EP1888732B1 - Renforcement du pouvoir detersif de detergents par l'intermediaire d'un polymere - Google Patents

Renforcement du pouvoir detersif de detergents par l'intermediaire d'un polymere Download PDF

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Publication number
EP1888732B1
EP1888732B1 EP06742985A EP06742985A EP1888732B1 EP 1888732 B1 EP1888732 B1 EP 1888732B1 EP 06742985 A EP06742985 A EP 06742985A EP 06742985 A EP06742985 A EP 06742985A EP 1888732 B1 EP1888732 B1 EP 1888732B1
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Prior art keywords
acid
polymer
weight
soil
release
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EP1888732A1 (fr
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Josef Penninger
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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    • 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
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions

Definitions

  • the present patent application relates to enhancing the detergency of laundry detergents in the washing of textiles through the use of a particular soil release 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”.
  • the US patent US 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 is substantially consists of C 10 - to C 13 -alkyl sulfate and up to 5 wt .-% C 14 alkyl sulfate and less than 5 wt .-% alkyl sulfate having alkyl radicals of C 15 and higher.
  • the US patent US 4,174,305 discloses detergents containing from 0.1% to 3% by weight of alkyl cellulose, hydroxyalkyl cellulose or Alkyl-hydroxyalkyl cellulose and 5 wt .-% to 50 wt .-% surfactant, wherein the surfactant component consists essentially of C 10 - to C 12 -alkylbenzenesulfonate and less than 5 wt .-% alkylbenzenesulfonate with alkyl radicals of C 13 and has higher.
  • the 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.
  • the European patent 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 methylcellulose and ethylcellulose, with weight ratio of peroxygen bleach (based on the active oxygen content of the bleaching agent) of 10: 1 to 1:10 should be used.
  • a detergent in liquid or granular form which imparts textile appearance benefits such as pilling / lint reduction, anti-color fading, improved abrasion resistance and / or enhanced softness to fabrics and textiles washed therewith, and from 1 to 80% by weight 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 must be present in amounts of 0.1-5 wt .-%, based on the cellulose ether material.
  • German Offenlegungsschrift describes DT 16 17 141 a washing process using polyethylene terephthalate-polyoxyethylene glycol copolymers.
  • the German disclosure DT 22 00 911 relates to detergents containing 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 5,000 and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate is 50:50 to 90:10, and their use in detergents are disclosed in the German Patent DE 28 57 292 described.
  • the 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.
  • the 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 3000 and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate is 0.6 to 0.95.
  • From the European patent application EP 272 033 are at least partially by C 1-4 alkyl or acyl radicals end-capped polyester with poly-propylene terephthalate and polyoxyethylene terephthalate units known.
  • the European patent EP 274 907 describes sulfoethyl end-capped terephthalate-containing soil release polyesters.
  • EP 357,280 are prepared by sulfonation of unsaturated end groups soil release polyester 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 repulping of dirt during the washing of synthetic fibers.
  • From the German patent DE 28 46 984 Detergents are known which contain, as soil release-capable polymer, a reaction product of a polyester having a terminal isocyanate group-containing prepolymer obtained from a diisocyanate and a hydrophilic nonionic macrodiol.
  • the US-A-2001/0036912 discloses soil release high net-worth polymers for cotton and cotton blended fabrics.
  • the invention therefore relates to the use of a polymer obtainable from the monomers styrene, methacrylic acid, hydroxyethyl methacrylate and methyl methacrylate, for enhancing the cleaning performance of detergents in the washing of textiles.
  • Particularly preferred polymers are block polymers, ie those in which first a monomer, in particular styrene, is grafted on, and then with the others Carbonchingre phenomenon- or carboxylate-containing monomers, together or in succession, is reacted polymerizing.
  • Polymers which are particularly suitable according to the invention have a molecular weight of not more than 10,000 D, in particular from 3,000 D to 8,000 D. The determination of the molecular weight can be carried out using conventional chromatographic methods using known standards.
  • the use according to the invention can be carried out as part of a washing process in such a way that the polymer is added separately to a detergent-containing liquor, or the polymer is introduced into the liquor as a constituent of the detergent.
  • Another object of the invention is therefore a detergent containing a polymer described above.
  • the use according to the invention in the context of a laundry aftertreatment process can be carried out in such a way that the polymer is added separately to the rinse liquor or is it incorporated as a constituent of the laundry aftertreatment agent, in particular a fabric softener.
  • said detergent may also contain, but may be free of, the polymer to be used according to the invention.
  • Another object of the invention is a method for washing textiles, in which a detergent and the aforementioned soil release polymer are used.
  • This method can be carried out manually or preferably by means of a conventional household washing machine. It is possible to use the detergent and the polymer essential to the invention simultaneously or successively. The simultaneous application can be particularly advantageous by the use of a detergent containing the polymer perform.
  • Detergents containing the polymer to be used according to the invention may contain all the usual ingredients of such agents which do not undesirably interact with it.
  • the soil release polymer is preferably incorporated in detergents in amounts of from 0.1% by weight to 2% by weight, in particular from 0.4% by weight to 1% 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 polymer used according to the invention has a positive effect on the action of certain other detergent ingredients and, conversely, that the effect of the polymer 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, with water-insoluble inorganic builders, with water-soluble inorganic and organic builders, especially based on oxidized carbohydrates, with peroxygen bleaching agents, especially with alkali percarbonate, with synthetic anionic surfactants of the sulfate and sulfonate type and at Grayness inhibitors, for example other, in particular anionic cellulose ethers such as carboxymethyl cellulose, which is why the use of at least one of said further ingredient together with the polymer to be used according to the invention is preferred.
  • such an agent contains 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.
  • alkoxylates in particular the ethoxylates, primary alcohols with linear, in particular 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 described in the international patent application WO 90/13533 as well as fatty acid polyhydroxyamides, as prepared according to the methods of US Pat US 1,985,424 .
  • 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.
  • 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 Oligomertechnischsgrad.
  • the degree of oligomerization n assumes as the value to be determined analytically generally broken numerical values; he is lying at values 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.
  • 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 polymer 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
  • alkali metal, ammonium or alkyl or hydroxyalkyl-substituted ammonium bases Such alkyl and / or alkenyl sulfates are preferably present in the compositions in amounts of from 0.1% by weight to 15% by weight, in particular from 0.5% by weight to 10% by weight.
  • 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 carbon atoms, preferably 1 to 4 carbon atoms, derivative sulfonation, 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 as a rule up to 20% by weight, can also be present.
  • an agent which comprises a polymer 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 containing a polymer 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 also the polymeric (poly) carboxylic acids, in particular the polycarboxylates of the international patent application obtainable by oxidation of polysaccharides WO 93/16110 , polymeric acrylic acids, methacrylic acids, Maleic acids and copolymers 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, although 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 40 wt .-% to 60 wt .-%, in particular 45 to 55 wt .-% of (meth) acrylic acid or (meth) acrylate, particularly preferably acrylic acid or acrylate, 10 wt .-% to 30 wt .-%, 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 may be, for example, a mono-, di-, oligo- or polysaccharide, mono-, di- or oligosaccharides being preferred, sucrose being particularly preferred.
  • the use of the third monomer presumably 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 described in the German patent DE 42 21 381 and the German patent application DE 43 00 772 are generally described, and generally have a molecular weight between 1000 and 200,000, preferably between 200 and 50,000 and in particular between 3000 and 10,000.
  • 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 used 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 .mu.m and preferably consist of at least 80% by weight of particles having a size of less than 10 .mu.m.
  • Their calcium binding capacity according to the information of the German Patent DE 24 12 837 can be determined lies in the range of 100 to 200 mg CaO per gram.
  • 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 metal silicates useful as builders in the compositions preferably have a molar ratio of alkali metal oxide to SiO 2 below 0.95, in particular from 1: 1.1 to 1:12, and may be present in amorphous or crystalline form.
  • 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 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 getting produced.
  • 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 the European patent application EP 0 164 514 described.
  • Preferred crystalline phyllosilicates are those in which x in the abovementioned general formula assumes the values 2 or 3.
  • both ⁇ - and ⁇ -sodium disilicates are preferred, whereby ⁇ -sodium disilicate can be obtained, for example, by the process described in International Patent Application WO 91/08171 is described.
  • ⁇ -Sodium silicates with a modulus between 1.9 and 3.2 can according to Japanese Patent Applications JP 04/238 809 or JP 04/260 610 getting produced.
  • Also prepared from amorphous alkali metal silicates practically anhydrous crystalline alkali metal silicates of the above general formula in which x is a number from 1.9 to 2.1, preparable as in the European patent applications EP 0 548 599 .
  • EP 0 502 325 and EP 0 425 428 can be used in agents which contain a combination used according to the invention.
  • a crystalline sodium layer silicate with a modulus of 2 to 3 is used, as it is by the process of European patent application EP 0 436 835 made from sand and soda.
  • 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. If alkali metal aluminosilicate, in particular zeolite, is present as an additional builder substance, the content of alkali silicate 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, in each case based on anhydrous active substances, is then preferably 4: 1 to 10: 1. In agents containing both amorphous and crystalline alkali metal silicates, the weight ratio of amorphous alkali metal silicate to crystalline alkali metal silicate is preferably 1: 2 to 2: 1 and especially 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 polymer 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
  • 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 polymer used according to the invention or the constituents of the combination used according to the invention are generally dissolved or in suspended form.
  • inventions 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 the German Offenlegungsschriften DE 19 40 488 . DE 20 44 161 . DE 21 01 803 and DE 21 21 397 , the US patents US Pat. No.
  • EP 218 272 or EP 204 284 or the international patent application WO 90/10695 described from Fusarium species, such as in the European patent application EP 130 064 described from Rhizopus species, such as in the European patent application EP 117 553 described or from Aspergillus species, such as in the European patent application EP 167,309 be described.
  • 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 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.
  • Cellulases of this type are known, for example, from German Offenlegungsschriften DE 31 17 250 . DE 32 07 825 . DE 32 07 847 . DE 33 22 950 or the European patent applications EP 265 832 . EP 269 977 . EP 270 974 .
  • EP 273 125 such as EP 339,550 and international patent applications WO 95/02675 and WO 97/14804 known and commercially available under the names Celluzyme®, Carezyme® and Ecostone®.
  • usual enzyme stabilizers include amino alcohols, such as 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 Boric acid or alkali borates, boric acid-carboxylic acid combinations, such as from the European patent application EP 451 921 known, boric acid esters, such as from the international patent application WO 93/11215 or the European patent application EP 511 456 known boronic acid derivatives, such as from the European patent application EP 583 536 known, calcium salts, for example from the European patent EP 28,865 known Ca-formic acid combination, magnesium salts, such as from the European patent application EP 378 262 known, and / or sulfur-containing reducing agents, such as from the European patent applications EP 080 748 or EP 080 223 known.
  • amino alcohols such as mono-, di-, triethanol- and -propanolamine and mixtures thereof
  • lower carboxylic acids
  • 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 attached to granular, water-soluble carrier substances bound, as for example in the German Offenlegungsschrift DE 34 36 194 , the European patent applications EP 262 588 . EP 301 414 . EP 309 931 or the European patent specification EP 150 386 described.
  • a further embodiment of such an agent which contains a polymer to be used according to the invention contains peroxygen-based bleaching agents, in particular in amounts ranging from 5% by weight to 70% by weight, and optionally bleach activator, in particular in amounts of 2% by weight % to 10% by weight.
  • peroxygen-based bleaching agents in particular in amounts ranging from 5% by weight to 70% by weight
  • optionally bleach activator in particular in amounts of 2% by weight % to 10% by weight.
  • These 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 polymer used in 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 commonly 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 tetraacetyl
  • 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 in the European patent specification EP 37 026 granulated 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine, as described in the German Patent DD 255 884 can be prepared, and / or according to those in the international patent applications WO 00/50553 . WO 00/50556 . WO 02/12425 .
  • WO 02/12426 or WO 02/26927 described method particulate formally prepared trialkylammonium acetonitrile 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, based in each case on the total agent.
  • polyester-active soil release polymer of dicarboxylic acid and diol which may also be a polymeric diol or a mixture of monomeric and polymeric diol, to enhance the cleaning performance of detergents in the washing of textiles.
  • polyester-active soil release polymers which can be used in addition to the polymer 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 radical Ph is preferably selected from terephthalic acid, isophthalic acid, phthalic acid, trimellitic acid, mellitic acid, the isomers of sulfophthalic acid, sulfoisophthalic acid and Sulfoterephtalsäwe 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 alkali or ammonium salt. Among these, the sodium and potassium salts are particularly preferable.
  • acids having at least two carboxyl groups may be included in the soil release-capable 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 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.
  • R 11 is hydrogen and a is a number from 2 to 6
  • 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.
  • valerian 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, elaeostearic acid, arachic acid , Gadoleic acid, arachidonic acid, behenic acid, erucic acid, brassidic acid, clupanodonic acid, lignoceric acid, cerotic acid, melissic acid, benzoic acid, which carry 1 to 5 substituents with a total of up to 25 C atoms, in particular 1 to 12 C atoms may, for example, ter
  • the end groups may 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 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 polymer to be used according to the invention have, as a laundry softening agent, 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.
  • 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. It is preferred to use technical C 12/18 coconut fatty acids and, in particular, partially hydrogenated C 16/18 tallow or palm oil fatty acids and also elaidic acid-rich C 16/18 fatty acid cuts.
  • 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 Fettchuretriethanolaminestersalze of formula (I), in which R 1 CO for an acyl radical with 16 bis 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 proved 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 arrive in Form 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 polymer 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 bleach, 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.
  • % 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 polymer 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 mixing a particle containing the soil release polymer with other detergent ingredients present in solid form.
  • a spray-drying step to prepare the particle which contains soil release-capable polymer.
  • a compacting compounding step for producing this particle and optionally also for producing the finished product.
  • Block Polymer P1 (MM: ⁇ 10 000) Styrene, methacrylic acid, hydroxyethyl methacrylate and methyl methacrylate were radically polymerized.
  • the soiled tissues were measured with a Minolta CR 200 and then aged for 7 days at RT. Thereafter, the soiled cloths were stapled on towels and washed under the conditions given above.
  • the fabrics were dried and measured again with a Minolta CR 200.

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)
  • Cleaning Implements For Floors, Carpets, Furniture, Walls, And The Like (AREA)
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Claims (12)

  1. Utilisation d'un polymère à pouvoir détachant, que l'on obtient par polymérisation des monomères de styrène, d'acide méthacrylique, de méthacrylate d'hydroxyéthyle et de méthacrylate de méthyle, pour le renforcement du pouvoir nettoyant d'agents de lavage lors du lavage de textiles.
  2. Utilisation d'un polymère à pouvoir détachant, que l'on obtient par polymérisation des monomères de styrène, d'acide méthacrylique, de méthacrylate d'hydroxyéthyle et de méthacrylate de méthyle, pour le renforcement du pouvoir nettoyant d'agents de lavage lors du lavage de textiles qui avaient déjà fait l'objet d'un lavage et/ou d'un traitement ultérieur en présence du polymère, avant de les exposer à une salissure.
  3. Utilisation selon la revendication 1 ou 2, caractérisée en ce que les textiles sont constitués de coton ou contiennent du coton.
  4. Utilisation selon l'une quelconque des revendications 1 à 3, caractérisée en ce qu'on obtient le polymère à partir des fractions de styrène à concurrence de 1 à 30 mol %, de méthacrylate de méthyle à concurrence de 10 à 40 mol %, d'acide méthacrylique à concurrence de 20 à 60 mol % et de méthacrylate d'hydroxyéthyle à concurrence de 1 à 20 mol %.
  5. Utilisation selon l'une quelconque des revendications 1 à 4, caractérisée en ce que le polymère est un polymère séquencé.
  6. Utilisation d'une combinaison d'un polymère à pouvoir détachant que l'on obtient par polymérisation des monomères de styrène, d'acide méthacrylique, de méthacrylate d'hydroxyéthyle et de méthacrylate de méthyle, et d'un polymère constitué d'un acide dicarboxylique et de diol, à pouvoir détachant possédant une activité de polyester, qui peut également représenter un diol polymère ou un mélange d'un diol monomère et d'un diol polymère, pour le renforcement du pouvoir nettoyant d'agents de lavage lors du lavage de textiles.
  7. Utilisation selon l'une quelconque des revendications 1 à 6, caractérisée en ce que la masse molaire moyenne du polymère, que l'on obtient par polymérisation des monomères de styrène, d'acide méthacrylique, de méthacrylate d'hydroxyéthyle et de méthacrylate de méthyle, est inférieure à 10.000 D, en particulier s'élève de 3000 D à 8000 D.
  8. Agents de lavage contenant un polymère à pouvoir détachant que l'on obtient par polymérisation des monomères de styrène, d'acide méthacrylique, de méthacrylate d'hydroxyéthyle et de méthacrylate de méthyle.
  9. Agent selon la revendication 8, caractérisé en ce qu'il contient le polymère à pouvoir détachant à concurrence de 0,1 % en poids à 2 % en poids, en particulier de 0,4 % en poids à 1 % en poids.
  10. Procédé pour la fabrication d'agents solides selon la revendication 8 ou 9, caractérisé en ce que l'on mélange une particule qui contient un polymère à pouvoir détachant avec d'autres constituants d'agents de lavage présents sous forme solide.
  11. Procédé selon la revendication 10, caractérisé en ce qu'on met en oeuvre, pour la fabrication de la particule qui contient un polymère à pouvoir détachant, une étape de séchage par pulvérisation.
  12. Procédé selon la revendication 10, caractérisé en ce qu'on met en oeuvre, pour la fabrication de la particule qui contient un polymère à pouvoir détachant, une étape de compoundage de compactant.
EP06742985A 2005-06-08 2006-05-19 Renforcement du pouvoir detersif de detergents par l'intermediaire d'un polymere Not-in-force EP1888732B1 (fr)

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PL1888732T3 (pl) 2010-08-31
JP5113043B2 (ja) 2013-01-09
US8034123B2 (en) 2011-10-11
ES2341672T3 (es) 2010-06-24
JP2008545857A (ja) 2008-12-18
EP1888732A1 (fr) 2008-02-20
US20080301883A1 (en) 2008-12-11
DE502006006513D1 (de) 2010-05-06
WO2006131197A1 (fr) 2006-12-14
DE102005026544A1 (de) 2006-12-14

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