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EP1592765B1 - Augmentation de la puissance de nettoyage de produits de lavage a l'aide d'un derive cellulosique et d'un polymere hygroscopique - Google Patents

Augmentation de la puissance de nettoyage de produits de lavage a l'aide d'un derive cellulosique et d'un polymere hygroscopique Download PDF

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Publication number
EP1592765B1
EP1592765B1 EP04707142A EP04707142A EP1592765B1 EP 1592765 B1 EP1592765 B1 EP 1592765B1 EP 04707142 A EP04707142 A EP 04707142A EP 04707142 A EP04707142 A EP 04707142A EP 1592765 B1 EP1592765 B1 EP 1592765B1
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EP
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Prior art keywords
acid
weight
cellulose derivative
soil release
hygroscopic polymer
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EP04707142A
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German (de)
English (en)
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EP1592765A1 (fr
Inventor
Josef Penninger
Thorsten Bastigkeit
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Priority claimed from DE10351324A external-priority patent/DE10351324A1/de
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP1592765A1 publication Critical patent/EP1592765A1/fr
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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
    • D06M15/03—Polysaccharides or derivatives thereof
    • D06M15/05—Cellulose or derivatives thereof
    • D06M15/09—Cellulose 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
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
    • 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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C11D3/225—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin etherified, e.g. CMC
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material

Definitions

  • the present patent application relates to enhancing the detergency of laundry detergents in the washing of textiles by the use of a combination of soil release cellulose derivative and hygroscopic polymer.
  • Detergents contain in addition to the indispensable for the washing process ingredients such as surfactants and builder materials usually further ingredients that can be summarized by the term washing aids and include as different drug groups such as foam regulators, grayness inhibitors, bleach, bleach activators and dye transfer inhibitors.
  • Such adjuvants also include substances which impart soil repellency properties to the laundry fiber and, if present during the wash, aid the soil release properties of the remaining detergent ingredients. The same applies mutatis mutandis to cleaners for hard surfaces.
  • soil release agents are often referred to as “soil release” agents or because of their ability to impart soil repellency to the treated surface, such as the fiber, as “soil repellents".
  • European Patent Application EP 0 213 729 discloses the reduced redeposition when using detergents containing a combination of soap and nonionic surfactant with alkyl hydroxyalkyl cellulose.
  • European Patent Application EP 0 213 730 discloses textile treatment compositions containing cationic surfactants and nonionic cellulose ethers having HLB values of from 3.1 to 3.8.
  • US Pat. No. 4,000,093 discloses detergents containing from 0.1% to 3% by weight of alkyl cellulose, hydroxyalkyl cellulose or alkyl hydroxyalkyl cellulose and from 5% to 50% by weight.
  • surfactant wherein the surfactant component consists essentially of C 10 - to C 13 alkyl sulfate and up to 5 wt .-% C 14 alkyl sulfate and less than 5% by weight of alkyl sulfate having alkyl radicals of C 15 and higher.
  • US Pat. No. 4,174,305 discloses laundry detergents containing from 0.1% to 3% by weight of alkyl cellulose, hydroxyalkyl cellulose or alkyl hydroxyalkyl cellulose and from 5% to 50% by weight.
  • % Surfactant wherein the surfactant component consists essentially of C 10 - to C 12 alkylbenzenesulfonate and less than 5 wt .-% alkylbenzenesulfonate having alkyl radicals of C 13 and higher.
  • European patent application EP 0 634 481 relates to a detergent containing alkali metal percarbonate and one or more nonionic cellulose derivatives. The latter expressly disclose only hydroxyethylcellulose, hydroxypropylcellulose and methylcellulose and, in the examples, the methylhydroxyethylcellulose Tylose® MH50, the hydroxypropylmethylcellulose Methocel® F4M and hydroxybutylmethylcellulose.
  • European Patent Specification EP 0 271 312 (P & G) relates to soil release agents, among these cellulose alkyl ethers and cellulose hydroxyalkyl ethers (having DS 1.5 to 2.7 and molecular weights of 2,000 to 100,000) such as methyl cellulose and ethyl cellulose, which are weight ratio (based on the weight ratio) of peroxygen bleach Active oxygen content of the bleaching agent) of 10: 1 to 1:10 should be used.
  • European Patent EP 0 948 591 B1 discloses a detergent in liquid or granular form which imparts textile appearance advantages such as pilling / lint reduction, anti-color fading, improved abrasion resistance and / or increased softness to fabrics and textiles washed therewith, and provides 1 to 80 wt .-% of surfactant, 1 to 80 wt .-% organic or inorganic builder, 0.1 to 80 wt .-% of a hydrophobically modified nonionic cellulose ether having a molecular weight of 10,000 to 2,000,000, wherein the modification in the Presence of optionally oligomerized (degree of oligomerization up to 20) ethyleneoxy or 2-propyleneoxy ether units and C 8-24 alkyl substituents and the alkyl substituents in amounts of 0.1-5 wt .-%, based on the cellulose ether material, must be present.
  • 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 which contain a copolymer of a dibasic carboxylic acid and an alkylene or Cycloalkylenpolyglykol and optionally an alkylene or cycloalkylene glycol.
  • Polymers of ethylene terephthalate and polyethylene oxide terephthalate in which the polyethylene glycol units have molecular weights of 750 to 5000 and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate 50:50 to 90:10, and their use in detergents are in the German patent DE 28 57,292.
  • Polymers having a molecular weight of 15,000 to 50,000 of ethylene terephthalate and polyethylene oxide terephthalate, wherein the polyethylene glycol units have molecular weights of 1000 to 10,000 and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate is 2: 1 to 6: 1, can according to the German Offenlegungsschrift DE 33 24 258 are used in detergents.
  • European patent EP 066 944 relates to textile treatment compositions containing a copolyester of ethylene glycol, polyethylene glycol, aromatic dicarboxylic acid and sulfonated aromatic dicarboxylic acid in certain molar ratios.
  • European Patent EP 185,427 discloses methyl or ethyl end-capped polyesters having ethylene and / or propylene terephthalate and polyethylene oxide terephthalate units and detergents containing such 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 also glycerol units.
  • polyesters which in addition to oxyethylene groups and terephthalic acid units containing 1,2-propylene, 1,2-butylene and / or 3-methoxy-1,2-propylene groups and glycerol units and with C 1 - Are capped to C 4 alkyl groups.
  • European Patent EP 253 567 relates to soil release polymers having a molecular weight of 900 to 9000 of ethylene terephthalate and polyethylene oxide terephthalate, wherein the polyethylene glycol units have molecular weights of 300 to 3,000 and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate is 0.6 to 0.95.
  • European Patent Application EP 272 033 discloses, at least in part, polyesters having poly-propylene terephthalate and polyoxyethylene terephthalate units which are end-capped by C 1-4 -alkyl or acyl radicals.
  • European Patent EP 274,907 describes sulfoethyl end-capped terephthalate-containing soil release polyesters.
  • European Patent Application EP 357,280 sulfonation of unsaturated end groups produces soil release polyesters with terephthalate, alkylene glycol and poly-C 2-4 glycol units.
  • the German patent application DE 26 55 551 describes the reaction of such polyesters with isocyanate group-containing polymers and the use of the polymers thus prepared against the re-raising of dirt during the washing of synthetic fibers.
  • Detergents are known from German Patent DE 28 46 984, which contain a reaction product of a polyester with a prepolymer containing terminal isocyanate groups, obtained from a diisocyanate and a hydrophilic nonionic Macrodiol, as a dirt-absorbent-capable polymer.
  • FR-A-2237960 discloses detergent compositions containing a derivative of an alkyl hydroxyalkyl cellulose and a copolymer of maleic anhydride and ethylene or methyl vinyl ether.
  • the invention therefore relates to the use of a combination of soil release-capable cellulose derivative obtainable by alkylation and hydroxyalkylation of cellulose, and hygroscopic polymer for enhancing the cleaning performance of detergents in the washing of textiles.
  • Preferred cellulose derivatives are those which are alkylated with C 1 to C 10 groups, in particular C 1 to C 3 groups, and additionally carry C 2 to C 10 hydroxyalkyl groups, in particular C 2 to C 3 hydroxyalkyl groups.
  • appropriate alkylating agents for example alkyl halides or alkyl sulfates, and subsequent reaction with corresponding alkylene oxides, such as, for example, ethylene oxide and / or propylene oxide.
  • a mean of 0.5 to 2.5, in particular 1 to 2, alkyl groups and 0.02 to 0.5, in particular 0.05 to 0.3, hydroxyalkyl groups per anhydroglycosemonomer unit are contained in the cellulose derivative.
  • the average molar mass of the cellulose derivatives used according to the invention is preferably in the range from 10,000 D to 150,000 D, in particular from 40,000 D to 120,000 D and particularly preferably in the range from 80,000 D to 110,000 D.
  • the determination of the degree of polymerization or of the molecular weight of the soil release-capable cellulose derivative is based on the determination of the limiting viscosity number of sufficiently dilute aqueous solutions by means of an Ubbelohde capillary viscometer (capillary 0c). Using a constant [H. Staudinger and F. Reinecke, “On Molecular Weight Determination on Cellulose Ethers", Liebigs Annalen der Chemie 535, 47 (1938)] and a Correction Factor [F.
  • Rodriguez and LAGoettler, "The Flow of Moderately Concentrated Polymer Solutions in Water", Transactions of the Society of Rheology VIII, 3 17 (1964)] can be calculated from the degree of polymerization and, taking into account the degrees of substitution (DS and MS), the corresponding molecular weight.
  • Hygroscopic is the term for the property of many substances to attract humidity during prolonged storage in air. In contrast to substances that accumulate water (and form hydrates), hygroscopic substances are normally decomposed during prolonged storage in air.
  • hygroscopic polymers are sugar alcohols (eg starch), polypeptides (eg gelatin, polyaspartate) polyvinylpyrrolidone, polyvinyl alcohol, polyacrylic acid and derivatives of polyacrylic acid or polymers of derivatives of acrylic acid, such as poly (acrylic acid) sodium salt, poly (hydroxyacrylic acid), poly (acrylic acid-co-allyl alcohol), poly (4-methoxytetramethylene-1,2-dicarboxylic acid), poly (tetramethylene-1,2-dicarboxylic acid), Poly (acrylic acid-co-maleic acid) sodium salt, poly (acrylic acid-co-ethylene glycol diglycidyl ether, N, N'-methylenebisacrylamide sodium acrylate copolymer with hexaphospho
  • hygroscopic polymers are ⁇ -caprolactam polyethylene glycol terephthalic acid block copolymers, unsaturated amide-substituted ether compounds and polyphosphoric diesters and triesters.
  • the hygroscopic polymer is preferably selected from polyvinylpyrrolidone, polyvinyl alcohol, the polyalkylene glycols and / or the homopolymers of acrylic acid, methacrylic acid and maleic acid and also copolymers thereof, with polyacrylic acids being particularly preferred.
  • the molecular weights are preferably in the range of 500,000 D to 700,000 D, in particular from 550,000 D to 650,000 D.
  • the use according to the invention can be carried out as part of a washing process such that one adds the cellulose derivative and the hygroscopic polymer of a detergent-containing liquor separately, or introduces the cellulose derivative and / or the hygroscopic polymer as a component of the detergent in the liquor, it being particularly preferred if both the cellulose derivative as well as the hygroscopic polymer is part of the detergent.
  • Another object of the invention is therefore a detergent containing a combination as described above.
  • said detergent may also contain the combination to be used according to the invention, but it may also be free of this or at least one of its components.
  • a further subject of the invention is a process for washing textiles in which a detergent and a combination of a soil release-capable cellulose derivative obtainable by alkylation and hydroxyalkylation of cellulose and hygroscopic polymer are used.
  • This method can be carried out manually or preferably by means of a conventional household washing machine. It is possible to apply the detergent and the invention essential combination simultaneously or successively. The simultaneous application can be particularly advantageous by the use of a detergent containing the combination perform.
  • Detergents containing a combination to be used according to the invention may contain all the usual other constituents of such agents which do not undesirably interact with the constituents of the combination essential to the invention.
  • the cellulose derivative in amounts of from 0.1 wt .-% to 5 wt .-%, in particular 0.5 wt .-% to 2.5 wt .-% is incorporated in detergent.
  • the content of hygroscopic polymer in the detergent is preferably 0.1% by weight to 5% by weight, in particular 0.5% by weight to 2.5% by weight, by weight.
  • Another aspect of the invention relates to enhancing the cleaning performance of detergents in the washing of textiles made of cotton or containing cotton.
  • the combination used according to the invention has a positive effect on the action of certain other detergent ingredients and, conversely, that the effect of the combination used according to the invention is enhanced by certain other detergent ingredients.
  • these effects occur in particular with enzymatic agents, in particular proteases and Lipases, in water-insoluble inorganic builders, in water-soluble inorganic and organic builders, in particular based on oxidized carbohydrates, peroxygen bleaching agents, in particular alkali percarbonate, in synthetic anionic surfactants of sulfate and sulfonate type and in grayness inhibitors, for example other, in particular anionic cellulose ethers such as carboxymethyl cellulose, why the use of at least one of the said further ingredients together with the combination to be used according to the invention is preferred.
  • such agent comprises nonionic surfactant selected from fatty alkyl polyglycosides, fatty alkyl polyalkoxylates, especially 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 of 2 wt .-% to 25 wt .-%.
  • Such agents comprises the presence of sulfate and / or sulfonate synthetic anionic surfactant, in particular fatty alkyl sulfate, fatty alkyl ether sulfate, sulfo fatty acid ester and / or sulfo fatty acid salt, in particular in an amount in the range from 2% 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.
  • Suitable nonionic surfactants 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 C atoms, preferably 12 to 18 C 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.
  • Particularly suitable are the derivatives of fatty alcohols, although their branched-chain isomers, in particular so-called oxo alcohols, can be used for the preparation of usable alkoxylates.
  • the alkoxylates in particular the ethoxylates, primary alcohols with linear, especially dodecyl, tetradecyl, hexadecyl or octadecyl radicals and mixtures thereof.
  • suitable alkoxylation products of alkylamines, vicinal diols and carboxamides, which correspond to the said alcohols with respect to the alkyl part usable.
  • the ethylene oxide and / or propylene oxide insertion products of fatty acid alkyl esters as can be prepared according to the process disclosed in International Patent Application WO 90/13533, and fatty acid polyhydroxyamides, as prepared according to the processes of US Pat. Nos.
  • alkylpolyglycosides which are suitable for incorporation in the compositions according to the invention are compounds of the general formula (G) n -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.
  • 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 are oligomers or polymers of naturally occurring aldose or ketose monomers, in particular glucose, mannose, fructose, galactose, talose, gulose, altrose, allose, idose, ribose, arabinose, Include xylose and lyxose.
  • the oligomers consisting of such glycosidically linked monomers are characterized not only by the nature of the sugars contained in them by their number, the so-called Oligomermaschinesgrad.
  • the degree of oligomerization n assumes as the value to be determined analytically generally broken numerical values; it is between 1 and 10, with the glycosides preferably used below a value of 1.5, in particular between 1.2 and 1.4.
  • Preferred monomer building block is glucose because of its good availability.
  • the alkyl or alkenyl moiety R 12 of the glycosides preferably also originates from readily available derivatives of renewable raw materials, in particular from fatty alcohols, although their branched-chain isomers, in particular so-called oxoalcohols, can also be used for the preparation of useful glycosides. Accordingly, the primary alcohols having linear octyl, decyl, dodecyl, tetradecyl, hexadecyl or octadecyl radicals and mixtures thereof are particularly suitable.
  • Nonionic surfactant is included in compositions containing a combination used in the invention, preferably in amounts of 1 wt .-% to 30 wt .-%, in particular from 1 wt .-% to 25 wt .-%, with amounts in the upper part of this Area are more likely to be found in liquid detergents and particulate detergent preferably contain rather lower amounts of up to 5 wt .-%.
  • compositions may instead or additionally contain further surfactants, preferably synthetic anionic surfactants of the sulfate or sulfonate type, such as, for example, alkylbenzenesulfonates, 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 total resources.
  • Suitable synthetic anionic surfactants which are particularly suitable for use in such compositions are the alkyl and / or alkenyl sulfates having 8 to 22 C atoms which carry an alkali, ammonium or alkyl or hydroxyalkyl-substituted ammonium ion as counter cation.
  • alkyl and alkenyl sulfates can be prepared in a known manner by reaction of the corresponding alcohol component with a conventional sulfating reagent, in particular sulfur trioxide or chlorosulfonic acid, and subsequent neutralization with alkali metal, ammonium or alkyl or hydroxyalkyl-substituted ammonium bases.
  • a conventional sulfating reagent in particular sulfur trioxide or chlorosulfonic acid
  • Such alkyl and / or alkenyl sulfates are in the compositions containing a urethane-based polymer according to the invention, preferably in amounts of 0.1 wt .-% to 15 wt .-%, in particular from 0.5 wt .-% to 10 wt .-% included.
  • Sulfur-type surfactants which can be used also include the sulfated alkoxylation products of the alcohols mentioned, known as ether sulfates.
  • ether sulfates preferably contain from 2 to 30, in particular from 4 to 10, ethylene glycol groups per molecule.
  • Suitable anionic surfactants of the sulfonate type include the ⁇ -sulfoesters obtainable by reaction of fatty acid esters with sulfur trioxide and subsequent neutralization, in particular those of fatty acids having 8 to 22 C atoms, preferably 12 to 18 C atoms, and linear alcohols having 1 to 6 C atoms, preferably 1 to 4 carbon atoms, derivative sulfonation products, as well as the formal saponification resulting from these sulfo fatty acids.
  • soaps suitable being saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid or stearic acid, and soaps derived from natural fatty acid mixtures, for example coconut, palm kernel or tallow fatty acids.
  • those soap mixtures are preferred which are composed of 50% to 100% by weight of saturated C 12 -C 18 fatty acid soaps and up to 50% by weight of oleic acid soap.
  • soap is included in amounts of from 0.1% to 5% by weight.
  • higher amounts of soap generally up to 20% by weight, can also be present.
  • an agent which contains a combination to be used according to the invention contains water-soluble and / or water-insoluble builders, in particular selected from alkali metal aluminosilicate, crystalline alkali metal silicate with modulus above 1, monomeric polycarboxylate, polymeric polycarboxylate and mixtures thereof, in particular in amounts in the range of From 2.5% to 60% by weight.
  • An agent which contains a combination to be used according to the invention preferably contains from 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 obtainable by oxidation of polysaccharides of the international patent application WO 93/16110, polymeric acrylic acids, methacrylic acids, maleic acids and mixed polymers of these, which may also contain polymerized small amounts of polymerizable substances without carboxylic acid functionality.
  • the molecular weight of the homopolymers of unsaturated carboxylic acids is generally between 5000 and 200,000, that of the copolymers between 2000 and 200,000, preferably 50,000 to 120,000, based on the free acid.
  • a particularly preferred acrylic acid-maleic acid copolymer has a molecular weight of 50,000 to 100,000 Suitable, though less preferred compounds of this class are copolymers of acrylic or methacrylic acid with vinyl ethers such as vinylmethyl ethers, vinyl esters, ethylene, propylene and styrene in which the acid content is at least 50% by weight.
  • the first acidic monomer or its salt is derived from a monoethylenically unsaturated C 3 -C 8 -carboxylic acid and preferably from a C 3 -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 -C 8 -dicarboxylic acid, with maleic acid being particularly preferred.
  • the third monomeric unit is formed in this case of vinyl alcohol and / or preferably an esterified vinyl alcohol.
  • vinyl alcohol derivatives which are an ester of short-chain carboxylic acids, for example C 1 -C 4 carboxylic acids, with vinyl alcohol.
  • Preferred terpolymers contain 60 wt .-% to 95 wt .-%, in particular 70 wt .-% to 90 wt .-% 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 .-% of 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, preferably with 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 from 40% by weight to 60% by weight, in particular from 45 to 55% by weight, of (meth) acrylic acid or (meth) acrylate, particularly preferably acrylic acid or acrylate, from 10% by weight to 30% by weight. %, preferably 15 wt .-% to 25 wt .-% methallylsulfonic acid or Methallylsulfonat and as the third monomer 15 wt .-% to 40 wt .-%, preferably 20 wt .-% to 40 wt .-% of a carbohydrate.
  • This carbohydrate can be, for example, a mono-, di-, oligo- or polysaccharide, with mono-, di- or oligosaccharides being preferred, particularly preferred being sucrose.
  • the use of the third monomer presumably incorporates predetermined breaking points in the polymer which are responsible for the good biodegradability of the polymer.
  • These terpolymers can be prepared in particular by processes which are described in German Patent DE 42 21 381 and German Patent Application DE 43 00 772, and generally have a molecular weight between 1000 and 200,000, preferably between 200 and 50,000 and in particular between 3000 and 10000 on.
  • polycarboxylic acids can be used, in particular for the preparation of liquid agents, in the form of aqueous solutions, preferably in the form of 30 to 50 percent by weight aqueous solutions.
  • All 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. Quantities close to the stated upper limit are preferably used in pasty or liquid, in particular hydrous, agents.
  • Crystalline or amorphous alkali metal aluminosilicates in amounts of up to 50% by weight, preferably not more than 40% by weight, and in liquid agents, in particular from 1% by weight to 5% by weight, are particularly suitable as water-insoluble, water-dispersible inorganic builder materials.
  • the detergent-grade crystalline aluminosilicates especially zeolite NaA and optionally NaX, are preferred. Amounts near the above upper limit are preferably used in solid, particulate agents.
  • suitable aluminosilicates have no particles with a particle size greater than 30 mm and preferably consist of at least 80% by weight of particles having a size of less than 10 mm.
  • Suitable substitutes or partial substitutes for the said aluminosilicate are crystalline alkali silicates which may be present alone or in a mixture with amorphous silicates.
  • the alkali silicates useful 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 may be amorphous or crystalline available.
  • Preferred alkali metal silicates are the sodium silicates, in particular the amorphous sodium silicates, with a molar ratio of Na 2 O: SiO 2 of 1: 2 to 1: 2.8.
  • Such amorphous alkali silicates are commercially available, for example, under the name Portil®.
  • Those with a molar ratio of Na 2 O: SiO 2 of 1: 1.9 to 1: 2.8 can be prepared by the process of European Patent Application EP 0 425 427. They are preferably added in the course of the production as a solid and not in the form of a solution.
  • the crystalline silicates which may be present alone or in admixture with amorphous silicates, are crystalline layer silicates with the general formula Na 2 Si x O 2x + 1 ⁇ are used yH 2 O, in which x, the so-called module, 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 phyllosilicates are those in which x in the abovementioned general formula assumes the values 2 or 3.
  • both ⁇ - and ⁇ -sodium Na 2 Si 2 O 5 ⁇ yH 2 O
  • ⁇ -sodium disilicate being obtainable, 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 prepared according to Japanese patent applications JP 04/238 809 or JP 04/260 610.
  • Crystalline sodium silicates with a modulus in the range from 1.9 to 3.5 are disclosed in another preferred embodiment of laundry detergents. or cleaning agents which contain a Kombiantion used in the invention used.
  • the content of alkali metal silicates is preferably 1 wt .-% to 50 wt .-% and in particular 5 wt .-% to 35 wt .-%, based on anhydrous active substance.
  • alkali metal silicate in particular zeolite
  • the content of alkali metal silicate is preferably from I% by weight to 15% by weight and in particular from 2% by weight to 8% by weight, based on anhydrous active substance.
  • the weight ratio of aluminosilicate to silicate, in each case based on anhydrous active substances, is then preferably 4: 1 to 10: 1.
  • the weight ratio of amorphous alkali silicate to crystalline alkali metal silicate is preferably 1: 2 to 2: 1 1 and especially 1: 1 1 to 2: 1.
  • inorganic builder In addition to the above-mentioned inorganic builder, other water-soluble or water-insoluble inorganic substances may be used in the agents containing a combination to be used in the present invention. Suitable in this context are the alkali metal carbonates, alkali metal bicarbonates and alkali metal sulfates and mixtures thereof. Such additional inorganic material may be present in amounts up to 70% by weight.
  • the agents may contain other ingredients customary in detergents and cleaners.
  • These optional ingredients 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, dye fixing agents, dye transfer inhibitors, for example polyvinylpyrrolidone or polyvinylpyridine N-oxide, foam inhibitors, for example organopolysiloxanes or paraffins, solvents , and optical brighteners, for example stilbene disulfonic acid derivatives.
  • enzymes enzyme stabilizers
  • bleaches bleach activators
  • complexing agents for heavy metals for example aminopolycarboxylic acids, aminohydroxypolycarboxylic acids, polyphosphonic acids and / or aminopolyphosphonic acids
  • dye fixing agents for example aminopolycarboxylic acids, aminohydroxypolycarboxylic acids, polyphosphonic acids and / or aminopoly
  • compositions which contain a combination used 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 wt .-%, in particular 0.1 wt .-% to 2 wt .-% complexing agent for Heavy metals, in particular Aminoalkylenphosphonklaren and their salts, up to 3 wt .-%, in particular 0.5 wt .-% to 2 wt .-% grayness inhibitors and up to 2 wt .-%, in particular 0.1 wt .-% to 1 Wt .-% foam inhibitors, wherein said weight fractions refer to the total agent.
  • optical brighteners in particular compounds from the class of the substituted 4,4 ' -Bis (2
  • Solvents which are used in particular for liquid agents are, in addition to water, preferably those which are water-miscible. These include the lower alcohols, for example, ethanol, propanol, isopropanol, and the isomeric butanols, glycerol, lower glycols, such as ethylene and propylene glycol, and the derivable from said classes of compounds ether.
  • the components of the combination used in the invention are usually dissolved or in suspended form.
  • present enzymes are preferably selected from the group comprising protease, amylase, lipase, cellulase, hemicellulase, oxidase, peroxidase or mixtures thereof.
  • proteases derived from microorganisms such as bacteria or fungi, come into question. It can be obtained in a known manner by fermentation processes from suitable microorganisms, for example, in German Offenlegungsschriften DE 19 40 488, DE 20 44 161, DE 21 01 803 and DE 21 21 397, US Pat. Nos. 3,623,957 and US 4,264,738, European Patent Application EP 006 638 and international patent application WO 91/02792.
  • Proteases are commercially available, for example, under the names BLAP®, Savinase®, Esperase®, Maxatase®, Optimase®, Alcalase®, Durazym® or Maxapem®.
  • the lipase which can be used can be prepared from Humicola lanuginosa, as described, for example, in European patent applications EP 258 068, EP 305 216 and EP 341 947, from Bacillus species, as described, for example, in international patent application WO 91/16422 or European patent application EP 384 717 , from Pseudomonas species, as for example in the European patent applications EP 468 102, EP 385 401, EP 375 102, EP 334 462, EP 331 376, EP 330 641, EP 214 761, EP 218 272 or EP 204 284 or the international Patent application WO 90/10695, from Fusarium species, as described for example in the European patent application EP 130,064, from Rhizopus
  • Suitable lipases are commercially available, for example, under the names Lipolase®, Lipozym®, Lipomax®, Lipex®, Amano® lipase, Toyo-Jozo® lipase, Meito® lipase and Diosynth® lipase.
  • Suitable amylases are for example, under the names Maxamyl®, Termamyl®, Duramyl® and Purafect® OxAm commercially available.
  • the usable cellulase may be a recoverable from bacteria or fungi enzyme, which has a pH optimum, preferably in the weakly acidic to slightly alkaline range of 6 to 9.5.
  • Such cellulases are known, for example, from German Offenlegungsschriften 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 and international patent applications WO 95/02675 and WO 97/14804 and commercially available under the names Celluzyme®, Carezyme® and Ecostone®.
  • customary enzyme stabilizers include amino alcohols, for example mono-, di-, triethanol- and -propanolamine and mixtures thereof, lower carboxylic acids, such as from the European patent applications EP 376 705 and EP 378 261 known 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, as for example from European patent application EP 583 536 known, calcium salts, for example, the known from European Patent EP 28 865 Ca-formic acid combination, magnesium salts, as known for example from European Patent Application EP 378 262, and / or sulfur-containing reducing agents, such as from European patent applications EP 080 748 or EP 080 223.
  • lower carboxylic acids such as from the European patent applications EP 376 705 and EP 378 261 known boric acid or Alkali borates, boric
  • Suitable foam inhibitors include long-chain soaps, especially behenic soap, fatty acid amides, paraffins, waxes, microcrystalline waxes, organopolysiloxanes and mixtures thereof, which moreover can contain microfine, optionally silanated or otherwise hydrophobicized silica.
  • foam inhibitors are preferably bound to granular, water-soluble carrier substances, as described, for example, in German Offenlegungsschrift DE 34 36 194, European patent applications EP 262 588, EP 301 414, EP 309 931 or European patent EP 150 386.
  • a further embodiment of such an agent which contains a combination to be used according to the invention contains peroxygen-based bleaches, in particular in amounts ranging from 5% to 70% by weight, and optionally bleach activator, in particular in amounts in the range of 2% by weight % to 10% by weight.
  • bleaches which are suitable are the per compounds generally used in detergents, such as hydrogen peroxide, perborate, which may be in the form of a tetra- or monohydrate, percarbonate, perpyrophosphate and persilicate, which are generally present as alkali metal salts, in particular as sodium salts.
  • Such bleaching agents are in detergents containing a combination used according to the invention, preferably in amounts of up to 25 wt .-%, in particular up to 15 wt .-% and particularly preferably from 5 wt .-% to 15 wt .-%, each based on total agent, present, in particular percarbonate is used.
  • the optionally present component of the bleach activators comprises the conventionally used N- or O-acyl compounds, for example polyacylated alkylenediamines, in particular tetraacetylethylenediamine, acylated glycolurils, in particular tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, urazoles, diketopiperazines, sulphurylamides and cyanurates, and also carboxylic acid anhydrides , in particular phthalic anhydride, carboxylic acid esters, in particular sodium isononanoylphenolsulfonat, and acylated sugar derivatives, in particular pentaacetylglucose, as well as cationic nitrile derivatives such as trimethylammoniumacetonitrile salts.
  • N- or O-acyl compounds for example polyacylated alkylenediamines, in particular tetraacety
  • the bleach activators may have been coated or granulated in a known manner with coating substances in order to avoid the interaction with the per compounds, with the aid of carboxymethylcellulose granulated tetraacetylethylenediamine having average particle sizes of 0.01 mm to 0.8 mm, as for example according to granulated 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine, as can be prepared according to the process described in German Patent DD 255,884 , and / or according to the in particulate form described in International Patent Applications WO 00/50553, WO 00/50556, WO 02/12425, WO 02/12426 or WO 02/26927 described method trialkylammoniumacetonitrile is particularly preferred.
  • such bleach activators are preferred in amounts of up to 8 wt .-%, in particular from 2 wt .-% to 6 wt .-%, each based on the total agent
  • polyester-active soil release polymers which can be used in addition to the combination essential to the invention 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 glycol 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 glycol or polypropylene glycol.
  • Preferred soil release polymers include those compounds which are formally accessible by esterification of two monomeric moieties, wherein the first monomer is a dicarboxylic acid HOOC-Ph-COOH and the second monomer is a diol HO- (CHR 11 -) a OH, also known as polymeric Diol H- (O- (CHR 11 -) a ) b OH may be present.
  • Ph is an o-, m- or p-phenylene radical which can carry 1 to 4 substituents selected from alkyl radicals having 1 to 22 C atoms, sulfonic acid groups, carboxyl groups and mixtures thereof
  • R 11 denotes hydrogen
  • a is a number from 2 to 6
  • b is a number from 1 to 300.
  • 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 is preferably in the range of 4 to 200, especially 12 to 140.
  • the molecular weight or the average molecular weight or the maximum molecular weight distribution of preferred soil release polyester is in the range of 250 to 100,000, especially 500 to 50,000
  • the acid underlying the remainder 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.
  • acids having at least two carboxyl groups are preferably in salt form, in particular as alkali metal or ammonium salt.
  • the sodium and potassium salts are particularly preferable.
  • in place of the monomer HOOC-Ph-COOH small proportions, in particular not more than 10 mol% based on the proportion of Ph having the meaning given above, of other acids having at least two carboxyl groups may be included in the soil release-capable polyester.
  • 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 11 -) 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 C-atoms is selected.
  • those of the formula HO-CH 2 -CHR 11 -OH in which R 11 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-octanediol, 1,2-decanediol, 1, 2-dodecanediol and neopentyl glycol.
  • Particularly preferred among the polymeric diols is polyethylene glycol having an average molecular weight in the range of 1000 to 6000.
  • the polyesters synthesized as described above may also be end-capped, alkyl groups having from 1 to 22 carbon atoms and esters of monocarboxylic acids being suitable as end groups.
  • the ester groups bound by end groups alkyl, alkenyl and Arylmonocarbonklaren with 5 to 32 carbon atoms, in particular 5 to 18 carbon atoms, based.
  • valeric acid caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, undecenoic acid, lauric acid, lauroleinic acid, tridecanoic acid, myristic acid, myristoleic acid, pentadecanoic acid, palmitic acid, stearic acid, petroselinic acid, petroselaidic acid, oleic acid, linoleic acid, linolaidic acid, linolenic acid, levostearic acid, arachidic acid , Gadoleic acid, arachidonic acid, behenic acid, erucic acid, brassidic acid, clupanodonic acid, lignoceric acid, cerotic acid, melissic acid, benzoic acid, which may carry 1 to 5 substituents having a total of up to 25 carbon atoms, in particular 1 to 12 carbon atoms, for example tert-butyl
  • the hydroxymonocarboxylic acids may in turn be linked to one another via their hydroxyl group and their carboxyl group and thus be present several times in an end group.
  • the number of hydroxymonocarboxylic acid units per end group is in the range from 1 to 50, in particular from 1 to 10.
  • the soil release polymers are preferably water-soluble, the term "water-soluble” being understood to mean a solubility of at least 0.01 g, preferably at least 0.1 g, of the polymer per liter of water at room temperature and pH 8.
  • preferred polymers have a solubility of at least 1 g per liter, in particular at least 10 g per liter, under these conditions.
  • Preferred laundry aftertreatment compositions containing a combination to be used according to the invention have, as a laundry softening active ingredient, a so-called esterquat, that is to say a quaternized ester of carboxylic acid and aminoalcohol.
  • esterquat that is to say a quaternized ester of carboxylic acid and aminoalcohol.
  • German Patent DE 43 08 794 moreover discloses a process for preparing solid ester quats, in which the quaternization of triethanolamine esters is carried out in the presence of suitable dispersants, preferably fatty alcohols.
  • suitable dispersants preferably fatty alcohols.
  • Reviews on this topic are, for example, by R. Puchta et al. in Tens.Surf.Det., 30, 186 (1993), M.Brock in Tens.Surf.Det. 30, 394 (1993), R. Lagerman et al. in J. Am. Chem. Soc., 71, 97 (1994) and I. Shapiro in Cosm. Toil. 109, 77 (1994).
  • Ester quats preferred in the compositions are quaternized fatty acid triethanolamine ester salts which follow formula (I), in the R 1 CO for an acyl radical having 6 to 22 carbon atoms, R 2 and R 3 are independently hydrogen or R 1 CO, R 4 is an alkyl radical having 1 to 4 carbon atoms or a (CH 2 CH 2 O) q H Group, m, n and p in total are 0 or numbers from 1 to 12, q is numbers from 1 to 12 and X is a charge-balancing anion such as halide, alkyl sulfate or alkyl phosphate.
  • R 1 CO for an acyl radical having 6 to 22 carbon atoms
  • R 2 and R 3 are independently hydrogen or R 1 CO
  • R 4 is an alkyl radical having 1 to 4 carbon atoms or a (CH 2 CH 2 O) q H Group
  • m, n and p in total are 0 or numbers from 1 to 12
  • q is numbers from 1 to 12
  • esterquats which can be used in the context of the invention are products based on caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, isostearic acid, stearic acid, oleic acid, elaidic acid, arachidic acid, behenic acid and erucic acid and their technical mixtures, such as They occur, for example, in the pressure splitting of natural fats and oils.
  • technical C 12/18 coconut fatty acids and in particular partially hydrogenated C 16/18 tallow or palm oil fatty acids and elaidic acid-rich C 16/18 fatty acid cuts are used.
  • the fatty acids and the triethanolamine can generally be used in a molar ratio of 1.1: 1 to 3: 1.
  • an employment ratio of 1.2: 1 to 2.2: 1, preferably 1.5: 1 to 1.9: 1 has proven to be particularly advantageous.
  • the preferred esterquats used are technical mixtures of mono-, di- and triesters with an average degree of esterification of 1.5 to 1.9 and are derived from technical C 16/18 tallow or palm oil fatty acid (iodine value 0 to 40) , Quaternized fatty acid triethanolamine ester salts of the formula (I) in which R 1 is CO for an acyl radical having 16 to 18 carbon atoms, R 2 is R 1 CO, R 3 is hydrogen, R 4 is a methyl group, m, n and p is 0 and X is methyl sulfate, have proven to be particularly advantageous.
  • quaternized ester salts of carboxylic acids with diethanolalkylamines of the formula (II) are also suitable as esterquats.
  • R 1 CO for an acyl radical having 6 to 22 carbon atoms
  • R 2 is hydrogen or R 1 CO
  • R 4 and R 5 are independently alkyl radicals having 1 to 4 carbon atoms
  • X is a charge-balancing anion such as halide, alkyl sulfate or alkyl phosphate.
  • R 1 CO for an acyl radical having 6 to 22 carbon atoms
  • R 2 is hydrogen or R 1 CO
  • R 4 , R 6 and R 7 are independently alkyl radicals having 1 to 4 carbon atoms
  • X is a charge-balancing anion such as halide, alkyl sulfate or alkyl phosphate.
  • ester quats in the form of 50 to 90 weight percent alcoholic solutions on the market, which can also be easily diluted with water, with ethanol, propanol and Isopropanol are the usual alcoholic solvents.
  • Esterquats are preferably used in amounts of from 5% by weight to 25% by weight, in particular from 8% by weight to 20% by weight, in each case based on the total laundry aftertreatment agent.
  • the laundry aftertreatment agents used in the present invention may additionally contain detergent ingredients listed above, unless they unduly interact negatively with the esterquat. It is preferably a liquid, water-containing agent which is accessible in a simple manner by mixing the ingredients.
  • an agent into which a combination to be used according to the invention is incorporated is particulate and contains up to 25% by weight, in particular from 5% by weight to 20% by weight, of bleaching agent, in particular alkali percarbonate, up to 15% by weight .-%, in particular 1 wt .-% to 10 wt .-% bleach activator, 20 wt .-% to 55 wt .-% inorganic builder, up to 10 wt .-%, in particular 2 wt .-% to 8 wt.
  • bleaching agent in particular alkali percarbonate
  • alkali percarbonate up to 15% by weight .-%, in particular 1 wt .-% to 10 wt .-% bleach activator, 20 wt .-% to 55 wt .-% inorganic builder, up to 10 wt .-%, in particular 2 wt .-% to 8 wt.
  • % water-soluble organic builder 10% to 25% by weight synthetic anionic surfactant, 1% to 5% by weight nonionic surfactant and up to 25% by weight, in particular 0.1% by weight to 25 wt .-% of inorganic salts, in particular alkali carbonate and / or bicarbonate.
  • an agent into which a combination to be used according to the invention is incorporated is liquid and contains 10% by weight to 25% by weight, in particular 12% by weight to 22.5% by weight, of nonionic surfactant , 2 wt .-% to 10 wt .-%, in particular 2.5 wt .-% to 8 wt .-% synthetic anionic surfactant, 3 wt .-% to 15 wt .-%, in particular 4.5 wt .-% to 12.5 wt .-% soap, 0.5 wt .-% to 5 wt .-%, in particular 1 wt .-% to 4 wt .-% organic builder, in particular polycarboxylate such as citrate, up to 1.5 wt .-%, in particular 0.1 wt .-% to 1 wt .-% complexing agent for heavy metals, such as phosphonate, and optionally enzyme, enzyme stabilizer, color and
  • Solid agents are preferably prepared by incorporating a particle containing soil release cellulose derivative and hygroscopic polymer other detergent ingredients present in solid form are mixed.
  • a spray-drying step for the preparation of the particle which contains soil release-capable cellulose derivative and hygroscopic polymer.
  • a compacting compounding step for producing this particle and optionally also for producing the finished product.

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Claims (15)

  1. Utilisation d'une combinaison d'un dérivé de cellulose à pouvoir de dissolution des salissures, que l'on peut obtenir par alkylation et hydroxyalkylation de cellulose, et d'un polymère hygroscopique choisi parmi les polypeptides, les hydrogels, l'alcool polyvinylique, les polyalkylèneglycols, les homopolymères de l'acide acrylique, de l'acide méthacrylique et de l'acide maléique ainsi que leurs copolymères, et de leurs mélanges, pour renforcer la puissance de nettoyage des produits détergents dans le lavage des textiles.
  2. Utilisation d'une combinaison de dérivé de cellulose à pouvoir de dissolution des salissures, que l'on peut obtenir par alkylation et hydroxyalkylation de cellulose, et d'un polymère hygroscopique, pour renforcer la puissance de nettoyage de détergents dans le lavage des textiles qui ont déjà été lavés et/ou post-traités en présence du dérivé de cellulose et le cas échéant du polymère hygroscopique, avant d'être salis.
  3. Utilisation selon la revendication 1 ou 2, caractérisée en ce que les textiles se composent de coton ou contiennent du coton.
  4. Utilisation d'une combinaison de dérivé de cellulose à pouvoir de dissolution des salissures, que l'on peut obtenir par alkylation et hydroxyalkylation de cellulose, et d'un polymère hygroscopique ainsi que d'un polymère à action de polyester et à pouvoir de dissolution des salissures, constitué d'un acide dicarboxylique et d'un diol éventuellement polymère, pour le renforcement de la puissance de nettoyage des produits de lavage dans le lavage des textiles.
  5. Utilisation selon l'une des revendications 1 à 4, caractérisée en ce que le dérivé de cellulose est alkylé avec des groupes en C1 à C10, en particulier des groupes en C1 à C3 et porte en outre des groupes hydroxyalkyle en C2 à C10, en particulier des groupes hydroxyalkyle en C2 à C3.
  6. Utilisation selon l'une des revendications 1 à 5, caractérisée en ce que sont contenus en moyenne, dans le dérivé de cellulose, de 0,5 à 2,5, en particulier de 1 à 2 groupes alkyle, et de 0,02 à 0,5, en particulier de 0,05 à 0,3 groupes hydroxyalkyle par unité monomère anhydroglycose.
  7. Utilisation selon l'une des revendications 1 à 6, carcatérisée en ce que la masse molaire moyenne du dérivé de cellulose se situe dans un intervalle de 10 000 D à 150 000 D.
  8. Utilisation selon la revendication 7, caractérisée en ce que la masse molaire moyenne du dérivé de cellulose se situe dans un intervalle de 40 000 D à 120 000 D, en particulier de 80 000 D à 110 000 D.
  9. Utilisation selon l'une des revendications 1 à 8, caractérisée en ce que le polymère hygroscopique est choisi parmi les acides polyacryliques.
  10. Utilisation selon l'une des revendications 1 à 9, caractérisée en ce que le polymère hygroscopique est choisi parmi l'alcool polyvinylique, les polyalkylèneglycols et/ou les homopolymères de l'acide acrylique, de l'acide méthacrylique et de l'acide maléique ainsi que leurs copolymères et présente une masse molaire moyenne allant de 500 000 D à 700 000 D, en particulier de 550 000 D à 650 000 D.
  11. Produit de lavage contenant un dérivé de cellulose à pouvoir de dissolution des salissures, que l'on peut obtenir par alkylation et hydroxyalkylation de cellulose, et un polymère hygroscopique choisi parmi les polypeptides, les hydrogels, l'alcool polyvinylique, les polyalkylèneglycols, les homopolymères de l'acide acrylique, de l'acide méthacrylique et de l'acide maléique ainsi que leurs copolymères, et leurs mélanges.
  12. Produit selon la revendication 11, caractérisé en ce qu'il contient de 0,1 % en poids à 5 % en poids, en particulier de 0,5 % en poids à 2,5 % en poids du dérivé de cellulose à pouvoir de dissolution des salissures et/ou de 0,1 % en poids à 5 % en poids, en particulier de 0,5 % en poids à 2,5 % en poids de polymère hygroscopique.
  13. Procédé de fabrication de produits solides selon la revendication 11 ou 12, caractérisé en ce qu'on mélange une particule qui contient un dérivé de cellulose à pouvoir de dissolution des salissures et un polymère hygroscopique, avec d'autres constituants de produits de lavage présents sous forme solide.
  14. Procédé selon la revendication 13, caractérisé en ce que, pour la fabrication de la particule qui contient le dérivé de cellulose à pouvoir de dissolution des salissures et le polymère hygroscopique, on utilise une étape de séchage par pulvérisation.
  15. Procédé selon la revendication 13, caractérisé en ce que, pour la fabrication de la particule qui contient le dérivé de cellulose à pouvoir de dissolution des salissures et le polymère hygroscopique, on utilise une étape de combinaison avec compactage.
EP04707142A 2003-02-10 2004-01-31 Augmentation de la puissance de nettoyage de produits de lavage a l'aide d'un derive cellulosique et d'un polymere hygroscopique Revoked EP1592765B1 (fr)

Applications Claiming Priority (5)

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DE10305306 2003-02-10
DE10305306 2003-02-10
DE10351324A DE10351324A1 (de) 2003-02-10 2003-10-31 Verstärkung der Reinigungsleistung von Waschmitteln durch Cellulosederivat und hygroskopisches Polymer
DE10351324 2003-10-31
PCT/EP2004/000870 WO2004069973A1 (fr) 2003-02-10 2004-01-31 Augmentation de la puissance de nettoyage de produits de lavage a l'aide d'un derive cellulosique et d'un polymere hygroscopique

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EP1592765B1 true EP1592765B1 (fr) 2007-05-30

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DE (1) DE502004003950D1 (fr)
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WO2004069975A1 (fr) * 2003-02-10 2004-08-19 Henkel Kommanditgesellschaft Auf Aktien Augmentation de la capacite d'absorption d'eau de textiles
WO2004069976A2 (fr) * 2003-02-10 2004-08-19 Henkel Kommanditgesellschaft Auf Aktien Utilisation de derives cellulosiques en tant que regulateurs de moussage
DE10351325A1 (de) * 2003-02-10 2004-08-26 Henkel Kgaa Wasch- oder Reinigungsmittel mit wasserlöslichem Buildersystem und schmutzablösevermögendem Cellulosederivat
JP4519122B2 (ja) * 2003-02-10 2010-08-04 ヘンケル・アクチェンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト・アウフ・アクチェン 水溶性ビルダー系および汚れ解離性セルロース誘導体を含んでなる漂白剤含有洗濯または洗浄剤
DE10351321A1 (de) * 2003-02-10 2004-08-26 Henkel Kgaa Verstärkung der Reinigungsleistung von Waschmitteln durch eine Kombination von Cellulosderivaten
DE102005026544A1 (de) * 2005-06-08 2006-12-14 Henkel Kgaa Verstärkung der Reinigungsleistung von Waschmitteln durch Polymer
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ATE363525T1 (de) 2007-06-15
WO2004069973A1 (fr) 2004-08-19
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