EP2922634A1

EP2922634A1 - Polymeric active ingredients which contain sulfonate groups and improve primary washing power

Info

Publication number: EP2922634A1
Application number: EP13791824.9A
Authority: EP
Inventors: Benoit Luneau; Inga Kerstin Vockenroth; Quang Ngoc TRAN; Trang Phan; Didier Gigmes; Denis Bertin
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 2012-11-22
Filing date: 2013-11-18
Publication date: 2015-09-30
Also published as: US9422510B2; FR2998305A1; FR2998305B1; WO2014079786A1; US20150252307A1

Abstract

The primary washing power of washing and cleaning compositions was to be improved, especially toward oily and/or greasy stains. This was achieved essentially through the incorporation of polymers containing styrenesulfonic acid.

Description

The primary washing power improving sulfonate group-containing polymeric agents

The present invention relates to the use of certain sulfonate group-containing polymers to enhance the Primärwaschkraft of detergents or cleaners in the washing of textiles or cleaning hard surfaces against particular pale or enzyme-sensitive stains, and detergents and cleaners containing such polymers.

In addition to the ingredients indispensable for the washing process, such as surfactants and builder materials, laundry detergents generally comprise further constituents which can be summarized under the term laundry detergents and which comprise such different active ingredient groups as foam regulators, grayness inhibitors, bleaches, bleach activators and color transfer inhibitors. Such excipients also include substances whose presence enhances the detergency of surfactants, without them usually having to exhibit a pronounced surfactant behavior itself. The same applies mutatis mutandis to cleaners for hard surfaces. Such substances are often referred to as Waschkraftverstärker.

International patent application WO 2010/024468 A1 discloses sulfonate-containing polymers which contain, for example, up to 30% by weight of components derived from the monomer 3-allyloxy-2-hydroxypropanesulfonate, which are suitable for use as builders in detergents, as described there are.

Surprisingly, it has been found that certain polymers containing sulfonate groups have particularly good primary washing strength-enhancing properties.

The invention relates to the use of polymers obtainable by copolymerization of styrene sulfonic acid and / or their ammonium or alkali metal salts with two or more times, in particular 2 times, ethylenically unsaturated monomers to enhance the primary washing power of detergents or cleaners when washing textiles or when cleaning hard surfaces against in particular bleach- or enzyme-sensitive soiling.

The first monomer is preferably selected from p-styrenesulfonic acid and its alkali metal salts, in particular their sodium salt, although the o- and m-isomers are also suitable. The fraction derived from the styrenesulfonic acid monomer in the polymer is preferably at least 60 mol%, in particular from 75 mol% to 99 mol%, based on the polymer. The second monomer which is ethylenically unsaturated by two or more times is preferably a linear or branched-chain hydrocarbon having in particular 4 to 12 carbon atoms. It is preferably selected from the group comprising buta-1, 3-diene, isoprene, penta-1,3-diene, hexa-1,3-diene, hexa-1,4-diene, hexa-1,5-diene, Hexa-2,4-diene, hepta-1, 6-diene, octa-1, 7-diene, their isomers, and mixtures thereof. The proportion in the polymer derived from the monomer which has two or more ethylenically unsaturated monomers is preferably not more than 40 mol%, in particular from 1 mol% to 25 mol%, based on the polymer.

The polymeric active ingredient preferably has an average molecular weight (here and below in the case of average molecular weight data: number average) in the range from 500 g / mol to 100 000 g / mol, in particular from 1000 g / mol to 40 000 g / mol.

Another object of the invention is a method for removing bleach or enzyme-sensitive soiling of textiles or hard surfaces, in which a detergent or cleaning agent and a named polymeric agent are used. This method can be carried out manually or mechanically, for example by means of a household washing machine or dishwasher. It is possible to apply the particular liquid agent and the active ingredient simultaneously or sequentially. The simultaneous application can be carried out particularly advantageously by the use of an agent which contains the active ingredient. Bleach- or enzyme-sensitive soiling is understood to mean those which are usually at least partially removable from bleaches or with the aid of enzymes.

The active compounds used in the invention can be prepared in a simple way by free-radical polymerization of the ethylenically unsaturated monomers. The polymerization can be carried out as a statistical or as a block polymerization.

The use of the active ingredients according to the invention leads to a significantly better detachment of particular pale or enzyme-sensitive stains on hard surfaces and textiles, including those made of cotton or with a share of cotton, as is the case when using compounds known for this purpose , Alternatively, significant levels of surfactants can be saved while maintaining soil release capability.

The use according to the invention can be carried out in the context of a washing or cleaning process by adding the active ingredient to a washing or cleaning agent-containing liquor or preferably introducing the active ingredient as a constituent of a washing or cleaning agent into the liquor, wherein the concentration of active ingredient in the liquor is preferably in the range of 0.01 g / l to 0.5 g / l, in particular from 0.02 g / l to 0.2 g / l. Another object of the invention is therefore a washing or cleaning agent containing a copolymer obtainable by copolymerization of styrene sulfonic acid and / or their ammonium or alkali metal salts with two or more times, in particular 2 times, ethylenically unsaturated monomer polymer.

The preferred embodiments of the polymer for use in the invention also apply to the aspects of the invention of the process and of the detergent or cleaner. Conversely, the preferred embodiments embodied in the center aspect of the invention with regard to the middle constituents also apply to the aspects of the invention of the method and the use.

Detergents or cleaning agents which contain or are used together with an active substance to be used according to the invention or are used in the process according to the invention may contain all customary other constituents of such agents which do not interact in an undesired manner with the active ingredient essential to the invention. Preferably, an active ingredient as defined above in amounts of from 0.1 wt .-% to 10 wt .-%, in particular 0.5 wt .-% to 5 wt .-% incorporated in detergents or cleaning agents.

Surprisingly, it has been found that such active ingredients positively influence the action of certain other detergent ingredients and, conversely, that the action of the active ingredient is additionally enhanced by certain other ingredients. These effects occur in particular in bleaching agents, in enzymatic active substances, in particular proteases and lipases, in water-soluble inorganic and / or organic builders, in particular based on oxidized carbohydrates or polymeric polycarboxylates and in synthetic anionic surfactants of the sulfate and sulfonate type, for which reason the use at least one of the said further ingredients is preferred together with the active ingredient to be used according to the invention.

An agent containing or used together with an active ingredient to be used or used in the method of the invention may preferably contain peroxygen bleaching agents, especially in amounts ranging from 5% to 70% by weight, and optionally Bleach activator, especially in amounts ranging from 2 wt .-% to 10 wt .-%, included. The bleaches in question are preferably the peroxygen compounds generally used in detergents, such as percarboxylic acids, for example dodecanedioic acid or phthaloylaminoperoxicaproic acid, hydrogen peroxide, alkali metal perborate, which may be present as tetra- or monohydrate, percarbonate, perpyrophosphate and persilicate, which are generally used as alkali metal salts, in particular as sodium salts. Such bleaching agents are in detergents containing an active ingredient 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 means, present, being especially 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, also carboxylic acid anhydrides, in particular phthalic anhydride, carboxylic acid esters, in particular sodium isononanoyl-phenolsulfonate, and acylated sugar derivatives, in particular pentaacetylglucose, and also cationic nitrile derivatives such as trimethylammonium acetonitrile salts. The bleach activators may have been coated and / or granulated in a known manner with coating substances in order to avoid the interaction with the per compounds, granulated tetraacetylethylenediamine having mean particle sizes of from 0.01 mm to 0.8 mm, granulated 1, with the aid of carboxymethylcellulose. 5-diacetyl-2,4-dioxohexahydro-1, 3,5-triazine, and / or formulated in particulate trialkylammoniumacetonitrile 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.

In a preferred embodiment, an agent according to the invention or used in the context of the invention comprises synthetic anionic surfactant of the sulfate and / or sulfonate type, in particular alkylbenzenesulfonate, fatty alkylsulfate, fatty alkyl ether sulfate, alkyl and / or dialkyl sulfosuccinate, sulfo fatty acid esters and / or sulfo fatty acid salts, in particular in an amount Range from 2% to 25% by weight. The anionic surfactant is preferably selected from the alkylbenzenesulfonates, 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. These are usually not individual substances, but cuts or mixtures. Of these, preference is given to those whose proportion of compounds having longer-chain radicals in the range from 16 to 18 C atoms is more than 20% by weight.

A further embodiment of such agents comprises the presence of nonionic surfactants selected from fatty alkyl polyglycosides, fatty alkyl polyalkoxylates, in particular ethoxylates and / or propoxylates, fatty acid polyhydroxyamides and / or ethoxylation and / or propoxylation products of fatty alkylamines, vicinal diols, fatty acid alkyl esters and / or fatty acid amides and mixtures thereof, in particular in an amount in the range from 2% by weight to 25% by weight.

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 be prepared with the corresponding alkylene oxides. Particularly suitable are the derivatives of the fatty alcohols, although also their branched-chain isomers, in particular so-called oxo alcohols, can be used for the preparation of usable alkoxylates. Useful are accordingly the alkoxylates, in particular the ethoxylates, primary alcohols with linear, in particular dodecyl, tetradecyl, hexadecyl or octadecyl radicals and mixtures thereof. In addition, suitable alkoxylation products of alkylamines, vicinal diols and carboxylic acid amides, which correspond to the said alcohols with respect to the alkyl part, usable. In addition, the ethylene oxide and / or propylene oxide insertion products of fatty acid alkyl esters and fatty acid polyhydroxy amides come into consideration. So-called alkylpolyglycosides which are suitable for incorporation into the compositions according to the invention are compounds of the general formula (G) _n -OR ² , in which R ^{2 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. 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, bose, arabinose, 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 Oligomerisierungsgrad. 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 ^{2 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 be used to prepare useful glycosides. Accordingly, the primary alcohols having linear octyl, decyl, dodecyl, tetradecyl, hexadecyl or octadecyl radicals and mixtures thereof are particularly suitable. Particularly preferred alkyl glycosides contain a coconut fatty alkyl radical, ie mixtures with essentially R ² = dodecyl and R ² = tetradecyl.

Nonionic surfactant is present in compositions which contain an active ingredient used according to the invention or are used in the context of the use according to the invention, preferably in amounts of from 1% by weight to 30% by weight, in particular from 1% by weight to 25% by weight. With amounts in the upper part of this range being more likely to be found in liquid detergents and particulate detergents preferably containing lower amounts of up to 5% by weight.

The agents may instead or additionally contain further surfactants, preferably synthetic anionic surfactants of the sulfate or sulfonate type, to which, for example, the abovementioned alkylbenzenesulfonates, in amounts of preferably not more than 20% by weight, in particular 0.1% by weight, are used .-% to 18 wt .-%, each based on the total agent included. As for use in such agents particularly suitable synthetic anionic surfactants are the alkyl and / or alkenyl sulfates with 8 to 22 carbon atoms, which carry an alkali, ammonium or alkyl or hydroxyalkyl-substituted ammonium ion as a counter cation. Preference is given to the derivatives of the fatty alcohols having in particular 12 to 18 carbon atoms and their branched-chain analogs, the so-called oxo alcohols. The 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. Sulfur-type surfactants which can be used also include the sulfated alkoxylation products of the alcohols mentioned, known as ether sulfates. Such 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 α-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. Preferred anionic surfactants are also the salts of sulfosuccinic acid esters, which are also referred to as alkylsulfosuccinates or dialkylsulfosuccinates, and which are monoesters or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contain C ₈ - to cis-fatty alcohol residues or mixtures of these. Particularly preferred sulfosuccinates contain an ethoxylated fatty alcohol radical, which in itself is a nonionic surfactant. Sulfosuccinates, whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are again particularly preferred.

Other optional surface-active ingredients are 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. Soap mixtures are preferred which are composed of 50 wt% to 100 wt .-% of saturated C ₂ -C ₈ fatty acid soaps and 50 wt .-% to oleic acid soap. Preferably, soap is included in amounts of 0.1 to 5% by weight. In particular, in liquid agents containing an active ingredient according to the invention, however, higher amounts of soap can be contained, usually up to 20 wt .-%.

If desired, the compositions may also contain betaines and / or cationic surfactants, which, if present, are preferably used in amounts of from 0.5% by weight to 7% by weight.

In a further embodiment, the agent contains water-soluble and / or water-insoluble builder, 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 ranging from 2.5 wt .-% to 60 wt .-%.

The agent preferably contains from 20% 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 obtainable by oxidation of polysaccharides, polymeric acrylic acids, methacrylic acids, maleic acids and mixed polymers thereof, which may also contain copolymerized small amounts of polymerizable substances without carboxylic acid functionality. The relative molecular mass of the homopolymers of unsaturated carboxylic acids is generally between 5000 g / mol and 200,000 g / mol, of the copolymers between 2000 g / mol and 200,000 g / mol, preferably 50,000 g / mol to 120,000 g / mol, based on the free acid , A particularly preferred acrylic acid-maleic acid copolymer has a molecular weight of 50,000 g / mol to

100000 g / mol. 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. Terpolymers which contain two carboxylic acids and / or salts thereof as monomers and also vinyl alcohol and / or a vinyl alcohol derivative or a carbohydrate as the third monomer may also be used as water-soluble organic builder substances. 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 may 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. Particularly preferred are vinyl alcohol derivatives which are an ester of short chain carboxylic acids, for example, C1-C4 carboxylic acids, with vinyl alcohol. Preferred terpolymers contain from 60% by weight to 95% by weight, in particular from 70% by weight to 90% by weight, of (meth) acrylic acid and / or (meth) acrylate, particularly preferably acrylic acid and / or acrylate, and maleic acid and / or maleate and also 5% by weight to 40% by weight, preferably 10% by weight to 30% by weight, of vinyl alcohol and / or vinyl acetate. Very particular preference is given to terpolymers in which the weight ratio of (meth) acrylic acid and / or (meth) acrylate to maleic acid and / or maleate is between 1: 1 and 4: 1, preferably between 2: 1 and 3: 1 and in particular 2: 1 and 2.5: 1. Both the amounts and the weight ratios are based on the acids. The second acidic monomer or its salt may also be a derivative of an allylsulfonic acid substituted 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. Preferred terpolymers contain from 40% by weight to 60% by weight, in particular from 45 to 55% by weight, of (meth) acrylic acid and / or (meth) acrylate, particularly preferably acrylic acid and / or acrylate, 10% by weight to 30 parts by weight %, preferably 15 wt .-% to 25 wt .-% methallylsulfonic acid and / or Methallylsulfonat and as a third monomer 15 wt .-% to 40 wt .-%, preferably 20 wt .-% to 40 wt .-% 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 generally have a molecular weight between 1000 g / mol and 200000 g / mol, preferably between 2000 g / mol and 50,000 g / mol and in particular between 3000 g / mol and 10,000 g / mol. They 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. used. Among these, the detergent-grade crystalline aluminosilicates, especially zeolite NaA and optionally NaX, are preferred. Amounts near the stated upper limit are preferably used in solid, particulate agents. In particular, suitable aluminosilicates have no particles with a particle size greater than 30 μm, and preferably consist of at least 80% by weight of particles having a size of less than 10 μm. Their calcium binding capacity, which can be determined according to the specifications of the German patent DE 24 12 837, is in the range of 100 to 200 mg CaO per gram. Suitable substitutes or partial substitutes for the said aluminosilicate are crystalline alkali metal 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 silicates are the sodium silicates, in particular the amorphous sodium silicates, with a molar ratio Na ₂ 0: Si0 ₂ of 1: 2 to 1: 2.8. Such amorphous alkali silicates are commercially available, for example, under the name Portil®. Those having a molar ratio of Na ₂ O: SiO ₂ of 1: 1, 9 to 1: 2.8 are preferably added as a solid and not in the form of a solution in the course of the preparation. The crystalline silicates which may be present alone or in admixture with amorphous silicates, are crystalline layer silicates with the general formula of Na ₂ Si _x 0 _{2x +} i yH employed ₂ 0 in which x, known as the modulus, an integer of 1, 9-4 and y is a number from 0 to 20 and preferred values for x 2, 3 or 4 are. 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. In particular, both β- and δ-sodium disilicates (Na ₂ Si ₂ O 5-yH ₂ O) are preferred. 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, can be used in compositions which contain an active substance to be used according to the invention. In a further preferred embodiment of the composition according to the invention, a crystalline sodium layer silicate with a modulus of 2 to 3 is used, as can be prepared from sand and soda. Crystalline sodium silicates with a modulus in the range from 1.9 to 3.5 are used in a further preferred embodiment of detergents containing an active ingredient used according to the invention. Their 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, based in each case 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.

In addition to the said inorganic builder, other water-soluble or water-insoluble inorganic substances may be contained in the agents containing an active ingredient to be used according to the present invention, used together with it or used in methods of the 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.

In addition, the agents may contain other ingredients customary in detergents or cleaners. These optional ingredients include, in particular, enzymes, enzyme stabilizers, complexing agents for heavy metals, for example aminopolycarboxylic acids, aminohydroxypolycarboxylic acids, polyphosphonic acids and / or aminopolyphosphonic acids, foam inhibitors, for example organopolysiloxanes or paraffins, solvents and optical brighteners, for example stilbene disulfonic acid derivatives. Preferably, in agents which contain an active substance 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% by weight, in particular 0, 1% by weight to 2% by weight Complexing agents for heavy metals, in particular aminoalkylenephosphonic acids and their salts and up to 2 wt .-%, in particular 0, 1 wt .-% to 1 wt .-% foam inhibitors, wherein said weight fractions refer to the total agent.

Solvents which can be 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, for example ethylene and propylene glycol, and the ethers derivable from the classes of compounds mentioned. In such liquid agents, the active compounds used in the invention are usually dissolved or in suspended form.

The preferably present enzymes are in particular selected from the group comprising protease, amylase, lipase, cellulase, hemicellulase, oxidase, peroxidase, pectinase and mixtures thereof. First and foremost, 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. 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 obtained, for example, from Humicola lanuginosa, from Bacillus species, from Pseudomonas species, from Fusarium species, from Rhizopus species or from Aspergillus species. 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 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. Such cellulases are commercially available under the names Celluzyme®, Carezyme® and Ecostone®. Suitable pectinases are, for example, under the names Gamanase®, Pektinex AR®, X-Pect® or Pectaway® from Novozymes, under the name Rohapect UF®, Rohapect TPL®, Rohapect PTE100®, Rohapect MPE®, Rohapect MA plus HC, Rohapect DA12L ®, Rohapect 10L®, Rohapect B1 L® from AB Enzymes and available under the name Pyrolase® from Diversa Corp., San Diego, CA, USA.

The customary enzyme stabilizers present, if appropriate, in particular in liquid agents include amino alcohols, for example mono-, di-, triethanol- and -propanolamine and mixtures thereof, lower carboxylic acids, boric acid, alkali borates, boric acid-carboxylic acid combinations, boric acid esters, boronic acid derivatives, calcium salts, for example Ca-formic acid combination, magnesium salts, and / or sulfur-containing reducing agents.

Suitable foam inhibitors include long-chain soaps, in particular behenic soap, fatty acid amides, paraffins, waxes, microcrystalline waxes, organopolysiloxanes and mixtures thereof, which may also contain microfine, optionally silanated or otherwise hydrophobicized silica. For use in particulate agents, such foam inhibitors are preferably bound to granular, water-soluble carrier substances.

The well-known polyester-active soil release polymers that can be used in addition to the essential ingredients of 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. Preferred soil release polymers include those compounds which are formally accessible by esterification of two monomeric moieties, the first monomer being a dicarboxylic acid HOOC-Ph-COOH and the second monomer being a diol HO- (CHR-) _a OH, also known as a polymeric diol H (O- (CHR _i ) _a ) _b OH may be present. Therein, Ph is an o-, m- or p-phenylene radical which may carry 1 to 4 substituents selected from alkyl radicals having 1 to 22 C atoms, sulfonic acid groups, carboxyl groups and mixtures thereof, R is hydrogen, an alkyl radical having 1 to 22 C atoms and mixtures thereof, a is a number from 2 to 6 and b is a number from 1 to 300. Preferably, in the polyesters obtainable from these, both monomer diol units -0- (CHR-i- | -) _a O- and polymer diol units - (0- (CHR ¹¹ -) _a ) _b O-. The molar ratio of monomer diol units to polymer diol units is preferably 100: 1 to 1: 100, in particular 10: 1 to 1:10. In the polymer diol units, the degree of polymerization b is preferably in the range from 4 to 200, in particular from 12 to 140. The molecular weight or the average molecular weight or the maximum of the molecular weight distribution of preferred soil release polyesters is in the range from 250 to 100,000, in particular from 500 to 50,000. The acid underlying the radical Ph is preferably selected from terephthalic acid, isophthalic acid, phthalic acid, trimellitic acid, metilitic acid, the isomers of sulfophthalic acid , Sulfoisophthalic acid and sulfoterephthalic acid and mixtures thereof. If their acid groups are not part of the ester bonds in the polymer, they are preferably in salt form, in particular as alkali or ammonium salt. Among these, the sodium and potassium salts are particularly preferable. If desired, 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. 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. Preferred diols HO- (CHR-) _a OH include those in which R is hydrogen and a is a number from 2 to 6, and those in which a is 2 and R is hydrogen and the alkyl radicals have from 1 to 10 , in particular 1 to 3 C-atoms is selected. Among the latter diols, those of the formula HO-CH ₂ -CHR -OH in which R has the abovementioned meaning are particularly preferred. Examples of 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. Polyethylene glycol having an average molecular weight in the range from 1000 g / mol to 6000 g / mol is particularly preferred among the polymeric diols.

If desired, these polyesters composed as described above may also be end-group-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 Arylmonocarbonsäuren with 5 to 32 carbon atoms, in particular 5 to 18 carbon atoms, based. These include 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, brasidoside 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-butylbenzoic acid. 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, the hydrogenation product of which includes 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. Preferably, the number of hydroxymonocarboxylic acid units per end group, that is to say their degree of oligomerization, is in the range from 1 to 50, in particular from 1 to 10. In a preferred embodiment of the invention, polymers of ethylene terephthalate and polyethylene oxide terephthalate in which the polyethylene glycol units have molecular weights of 750 g / mol to 5000 g / mol and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate is 50:50 to 90:10, used in combination with an essential ingredient of the invention.

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. Preferably used polymers have these conditions However, a solubility of at least 1 g per liter, in particular at least 10 g per liter.

The preparation of solid compositions according to the invention presents no difficulties and can be carried out in a known manner, for example by spray-drying or granulation, enzymes and possibly other thermally sensitive ingredients such as, for example, bleaching agents optionally being added separately later. For the preparation of compositions according to the invention having an increased bulk density, in particular in the range from 650 g / l to 950 g / l, a process comprising an extrusion step is preferred. For the preparation of compositions according to the invention in tablet form, which may be monophasic or multiphase, monochromatic or multicolor and in particular consist of one or more layers, in particular two layers, the procedure is preferably such that all constituents - if appropriate one per layer - in one Mixer mixed together and the mixture by means of conventional tablet presses, such as eccentric or rotary presses, with compression forces in the range of about 50 to 100 kN, preferably compressed at 60 to 70 kN. Particularly in the case of multilayer tablets, it can be advantageous if at least one layer is pre-compressed. This is preferably carried out at pressing forces between 5 and 20 kN, in particular at 10 to 15 kN. This gives fracture-resistant, yet sufficiently rapidly soluble tablets under application conditions with fracture and flexural strengths of normally 100 to 200 N, but preferably above 150 N. Preferably, a tablet produced in this way has a weight of 10 g to 50 g, in particular 15 g up to 40 g. The spatial form of the tablets is arbitrary and can be round, oval or angular, with intermediate forms are also possible. Corners and edges are advantageously rounded. Round tablets preferably have a diameter of 30 mm to 40 mm. In particular, the size of rectangular or cuboid-shaped tablets, which are introduced predominantly via the metering device, for example the dishwasher, is dependent on the geometry and the volume of this metering device. Exemplary preferred embodiments have a base area of (20 to 30 mm) x (34 to 40 mm), in particular of 26x36 mm or 24x38 mm.

Liquid or pasty compositions according to the invention in the form of customary solvents, in particular water, containing solutions are usually prepared by simply mixing the ingredients, which can be added in bulk or as a solution in an automatic mixer.

In a preferred embodiment, an agent which is incorporated into the active ingredient to be used according to the invention is liquid and contains 1% by weight to 15% by weight, in particular 2% by weight to 10% by weight, of nonionic surfactant, 2% by weight. % to 30% by weight, in particular 5% by weight to 20% by weight of synthetic anionic surfactant, up to 15% by weight, in particular 2% by weight to 12.5% by weight of 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 in addition to optionally contained enzyme, enzyme stabilizer, dye and / or perfume, water and / or water-miscible solvent.

In a further preferred embodiment, an agent in which the active ingredient 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 from 1% by weight to 10% by weight of bleach activator, from 20% by weight to 55% by weight of inorganic builder of, up to 10 wt .-%, in particular 2 wt .-% to 8 wt .-% of water-soluble organic Bu der, 10 wt .-% to 25 wt .-% synthetic anionic surfactant, 1 wt .-% to 5 wt .-% nonionic surfactant and up to 25 wt .-%, in particular 0.1 wt .-% to 25 wt .-% of inorganic salts, in particular alkali carbonate and / or bicarbonate.

Examples

Example 1: Preparation of the polymers Preparation of polymer P1

61.1 g of the sodium salt of p-styrenesulfonate (90% wt.) And 7.78 g of isoprene were dissolved in a metal reactor of Parr provided with a magnetic stirrer with 1.04 g of BlocBuilder MA® (Arma) and Added 190 ml of dimethyl sulfoxide (DMSO), degassed under argon for 15 minutes and then kept under an argon protective atmosphere. The polymerization was carried out at 120 ° C for 72 hours. The copolymer was precipitated in acetone / water (95/5 v / v), redissolved in water and precipitated again in acetone, then filtered and washed several times with acetone.

The H-NMR analysis showed for the copolymer a monomer brick content of 78 mol% styrene sulfonate and 22 mol% isoprene.

60 g of poly (styrenesulfonate-sfaf-isoprene) thus obtained and 33 g of toluene-sulfonohydrazide

([Isoprene] / [TSH] = 0.5) were added to 350 ml of distilled water in a 3-neck round bottom flask equipped with a magnetic stirrer and reflux condenser, degassed under argon for 15 minutes, and then held under an argon atmosphere. The hydrogenation was carried out at 110 ° C. for 20 hours. Polymer P1 was precipitated in acetone, redissolved in water and precipitated again in acetone, then filtered and washed several times with acetone.

The H-NMR analysis showed a degree of hydrogenation of 100%. Preparation of polymer P2

61.1 g of the sodium salt of p-styrenesulfonate (90% wt.) And 7.78 g of isoprene were dissolved in a metal reactor of Parr provided with a magnetic stirrer with 10.4 g of BlocBuilder MA® (Arma) and Added 190 ml of dimethyl sulfoxide (DMSO), degassed under argon for 15 minutes and then kept under an argon protective atmosphere. The polymerization was carried out at 120 ° C for 72 hours. The copolymer was precipitated in acetone / water (95/5 v / v), redissolved in water and precipitated again in acetone, then filtered and washed several times with acetone. The H-NMR analysis revealed a monomer brick content of 79 mole% styrene sulfonate and 21 mole% isoprene for the copolymer.

([Isoprene] / [TSH] = 0.5) were added to 350 ml of distilled water in a 3-neck round bottom flask equipped with a magnetic stirrer and reflux condenser, degassed under argon for 15 minutes, and then held under an argon atmosphere. The hydrogenation was carried out at 110 ° C. for 15 hours. The polymer P2 was precipitated in acetone, redissolved in water and precipitated again in acetone, then filtered and washed several times with acetone.

The H-NMR analysis showed a degree of hydrogenation of 100%. Preparation of polymer P3

61.1 g of the sodium salt of p-styrenesulfonate (90% wt.) And 4.54 g of isoprene were dissolved in a metal reactor from Parr provided with a magnetic stirrer with 0.99 g of BlocBuilder MA® (Arma) and Added 190 ml of dimethyl sulfoxide (DMSO), degassed under argon for 15 minutes and then kept under an argon protective atmosphere. The polymerization was carried out at 120 ° C for 72 hours. The copolymer was precipitated in acetone / water (95/5 v / v), redissolved in water and precipitated again in acetone, then filtered and washed several times with acetone.

The H-NMR analysis showed a monomer brick content of 87 mole% styrene sulfonate and 13 mole% isoprene for the copolymer.

60 g of poly (styrenesulfonate-sfaf-isoprene) thus obtained and 23 g of toluene-sulfonohydrazide

([Isoprene] / [TSH] = 0.5) were added to 350 ml of distilled water in a 3-neck round bottom flask equipped with a magnetic stirrer and reflux condenser, degassed under argon for 15 minutes, and then held under an argon atmosphere. The hydrogenation was carried out at 110 ° C. for 20 hours. The polymer P3 was precipitated in acetone, redissolved in water and precipitated again in acetone, then filtered and washed several times with acetone.

The H-NMR analysis showed a degree of hydrogenation of 100%. Preparation of polymer P4

60 g of the sodium salt of p-styrenesulfonate were dissolved in a metal reactor of Parr provided with a magnetic stirrer, with 1. 03 g of BlocBuilder MA® (Arkema), 0.04 g of free SG1 nitroxide (Arkema) and 200 ml of dimethyl sulfoxide (DMSO ), degassed under argon for 15 minutes and then held under an argon atmosphere. The polymerization was carried out at 110 ° C. for 3 hours.

60 g of this polystyrenesulfonate were added to a metal reactor of Parr provided with a magnetic stirrer, with 12 ml of 1, 4-isoprene and 200 ml of DMSO, degassed under argon for 15 minutes and then kept under an argon protective atmosphere. The copolymerization was carried out at 120 ° C for 72 hours. The copolymer was precipitated in acetone, redissolved in water and precipitated again in acetone, then filtered and washed several times with acetone.

The H-NMR analysis showed for the copolymer a monomer brick content of 77 mol% styrene sulfonate and 23 mol% isoprene.

43 g of poly (styrenesulfonate-b / oc / c-isoprene) thus obtained and 25 g of toluene-sulfonohydrazide

([isoprene] / [TSH] = 0.5) in a three-necked round bottom flask equipped with a magnetic stirrer and a reflux condenser, added with 300 ml of distilled water, degassed under argon for 15 minutes and then kept under an argon protective atmosphere. The hydrogenation was carried out at 110 ° C. for 20 hours. The polymer P4 was precipitated in acetone, redissolved in water and precipitated again in acetone, then filtered and washed several times with acetone.

The H-NMR analysis showed a degree of hydrogenation of 100%. Preparation of polymer P5

60 g of the sodium salt of p-styrenesulfonate were dissolved in a Parr metal reactor equipped with a magnetic stirrer with 10.3 g of BlocBuilder MA® (Arkema), 0.04 g of free SG1 nitroxide (Arkema) and 200 ml of dimethyl sulfoxide (DMSO ), degassed under argon for 15 minutes and then held under an argon atmosphere. The polymerization was carried out at 110 ° C. for 2 hours.

60 g of this polystyrenesulfonate were mixed in a Parr metal reactor equipped with a magnetic stirrer with 12 ml of 1,4-isoprene and 200 ml of DMSO, which were left under argon for 15 minutes. and then kept under an argon protective atmosphere. The copolymerization was carried out at 120 ° C for 72 hours. The copolymer was precipitated in acetone, redissolved in water and precipitated again in acetone, then filtered and washed several times with acetone.

H-NMR analysis indicated a monomer brick content of 76 mole% styrene sulfonate and 24 mole% isoprene for the copolymer.

60 g of poly (styrenesulfonate-b / oc / c-isoprene) thus obtained and 33 g of toluene-sulfonohydrazide

([isoprene] / [TSH] = 0.5) in a three-necked round bottom flask equipped with a magnetic stirrer and a reflux condenser, mixed with 350 mL of distilled water, degassed for 15 minutes under argon and then kept under an argon protective atmosphere. The hydrogenation was carried out at 110 ° C. for 20 hours. The polymer P5 was precipitated in acetone, redissolved in water and precipitated again in acetone, then filtered and washed several times with acetone.

The H-NMR analysis showed a degree of hydrogenation of 100%.

Example 2: Detergent

Table 1: Detergent compositions (in% by weight)

A B c D E F G H

C 9-13 -alkylbenzenesulfonate, Na salt 9 10 6 7 5 15 15 9

C12-18 fatty alcohol with 7 EO 8 9 6 7 5 6 1 1 10

C12-14 fatty alcohol sulphate with 2EO - - 8 7 10 2 2 5

C12-18 fatty acid, Na salt 4 3 3 3 4 2 4 7

Citric acid 2 3 3 2 2 2 2 3

Sodium hydroxide, 50% 3 3 2 3 3 3 3 4

Boric acid 1 1 1 1 1 1 1 1

Enzymes (amylase, protease, cellulase) + + + + + + + +

Perfume 1 0.5 0.5 1 1 1 1 1

Propanediol - - - - - 5 5 -

Ethanol 1, 5 1, 5 1, 5 1, 5 1, 5 1, 5 1, 5 5

PVA / maleic acid copolymer 0, 1 - 0, 1 - - - - -

Optical brightener - 0, 1 - 0.1 0.2 0.2 0.2 0.2

Opacifier 0.2 Phosphonic acid, Na salt 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Invention-essential polymer 2 2 2 2 2 2 2 2

Water at 100

Example 3: Washing Tests

Household washing machines (Miele® W 1514) were treated with 3.5 kg of clean accompanying laundry and with standardized soiling (A: whole egg / pigment; B: blood; C: blood / milk / ink; D: chocolate milk / soot; E: cocoa; F: Mousse au chocolat) loaded test textiles made of cotton and dirt ballast. 75 ml of the detergent C listed in Example 2 with one of the polymers prepared in Example 1 were metered in and washed at 40.degree. After hanging drying and mangling of the test textiles, their whiteness was determined spectrophotometrically (Minolta® CR200-1). Table 2 below shows the differences between the remission values for the otherwise identically composed detergent without polymer essential to the invention as averages of 4 determinations and the errors in the 4-fold determination (LSD).

Table 2: Washing results (Angabi

nb: not determined

The detergents with an active ingredient to be used according to the invention showed a significantly better primary washing performance than an otherwise equally composed composition lacking them.

Claims

claims

1. Use of polymers obtainable by copolymerization of styrenesulfonic acid and / or their ammonium or alkali salts with di- or polyethylenically unsaturated monomers to enhance the Primärwaschkraft of washing or cleaning agents when washing textiles or when cleaning hard surfaces against stains.

2. Use according to claim 1, characterized in that it is the stains to pale or enzyme-sensitive stains.

3. Use according to claim 1 or 2, characterized in that the content derived from the styrenesulfonic acid monomer in the polymer is at least 60 mol%, in particular 75 mol% to 99 mol%, based on the polymer.

4. Use according to one of claims 1 to 3, characterized in that it is the di- or polyethylenically unsaturated monomer is a linear or branched chain hydrocarbon having 4 to 12 carbon atoms, in particular selected from the group comprising buta-1, 3rd -diene, isoprene, penta-1,3-diene, hexa-1, 3-diene, hexa-1, 4-diene, hexa-1, 5-diene, hexa-2,4-diene, hepta-1, 6 -diene, octa-1, 7-diene, their isomers, and mixtures of these.

5. Use according to one of claims 1 to 4, characterized in that originating from the di- or polyethylenically unsaturated monomer content in the polymer at most 40 mol%, in particular 1 mol% to 25 mol%, based on the polymer , is.

6. Use according to one of claims 1 to 5, characterized in that the polymer has an average molecular weight in the range of 500 g / mol to 100,000 g / mol, in particular from 1000 g / mol to 40,000 g / mol.

7. Use according to one of claims 1 to 6, characterized in that the polymer is added to a washing or cleaning agent-containing liquor or as a component of a washing or cleaning agent in the fleet.

8. A method for removing bleach- or enzyme-sensitive soiling of textiles or hard surfaces, in which a washing or cleaning agent and a copolymerization of styrene sulfonic acid and / or their ammonium or alkali metal salts with or multi-ethylenically unsaturated monomers available polymer can be used.

Washing or cleaning agent containing a polymer obtainable by copolymerization of styrenesulfonic acid and / or its ammonium or alkali metal salts with a monoethylenically or multiply ethylenically unsaturated monomer.

Composition according to claim 9, characterized in that it contains the polymer in amounts of 0, 1 wt .-% to 10 wt .-%, in particular 0.5 wt .-% to 5 wt .-%. 1. Composition according to claim 9 or 10, characterized in that it is the di- or polyethylenically unsaturated monomer is a linear or branched chain hydrocarbon having 4 to 12 carbon atoms.

Composition according to one of claims 9 to 1 1, characterized in that the di- or polyethylenically unsaturated monomer is selected from the group comprising buta-1, 3-diene, isoprene, penta-1, 3-diene, hexa-1, 3-diene, hexa-1, 4-diene, hexa-1, 5-diene, hexa-2,4-diene, hepta-1, 6-diene, octa-1, 7-diene, their isomers, and mixtures of this.