethoxylation and / or propoxylation products of fatty alkylamines, 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.
  • Another embodiment of such agents comprises the presence of synthetic anionic surfactants of the sulfate and / or sulfonate type.
  • 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 non-ionic 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 20, preferably between 3 and 10. They can be prepared in a known manner by reacting the corresponding alcohols 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 octadecyl radicals, and mixtures thereof, can be used.
  • Corresponding alkoxylation products of alkylamines, vicinal diols and carboxamides which correspond to the alcohols mentioned with regard to the alkyl part can also be used.
  • there are the ethylene oxide and / or propylene oxide insertion products of fatty acid alkyl esters as can be prepared in accordance with the process specified in international patent application WO 90/13533, and fatty acid polyhydroxyamides, as in accordance with the processes in US Pat.
  • alkyl polyglycosides suitable for incorporation into the agents according to the invention are compounds of the general formula (G) "- OR 12 , in which R 12 is an alkyl or alkenyl radical having 8 to 22 C atoms, G is a glycose unit and n is a number between 1 and 10 mean.
  • G general formula
  • R 12 is an alkyl or alkenyl radical having 8 to 22 C atoms
  • G is a glycose unit
  • n is a number between 1 and 10 mean.
  • Such compounds and their preparation are described, for example, in European patent applications EP 92 355, EP 301 298, EP 357 969 and EP 362 671 or US Pat. No. 3,547,828.
  • the glycoside component (G) n is an oligomer or polymer made from naturally occurring aldose or ketose monomers, in particular glucose. Mannose. Fructose, galactose, talose, gulose, altrose, allose, idose, ribose, arabinose, xylose and lyxose include.
  • 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 oligomerization.
  • the degree of oligomerization n generally takes fractional 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 12 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.
  • Nonionic surfactant is contained in agents which contain a soil release active ingredient used according to the invention, preferably in amounts of 1% by weight to 30% by weight, in particular from 1% by weight to 25% by weight.
  • such agents can each be based on additional 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 on total means included.
  • additional 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 on total means included.
  • Synthetic anionic surfactants which are particularly suitable for use in agents of this type are the alkyl and / or alkenyl sulfates having 8 to 22 C atoms and carrying 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 in a known manner by reaction of the corresponding alcohol component with a conventional sulfation reagent, in particular sulfur trioxide or chlorosulfonic acid. and subsequent neutralization with alkali. Ammonium- or alkyl- or hydroxyalkyl-substituted ammonium bases can be produced.
  • Such alkyl and / or alkenyl sulfates are in the compositions which contain a polymer according to the invention, preferably in amounts from 0.1% by weight to 20% by weight, in particular from 0.5% by weight to 18% by weight. % contain.
  • the sulfate-type surfactants that can be used also include the sulfated alkoxylation products of the alcohols mentioned, so-called ether sulfates.
  • ether sulfates preferably contain 2 to 30, in particular 4 to 10, ethylene glycol groups per molecule.
  • 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 with 8 to 22 carbon atoms, preferably 12 to 18 carbon atoms, and linear alcohols with 1 up 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 can be 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 C 2 -C 8 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 compositions which contain a polymer used according to the invention, higher amounts of soap, as a rule up to 20% by weight, can also be present.
  • 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 also the polymeric (poly) carboxylic acids.
  • the polycarboxylates of international patent application WO 93/16110 which are accessible by oxidation of polysaccharides, polymeric acrylic acids, methacrylic acids, maleic acids and copolymers thereof, which can also contain small amounts of polymerizable substances without carboxylic acid functionality in copolymerized form.
  • the relative molecular weight 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 methyl ethers, vinyl esters, ethylene, propylene and styrene, in which the proportion of acid is at least 50% by weight.
  • Terpolymers which contain two carboxylic acids and / or their salts as monomers and vinyl alcohol and or a vinyl alcohol derivative or a carbohydrate as monomers can also be used as water-soluble organic builder substances.
  • the first acidic monomer or its salt is derived from a monoethylenically unsaturated C 8 -C 8 -carboxylic acid and preferably from a C -C 4 -monocarboxylic acid, in particular from (meth) acrylic acid.
  • the second acidic monomer or its salt can be a derivative of a C 4 -Cg 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 Maleinate and 5 wt .-% to 40 wt .-%, preferably 10 wt .-% to 30 wt .-% vinyl alcohol and / or vinyl acetate.
  • Terpolymers are very particularly preferred which the weight ratio (meth) acrylic acid or (meth) acrylate to maleic acid or maleate is between 1: 1 and 4: 1, preferably between 2: 1 and 3: 1 and in particular 2: 1 and 2.5: 1. Both the amounts and the weight ratios are based on the acids.
  • the second acidic monomer or its salt can also be a derivative of an allylsulfonic acid which, in the 2-position, has an alkyl radical, preferably a C 1 -C 4 -alkyl radical, or an aromatic radical which is preferably derived from benzene or benzene derivatives. is substituted.
  • 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 methallylsulfonic acid or methallylsulfonate 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-. Be oligosaccharide 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.
  • terpolymers can be produced in particular by processes which are described in German patent specification DE 42 21 381 and German patent application DE 43 00 772 and generally have a relative molecular mass between 1000 and 200000, preferably between 200 and 50,000 and in particular between 3000 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 in which the polymer according to the invention is contained.
  • the water-insoluble, water-dispersible inorganic builder materials are particularly kris t alline or amorphous alkali aluminosilicates. 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% by weight. Among these are the crystalline aluminosilicates in detergent quality, in particular zeolite NaA and optionally NaX.
  • Suitable aluminosilicates in particular have no particles with a grain size above 30 mm and preferably consist of at least 80% by weight of particles with a size below 10 mm.
  • Their calcium binding capacity which can be determined according to the information in German patent DE 24 12 837, is in the range from 100 to 200 mg CaO per gram.
  • Suitable substitutes or partial substitutes for the aluminosilicate mentioned are crystalline alkali silicates, which can be present alone or in a mixture with amorphous silicates.
  • the alkali silicates which can be used as builders in the compositions 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: SiO 2 molar ratio of 1: 2 to 1: 2.8.
  • Such amorphous alkali silicates are commercially available, for example, under the name Portil®. Those with a Na 2 O: SiO 2 molar ratio of 1: 1.9 to 1: 2.8 can be produced by the process of European patent application EP 0 425 427.
  • Crystalline phyllosilicates of the general formula Na 2 Si x O 2x + ⁇ yH 2 O, in which x, the so-called modulus, is a number from 1.9 to 4, are preferably used as crystalline silicates, which may be present alone or in a mixture with amorphous silicates 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 ⁇ -sodium disilicate are preferred, with ⁇ -sodium disilicate being able to be obtained, for example, by the method described in international patent application WO 91/08171.
  • ⁇ -sodium silicates with a modulus between 1.9 and 3.2 can be made according to Japanese patent applications JP 04/238 809 or JP 04/260 610.
  • Practically anhydrous crystalline alkali silicates of the above general formula, in which x denotes a number from 1.9 to 2.1, can also be prepared from amorphous alkali silicates, as described in European patent applications EP 0 548 599, EP 0 502 325 and EP 0452 428 , can be used in agents which contain a polymer 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 0 436 835.
  • Crystalline sodium silicates with a modulus in the range from 1.9 to 3.5 are used in a further preferred embodiment of washing or cleaning agents which contain a polymer according to the invention.
  • Their alkali silicate content 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. If alkali alumosilicate, in particular zeolite, is also present as an additional builder substance, 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.
  • the 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, bleaches. 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 inhibitors. for example polyvinylpyrrolidone or polyvinylpyrdine-N-oxide.
  • Foam inhibitors for example organopolysiloxanes or paraffins, solvents and optical brighteners, for example stilbene disulfonic acid derivatives.
  • agents which contain a polymer according to the invention up to 1% by weight, in particular 0.01% by weight to 0.5% by weight, of 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 refer to the entire average.
  • Solvents which are used in particular in the case of liquid compositions which contain a polymer according to the invention are, in addition to water, 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 polyesters according to the invention are generally dissolved or in suspended form in such liquid compositions.
  • Any enzymes present are preferably selected from the group comprising protease, amylase, lipase, cellulase, hemicellulase, oxidase, peroxidase or mixtures thereof.
  • Protease obtained from microorganisms such as bacteria or fungi, is primarily suitable. They can be obtained in known manner by fermentation processes from suitable microorganisms, for example, in the eng t's published patent applications DE 1940488, DE 20 44 161, DE 22 01 803 and DE 21 21 397, the US patents US 3,632,957 and US 4,264,738, European patent application EP 006 638 and international patent application WO 91/02792 are described.
  • Proteases are commercially available for wise under the names BLAP®, Savinase®, Esperase®, Maxatase®. Optimase®. Alcalase®, Durazym® or Maxapem® available.
  • the lipase which can be used can be obtained from Humicola lanuginosa, as described, for example, in European patent applications EP 258 068, EP 305 216 and EP 341 947, from Bacillus species.
  • Suitable lipases are commercially available, for example, under the names Lipolase®, Lipozym®, Lipomax®, Amano® lipase, Toyo-Jozo® lipase, Meito® lipase and Diosynth® lipase.
  • Suitable amylases are commercially available, for example, under the names Maxamyl®, Termamyl®, Duramyl® and Purafect® OxAm.
  • 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 published applications DE 31 17 250, DE 32 07 825, DE 32 07 847, DE 33 22 950 or European patent applications EP 265 832, EP 269 977, EP 270 974, EP 273 125 and EP 339 550 known.
  • the usual enzyme stabilizers which may be present, in particular in liquid agents include amino alcohols, for example mono-, di-, triethanol- and propanolamine and mixtures thereof, lower carboxylic acids, as known, for example, from European patent applications EP 376 705 and EP 378 261, Boric acid or alkali borates, boric acid-carboxylic acid combinations, as known, for example, from European patent application EP 451 921, boric acid esters, as known for example from international patent application WO 93/11215 or European patent application EP 511 456, boronic acid derivatives, such as from European patent application EP 583 536 known calcium salts, for example those from the European patent EP 28 865 known Ca-formic acid combination.
  • Magnesium salts such as known from European patent application EP 378 262, and / or sulfur-containing reducing agents, such as known from European patent applications EP 080 748 or EP 080 223.
  • Suitable foam inhibitors include long-chain soaps, in particular beech soap, fatty acid amides, paraffins, waxes, microcrystalline waxes, organopolysiloxanes and mixtures thereof, which may 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 309 931 or European patent EP 150 386.
  • an agent which contains a polymer used 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 the graying of the fibers.
  • Water-soluble colloids of mostly organic nature are suitable for this , 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 such an agent which contains a soil-release polymer to be used 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% to 10% by weight.
  • 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% to 10% by weight.
  • These bleaches in question are the per compounds generally used in detergents, such as hydrogen peroxide, perborate, or as the tetra- Monohydrate can be present, percarbonate, pyrophosphate and persilicate, which are generally present as alkali metal salts, in particular as sodium salts.
  • Such bleaching agents are in detergents which contain a polymer used according to the invention, preferably in amounts of up to 25% by weight, in particular up to 15% by weight and particularly preferably from 5% by weight to 15% by weight, in each case on all means, available.
  • the optional component of the bleach activators comprises the N- or O-acyl compounds commonly used, for example multiply acylated alkylenediamines, in particular tetraacetylethylenediamine, acylated glycolurils, in particular tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles. Urazole.
  • Diketopiperazines, sulfurylamides and cyanurates also carboxylic anhydrides, especially phthalic anhydride, carboxylic acid esters, especially sodium isononanoyl phenol sulfonate, and acylated sugar derivatives, especially pentaacetyl glucose.
  • the bleach activators can be coated or granulated with coating substances in a known manner in order to avoid the interaction with the per-compounds during storage, with tetraacetylethylenediamine granulated with carboxymethyl cellulose with average grain sizes of 0.01 mm to 0.8 mm, as described, for example, by can be prepared in the European patent specification EP 37 026, and / or granulated 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine, as it is according to the method described in the German patent specification DD 255 884 can be produced, is particularly preferred.
  • 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 into which the soil-release polymer according to the invention or according to the invention is incorporated is particulate and 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, 2.5% to 20% by weight of synthetic anionic surfactant, 1% to 20% by weight of nonionic surfactant, up to 25% by weight, in particular 1% by weight to 15% by weight of bleach, up to 8% by weight, in particular 0.5% by weight to 6% by weight of bleach activator and up to 20% by weight, in particular 0.1 % By weight to 15% by weight of inorganic salts, in particular alkali carbonate and / or sulfate.
  • such a powdery agent contains, in particular for use as a mild detergent. 20% by weight to 55% by weight of inorganic builders, up to 15% by weight, in particular 2% by weight to 12% by weight of water-soluble organic builders, 4% by weight to 24% by weight nonionic Surfactant. up to 15% by weight, in particular 1% by weight to 10% by weight, synthetic anionic surfactant. up 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.
  • Sokalan® DCS Manufacturer BASF
  • Polymer-free detergent containing 4% by weight Na-C 2 alkylbenzenesulfonate, 4% by weight Na-Ci 6 / ⁇ g alkyl sulfate, 6% by weight nonionic surfactant (mixture of ethoxylated fatty alcohols), 1% by weight soap, 25% by weight of zeolite Na-A, 6% by weight of Na polycarboxylate (Sokalan® CP 5), 20% by weight of Na perborate (tetrahydrate), 6% by weight of TAED, 10% by weight of Na -Carbonate, 4 wt .-% Na sulfate.
  • nonionic surfactant mixture of ethoxylated fatty alcohols
  • soap 25% by weight of zeolite Na-A
  • 6% by weight of Na polycarboxylate Sokalan® CP 5
  • Na perborate tetrahydrate
  • TAED 10% by weight of Na -Carbonate, 4 wt .-% Na s

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

L'objectif de l'invention est d'améliorer les performances de nettoyage d'agents de lavage lors du lavage de textiles qui sont constitués de coton ou contiennent du coton. Cet objectif est atteint essentiellement par introduction dans ses agents de lavage d'un polymère facilitant le lavage hydrosoluble, azoté.
PCT/EP1997/006448 1996-11-28 1997-11-19 Polymeres facilitant le lavage, agissant sur le coton WO1998023714A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP97951237A EP0944701A1 (fr) 1996-11-28 1997-11-19 Polymeres facilitant le lavage, agissant sur le coton

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE1996149288 DE19649288A1 (de) 1996-11-28 1996-11-28 Baumwollaktive schmutzablösevermögende Polymere
DE19649288.2 1996-11-28

Publications (1)

Publication Number Publication Date
WO1998023714A1 true WO1998023714A1 (fr) 1998-06-04

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DE (1) DE19649288A1 (fr)
WO (1) WO1998023714A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001057171A1 (fr) * 2000-02-02 2001-08-09 Unilever Plc Polymeres pour applications de nettoyage
EP1375633A1 (fr) * 2002-06-25 2004-01-02 Cognis Iberia, S.L. Compositions détergentes contenant des polymères
US7659354B2 (en) 2002-12-23 2010-02-09 Ciba Specialty Chemiclas Corporation Hydrophobically modified polymers as laundry additives
WO2016146429A1 (fr) * 2015-03-19 2016-09-22 Henkel Ag & Co. Kgaa Esters polymères d'acides dicarboxyliques aromatiques utilisés comme substances actives à pouvoir détachant

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6642200B1 (en) * 1999-03-25 2003-11-04 The Procter & Gamble Company Fabric maintenance compositions comprising certain cationically charged fabric maintenance polymers
US6733538B1 (en) 1999-03-25 2004-05-11 The Procter & Gamble Company Laundry detergent compositions with certain cationically charged dye maintenance polymers
MXPA01009728A (es) * 1999-03-25 2002-03-14 Procter & Gamble Composiciones detergentes para lavanderia con ciertos polimeros de conservacion de colorante cargados cationicamente.
US6703358B1 (en) * 2000-07-13 2004-03-09 Rhodia Chimie Cleaning composition for hard surfaces

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2104227A5 (fr) * 1970-08-12 1972-04-14 Unilever Nv
DE4313085A1 (de) * 1993-04-21 1994-10-27 Stockhausen Chem Fab Gmbh Stabile wäßrige Dispersionen von quartären Ammoniumverbindungen und Imidazolin-Derivaten
WO1997042285A1 (fr) * 1996-05-03 1997-11-13 The Procter & Gamble Company Polymeres de detachage des cotons

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2104227A5 (fr) * 1970-08-12 1972-04-14 Unilever Nv
DE4313085A1 (de) * 1993-04-21 1994-10-27 Stockhausen Chem Fab Gmbh Stabile wäßrige Dispersionen von quartären Ammoniumverbindungen und Imidazolin-Derivaten
WO1997042285A1 (fr) * 1996-05-03 1997-11-13 The Procter & Gamble Company Polymeres de detachage des cotons

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001057171A1 (fr) * 2000-02-02 2001-08-09 Unilever Plc Polymeres pour applications de nettoyage
US6554869B2 (en) 2000-02-02 2003-04-29 Unilever Home & Personal Care Usa, A Division Of Conopco, Inc. Polymers for laundry applications
EP1375633A1 (fr) * 2002-06-25 2004-01-02 Cognis Iberia, S.L. Compositions détergentes contenant des polymères
US7659354B2 (en) 2002-12-23 2010-02-09 Ciba Specialty Chemiclas Corporation Hydrophobically modified polymers as laundry additives
EP2650353A2 (fr) 2002-12-23 2013-10-16 Basf Se Produits d'entretien du linge contenant des polymères modifiés hydrophobes en tant qu'additifs
WO2016146429A1 (fr) * 2015-03-19 2016-09-22 Henkel Ag & Co. Kgaa Esters polymères d'acides dicarboxyliques aromatiques utilisés comme substances actives à pouvoir détachant

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Publication number Publication date
DE19649288A1 (de) 1998-06-04
EP0944701A1 (fr) 1999-09-29

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