EP3227421A1

EP3227421A1 - Detergents and cleaning products containing a polymer active ingredient

Info

Publication number: EP3227421A1
Application number: EP15798139.0A
Authority: EP
Inventors: Hendrik Hellmuth; Benoit Luneau; Nicole BODE; Alexander Schulz; Andreas Buhl; Yvonne Willemsen; André LASCHEWSKY; Erik Wischerhoff; Michael PÄCH
Original assignee: Henkel AG and Co KGaA; Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
Current assignee: Henkel AG and Co KGaA; Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
Priority date: 2014-12-05
Filing date: 2015-11-24
Publication date: 2017-10-11
Anticipated expiration: 2035-11-24
Also published as: EP3227421B1; US10316276B2; KR20170091701A; DE102014017964A1; AU2015357388A1; WO2016087258A1; ES2704118T3; PL3227421T3; AU2015357388B2; US20170267953A1

Abstract

The aim of the invention is to improve the primary detergent power of detergents and cleaning products, in particular with respect to soiling containing oil and/or grease. For this purpose, polymers comprising N-vinyl imidazole-derived betaine units are incorporated into the products.

Description

Detergents and cleaning agents with polymeric agent

The present invention relates to the use of certain polymers containing betaine units to enhance the primary detergency of laundry detergents or cleaners when washing textiles or cleaning hard surfaces against, in particular, oil and / or greasy soils, 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 a detergency booster or because of their particularly pronounced effect against oil or fat-based stains as a "fat booster".

International patent application WO 01/57171 A1 discloses washing or rinsing agents which, in addition to surfactant, comprise copolymers of anionic and cationic monomers and, if appropriate, additionally nonionic monomers.

From international patent application WO 00/56849 A1, the color and shape-retaining effect of cationically charged polymers in the washing of textiles is known.

The soil-release effect of block copolymers of ethylenically unsaturated monomers and alkylene oxides, alkylene glycols or cyclic ethers is known from international patent application WO 03/054044 A2.

International Patent Application WO 03/066791 A1 describes polymers associated with substrate surfaces which comprise at least 1 mol% of amide group-containing monomers.

Surprisingly, it has been found that polymers having betaine units derived from N-vinylimidazole have particularly good primary washing strength-enhancing properties.

The invention relates to the use of polymers of the units A and B,

A B wherein R is a zweibindingen hydrocarbon radical having 1 to 6, in particular 1 to 3 carbon atoms, to enhance the Primärwaschkraft of detergents or cleaning agents when washing textiles or when cleaning hard surfaces against particular oil and / or greasy stains.

The polymers essential to the invention are prepared by free-radical copolymerization of 1-vinylimidazole with N-vinyl-2-pyrrolidone, which can be carried out as blockwise or preferably random copolymerization, and subsequent reaction of the resulting copolymer with haloalkanoic acids. such as chloroacetic acid, or ethylenically unsaturated carboxylic acids such as acrylic acid or methacrylic acid accessible. Apart from the units A and B, they have no other units, with at least a small amount of vinylimidazole groups which can not be quaternized as a result of the preparation being present, and units which can be present at the ends of the polymer from the free radical initiator. The proportion of non-quaternized vinylimidazole groups, based on the sum of quaternized vinylimidazole groups and non-quaternized vinylimidazole groups in the polymer, is preferably less than 20

Mol%.

In the polymer essential to the invention, the units A and B are preferably present in molar ratios in the range from 1:99 to 99: 1, in particular from 50:50 to 80:20, and particularly preferably from about 75:25. The polymeric active ingredient preferably has an average molecular weight (here and below with average molecular weight data: number average) in the range from 1000 g / mol to 300000 g / mol, in particular from 2000 g / mol to 200000 g / mol.

When a polymer essential to the invention is introduced together with linear alkylbenzenesulfonate into water, an increase in the surface tension in the presence of the polymer is observed in the region of the critical micelle concentration (of about 0.1 g / l) compared to the same concentration of the surfactant in the absence of the polymer , Without wishing to be bound by theory, this suggests that if the polymer is present through formation a detergent-active surfactant-polymer aggregate more surfactant in the solution and thus less surfactant is present at the water-air interface and thus increases the surface tension. Another object of the invention is therefore the use of a combination of polymers of said units A and B and alkyl benzene sulfonate with linear C7-15 alkyl groups, in particular linear C9-13 alkyl groups, to enhance the Primärwaschkraft of detergents or cleaning agents in the washing of Textiles or when cleaning hard surfaces against particular oily and / or greasy stains. The alkylbenzenesulfonates have counter cations from the group of the alkali metal ions and / or ammonium ions, where sodium, potassium, NhV and / or N (R) 4 ⁺ ions with R = hydrogen, Ci-4-alkyl and / or C2-4- Hydroxyalkyl are preferred. In these combinations, the weight ratio of linear alkylbenzenesulfonate to polymer essential to the invention is preferably in the range from 20: 1 to 1: 1, in particular from 8: 1 to 3: 1.

The use of the active ingredient used according to the invention leads to a significantly better detachment of, in particular, grease and cosmetic soiling on hard surfaces and on textiles, including those made of cotton or with a proportion of cotton, than is the case when compounds previously known for this purpose are used is. Alternatively, significant amounts of surfactants can be saved while retaining the ability to remove grease.

The use according to the invention can be carried out in the context of a washing or cleaning process by adding the polymer essential to the invention to an aqueous or detergent-containing aqueous liquor or preferably introducing it into the liquor as a constituent of a washing or cleaning agent, the concentration of the active ingredient in the liquor is preferably in the range from 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 a method for removing particular oil and / or greasy soiling of textiles or hard surfaces by contacting the textile or the hard surface with an aqueous liquor, in which a detergent or a specified polymeric active substance for Use come. This method can be carried out manually or mechanically, for example by means of a household washing machine or dishwasher. It is possible to use the particular liquid detergent or cleaning 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.

Another object of the invention is therefore a washing or cleaning agent containing a polymer from said units A and B. 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, a polymeric active substance as defined above is incorporated in detergents or cleaners in amounts of from 0.1 to 10% by weight, in particular from 0.5 to 2% by weight.

An agent which contains an active ingredient to be used according to the invention or is used together or used in the process according to the invention preferably contains synthetic anionic surfactant of the sulfate and / or sulfonate type, in particular alkylbenzenesulfonate, fatty alkylsulfate, fatty alkyl ether sulfate, alkyl and / or Dialkylsulfosuccinate, sulfo fatty acid esters and / or sulfo fatty acid, especially in an amount in the range of 2 wt .-% to 25 wt .-% and particularly preferably from 5 wt .-% to 15 wt .-%. 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 content of compounds having longer-chain radicals in the range from 16 to 18 carbon atoms is more than 20% by weight. Particularly preferred is the presence of the above-mentioned combination of polymer essential to the invention and alkylbenzenesulfonate with linear C9-13-alkyl groups in the agents.

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 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. 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, corresponding 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 Fettsäurepolyhydroxyamide 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 other surfactants, preferably synthetic anionic surfactants of the sulfate or sulfonate type. Suitable synthetic anionic surfactants which are particularly suitable for use in such compositions are, in addition to the already mentioned alkylbenzenesulfonates, the alkyl and / or alkenyl sulfates having 8 to 22 carbon atoms which carry an alkali metal, ammonium or alkyl or hydroxyalkyl-substituted ammonium ion as a counter cation , to call. Preference is given to the derivatives of fatty alcohols containing 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. Sulphate-type surfactants which can be used also include the sulfated alkoxylation products of the alcohols mentioned, so-called 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 with 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, derivative sulfonation products, 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 the monoesters or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contain Cs 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. In particular, those soap mixtures are preferred which are composed of 50% by weight to 100% by weight of saturated C 12-18 fatty acid soaps and up to 50% by weight of 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 betaine surfactants and / or cationic surfactants which, if present, are preferably used in amounts of from 0.5% to 7% by weight. Among them, the esterquats discussed below are particularly preferred.

If desired, the compositions may contain peroxygen bleaching agents, in particular in amounts ranging from 5% to 70% by weight, and optionally bleach activators, especially in amounts ranging from 2% to 10% by weight. 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 present in detergents containing an active ingredient used according to the invention, preferably in amounts of up to 25% by weight, in particular up to 15% by weight. % and more preferably from 5 wt .-% to 15 wt .-%, each based on the total agent, present, in particular percarbonate is used. The optionally present component of the bleach activators comprises the conventionally used N- or O-acyl compounds, for example polyacylated alkylenediamines, in particular tetraacetylethylenediamine, acylated glycolurils, in particular tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, urazoles, diketopiperazines, sulphurylamides and Cyanurates, also carboxylic acid anhydrides, in particular phthalic anhydride, carboxylic acid esters, in particular sodium isononanoyl-phenolsulfonat, and acylated sugar derivatives, in particular pentaacetylglucose, and cationic nitrile derivatives such as trimethylammoniumacetonitrile salts. The bleach activators may have been coated and / or granulated in a known manner with enveloping substances during storage 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 by means of carboxymethylcellulose 1, 5-diacetyl-2,4-dioxohexahydro-1, 3,5-triazine, and / or formulated in particulate 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.

In a further embodiment, the composition 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, that 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 C3-Cs carboxylic acid and preferably from a C3-C4 monocarboxylic acid, in particular from (meth) acrylic acid. The second acidic monomer or its salt may be a derivative of a C4-Cs 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% by weight, preferably from 15% by weight to 25% by weight, of methallylsulfonic acid and / or methallylsulfonate and, as the third monomer, from 15% by weight to 40% by weight, preferably from 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 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, are preferably not suitable as water-insoluble, water-dispersible inorganic builder materials above 40 wt .-% and in liquid agents, in particular from 1 wt .-% to 5 wt .-%, used. Among these, 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. 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 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 metal silicates are the sodium silicates, in particular the amorphous sodium silicates, with a molar ratio of Na 2 O: SiO 2 of from 1: 2 to 12.8. Such amorphous alkali silicates are commercially available, for example, under the name Portil®. Those with a molar ratio of Na 2 O: SiO 2 of 1: 1, 9 to 1: 2.8 are preferably added in the course of the production as a solid and not in the form of a solution. Crystalline silicates which may be present alone or in a mixture with amorphous silicates are preferably crystalline phyllosilicates of the general formula Na.sub.2SixO.sub.2 O.sub.x + VH.sub.2O, in which x, the so-called modulus, is a number from 1.9 to 4 and y is a number from 0 is up to 20 and preferred values for x are 2, 3 or 4. Crystalline layered silicates which fall under this general formula are described, for example, in European Patent Application EP 0 164 514. Preferred crystalline phyllosilicates are those in which x in the abovementioned general formula assumes the values 2 or 3. In particular, both .beta. And .delta.-sodium disilicates (Na.sub.2Si.sub.20.sup.yH.sub.2O.sub.2) 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. 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, based in each case on anhydrous active substances, is then preferably 4: 1 to 10: 1. In compositions containing both amorphous and crystalline alkali silicates, the weight ratio of amorphous alkali silicate to crystalline alkali 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 in the present invention, used together with the same or used in the method of 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.

In addition, the agents may contain other ingredients customary in detergents or cleaners. These optional constituents 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% by weight, in particular 0.1% to 1% by weight, of foam inhibitors, the weight proportions in each case referring 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.

Optionally present enzymes are preferably 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 an enzyme recoverable from bacteria or fungi which has a pH optimum preferably in the weakly acidic to weakly 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 moreover can 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- (0- (CHR -) _a ) bOH 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 -) _a O- and also polymeric diol units - (0- (CHR ¹¹ -) _a ) bO-. 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 polymers is in the range of 250 g / mol to 100,000 g / mol, in particular from 500 g / mol to 50,000 g / mol. 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 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. Particularly preferred among the polymeric diols is polyethylene glycol having an average molecular weight in the range from 1000 g / mol to 6000 g / mol.

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 bonded via end groups can be based on alkyl, alkenyl and aryl monocarboxylic acids having 5 to 32 carbon atoms, in particular 5 to 18 carbon atoms. These include valeric acid, caproic acid, 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 molar weights of from 750 g / mol to 5000 g / mol and the molar ratio of ethylene terephthalate to polyethylene terephthalate are from 50:50 to 90: 10, used in combination with a substance essential to 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, pressed with compressive forces in the range of about 50 to 100 kN, preferably 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 breaking and bending 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 predominantly introduced 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 .-% up to 1% by weight complexing agent for heavy metals, such as phosphonate, and in addition to optionally contained enzyme, enzyme stabilizer, dye and / or fragrance, 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 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.

Examples

Example 1: Preparation of poly (N-vinyl-2-pyrrolidone-co-1-vinyl-3- (1-carboxymethyl) imidazolium betaine)

N-vinyl-2-pyrrolidone and 1-vinylimidazole were purified by distillation in vacuo before use (N-vinyl-2-pyrrolidone: 3-4 mbar, 100 ° C. oil bath, head temperature of 77-83 ° C., vacuum jacket, 1-vinylimidazole: 12 mbar, 90 ° C oil bath, 70 ° C head temperature, vacuum jacket stillness). The amount of 1-vinylimidazole indicated in Table 1, the amount of N-vinyl-2-pyrrolidone indicated in Table 1 and 250 ml of methanol were weighed into a 500 ml Schlenk flask and purged with nitrogen for 25 minutes. Then, 15 mg azobisisobutyronitrile was added to the batches intended for the preparation of lower molecular weight polymers V1 and V3 and the batches intended for the preparation of higher molecular weight polymers V2 and V4 and purged with nitrogen for a further 25 minutes, then the batches were stirred at 60 ° C. for 48 h. The same amounts of azobisisobutyronitrile were again added to the batches prepared for the preparation of higher molecular weight polymers V2 and V4 after this time and once more after a total of 72 hours, in each case purged again with nitrogen, and the polymerization was carried out at 60 ° C. for a total period continued for 96 hours.

After removal of the solvent on a rotary evaporator, the residue was dissolved in water and then freeze-dried.

The polymeric intermediates thus obtained were dissolved in 80 ml of dimethylacetamide at 75 ° C, 10 ml of bromoacetic acid tert-butyl ester were added and the reaction mixture was stirred at 75 ° C for 48 h. Thereafter, the precipitate which had been precipitated by addition of 600 ml of diethyl ether was filtered off under nitrogen with a Schlenk frit, washed several times with 100 ml of diethyl ether each time and dried in a stream of nitrogen.

To remove the tert-butyl protecting groups, the resulting intermediate product was mixed with 30 ml of trifluoroacetic acid and stirred for 24 hours at room temperature. After condensing the trifluoroacetic acid, the polymers were dissolved in water and isolated by freeze-drying.

The following variants of poly (N-vinyl-2-pyrrolidone-co-1-vinyl-3- (1-carboxymethyl) imidazolium betaines) with the average molar masses and molar ratios of imidazolium betaine to vinylpyrrolidone given in Table 1 for the resulting polymers were obtained as follows synthesized: Polymer Quantity 1-Vinylimidazole Amount N-Vinyl-2-pyrrolidone Molar Molar Ratio

V1 36 g 14 g 5000 g / mol 50:50

V2 36 g 14 g 50,000 g / mol 50:50

V3 1 1 g 39 g 5000 g / mol 75:25

V4 1 1 g 39 g 50,000 g / mol 75:25

Example 2:

Table 2: Detergent compositions (in% by weight)

Example 3: Washing Tests

With standardized stains (A: CS-46b, used frying fat, B: C-01, carbon black / mineral oil, C: C-03, chocolate milk / carbon black, all available from Center for Testmaterials BV) Cotton fabrics were washed at 25 ° C with the detergent C listed in Example 2, each with a polymer prepared in Example 1 V1 to V4 at a dosage of the detergent of 4.2 g / l for 1 hour. After washing with water and hanging drying of the test textiles, their whiteness was determined spectrophotometrically (Minolta® CR400-1). In Table 3 below, the differences of the remission values (in each case in%) for the same use of the otherwise identically composed detergent without polymer essential to the invention are given as mean values from 5 determinations.

Table 3: Wash results (remission difference)

nb .: not determined

The detergents containing the active ingredients to be used according to the invention showed a significantly better primary washing performance than an otherwise equally composed composition which lacked them.

Claims

claims

1. Use of polymers from the units A and B,

A B wherein R is a two-membered hydrocarbon radical having 1 to 6, in particular 1 to 3 carbon atoms, to enhance the Primärwaschkraft of detergents or cleaners when washing textiles or when cleaning hard surfaces against stains.

Use of a combination of polymers of units A and B,

AB where R is a divalent hydrocarbon radical having 1 to 6, in particular 1 to 3 carbon atoms, and alkylbenzenesulfonate with linear Cz -is-alkyl groups to enhance the Primärwaschkraft of detergents or cleaning agents when washing textiles or when cleaning hard surfaces against stains.

3. Use according to claim 2, characterized in that the weight ratio of linear alkylbenzenesulfonate to polymer from the units A and B in the range of 20: 1 to 1: 1, in particular from 8: 1 to 3: 1.

Use according to one of claims 1 to 3, characterized in that the soils are oil and / or greasy stains.

Use according to one of claims 1 to 4, characterized in that the polymer is added from the units A and B of a washing or cleaning agent-containing aqueous liquor or introduces it as a constituent of a washing or cleaning agent in the liquor, wherein the concentration of polymer the units A and B in the liquor 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.

Process for removing, in particular, oil and / or greasy stains from textiles or hard surfaces by contacting the textile or the hard surface with an aqueous liquor in which a washing or cleaning agent and a polymer comprising units A and B,

A B wherein R is a zweibindingen hydrocarbon radical having 1 to 6, in particular 1 to 3 carbon atoms are used.

7. washing or cleaning compositions containing a polymer of units A and B,

A B where R is a divalent hydrocarbon radical having 1 to 6, in particular 1 to 3 carbon atoms.

Composition according to claim 7, characterized in that it contains 0, 1 wt .-% to 10 wt .-%, in particular 0.5 wt .-% to 2 wt .-% polymer of the units A and B.

Use, method or means according to any one of the preceding claims, characterized in that in the polymer the units A and B are present in molar ratios in the range from 1:99 to 99: 1, in particular from 50:50 to 80:20.

Use, method or means according to any one of the preceding claims, characterized in that the polymer of the units A and B has an average molecular weight in the range from 1000 g / mol to 300000 g / mol, in particular from 2000 g / mol to 200000 g / mol having.