EP3320073B1 - Principes actifs polymères améliorant le pouvoir détergent - Google Patents

Principes actifs polymères améliorant le pouvoir détergent Download PDF

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EP3320073B1
EP3320073B1 EP16732315.3A EP16732315A EP3320073B1 EP 3320073 B1 EP3320073 B1 EP 3320073B1 EP 16732315 A EP16732315 A EP 16732315A EP 3320073 B1 EP3320073 B1 EP 3320073B1
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meth
weight
acrylate
acid
alkyl
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EP3320073A1 (fr
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Benoit Luneau
Alexander Schulz
Hendrik Hellmuth
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • C11D3/3776—Heterocyclic compounds, e.g. lactam

Definitions

  • the present invention relates to the use of certain terpolymers for enhancing the primary washing power of detergents or cleaning agents when washing textiles or cleaning hard surfaces against, in particular, bleach-sensitive or enzyme-sensitive stains, and washing and cleaning agents which contain such polymers.
  • detergents In addition to the ingredients that are indispensable for the washing process, such as surfactants and builder materials, detergents usually contain other components that can be summarized under the term washing auxiliaries and that include such different groups of active ingredients as foam regulators, graying inhibitors, bleaching agents, bleach activators and color transfer inhibitors.
  • auxiliaries also include substances the presence of which increases the detergency of surfactants without, as a rule, themselves having to exhibit pronounced surfactant behavior. The same applies to cleaning agents for hard surfaces. Such substances are often referred to as detergency boosters.
  • poly (N-vinylpyrrolidone) in detergents is known.
  • WO 2011/001173 A1 Liquid detergents containing 0.01 to 5% by weight of cellulase and 0.01 to 5% by weight of poly (N-vinylpyrrolidone) and / or its salt with an average molecular weight of 20,000 g / mol to 60,000 g / mol .
  • crosslinked polymers of 10 to 50% by weight of N-vinylcaprolactam and 50 to 90% by weight of N-vinylpyrrolidone are known, which in the presence of 0.5 to 7% by weight of a crosslinker, which also generates 1- Vinyl-3 (E) -ethylidenepyrrolidone can be produced.
  • Such crosslinked polymers are suitable for filtering out polyphenols from beer.
  • N-vinylcaprolactam homopolymers and copolymers with minor amounts of other monomers such as, for example, N-vinylpyrrolidone is from the European patent application EP 0 181 204 A2 known. From the European patent application EP 0 181 205 A2 it is known that such polymers can also be applied as coating materials to fibers, in particular made of polyester, in order to achieve the soil release effect.
  • the international patent application WO 2004/014326 A1 describes shampoos containing anionic surfactants, silicone derivatives containing amino and hydroxyl groups and water-soluble cationic polymers with an average molecular weight of 100,000 g / mol to 2,000,000 g / mol and charge densities of 0.6 to 4 meq / g, including N-vinylpyrrolidone / alkylaminoacrylate / N-vinylcaprolactam copolymers and which are used there because of their conditioning effect.
  • the European patent application EP 1 570 037 A1 relates to detergents that contain polymers with a vinyl pyrrolidone backbone and C 4-20 alkyl side chains. From the international patent application WO 2013/034437 A1 it is known that poly (N, N-dimethylacrylamide) and / or by copolymerization of N, N-dimethylacrylamide with a comonomer selected from acrylamide, methacrylamide, N, N-disubstituted acrylamide, N, N-disubstituted methacrylamide, N ' , N'-Disubstituted aminoalkyl methacrylamide, N, N-disubstituted aminoalkylacrylamide, N-acryloylmorpholine, N-acryloylpyrrolidine, N-acryloylpyrrolidone, N-acryloylpiperidone, N-acryloylcaprolactam, N-acryloylpyrrolidone, N-acrylo
  • the invention relates to the use of N-vinylpyrrolidone, N-vinylcaprolactam and a further ethylenically unsaturated compound selected from optionally alkoxylated C 1 -C 24 -alkyl (meth) acrylate, polyalkylene glycol (meth) acrylate, N- Alkyl-substituted (meth) acrylamide, acrylonitrile and mixtures thereof for enhancing the primary washing power of detergents or cleaning agents when washing textiles or when cleaning hard surfaces against, in particular, bleach-sensitive or enzyme-sensitive soiling.
  • a further ethylenically unsaturated compound selected from optionally alkoxylated C 1 -C 24 -alkyl (meth) acrylate, polyalkylene glycol (meth) acrylate, N- Alkyl-substituted (meth) acrylamide, acrylonitrile and mixtures thereof for enhancing the primary washing power of detergents or cleaning agents when washing textiles or
  • polyalkylene glycol methacrylates and, among them, polyethylene glycol methacrylates are preferred, the degrees of polymerization, which can assume whole or fractional numerical values, in these compounds preferably in the range from greater than 1 to 60, in particular 2 to 60, lie.
  • C 1 -C 24 -alkyl (meth) acrylates in which the alkyl group can be linear or branched, are preferably selected from methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, ethylhexyl (meth) acrylate, Octyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate and mixtures of at least two of these, the presence of butyl methacrylate being particularly preferred.
  • the compounds mentioned here as being preferred can be used alone or in mixtures.
  • the copolymers used according to the invention are preferably not crosslinked and, with the exception of groups which may arise from customary free radical initiator and / or free radical chain termination compounds, do not have any components derived from monomers other than those mentioned. They are preferably obtainable by copolymerizing 60% by weight to 98% by weight N-vinylpyrrolidone, 1% by weight to 39% by weight N-vinylcaprolactam and 1% by weight to 20% by weight of the above further ethylenically unsaturated compound, the percentages by weight here referring to the total amount of monomers present in the copolymerization.
  • the polymeric active ingredient preferably has an average molecular weight (here and below for average molecular weights: numerical average) in the range from 1000 g / mol to 500,000 g / mol, in particular from 1100 g / mol to 150,000 g / mol.
  • Another object of the invention is a method for removing, in particular, bleach-sensitive or enzyme-sensitive soiling from textiles or hard surfaces, in which a washing or cleaning agent and a named polymeric active ingredient are used.
  • This method can be carried out manually or by machine, for example with the aid of a household washing machine or dishwasher. It is possible here to use the particularly liquid agent and the active ingredient simultaneously or in succession. Simultaneous use can be carried out particularly advantageously through the use of an agent which contains the active ingredient.
  • Bleach-sensitive or enzyme-sensitive stains are understood as meaning those which can usually be at least partially removed by bleaching agents or with the aid of enzymes, such as, for example, stains from red wine or chocolate mousse.
  • the active ingredients used according to the invention can be prepared in a simple way by radical polymerization of the ethylenically unsaturated monomers.
  • the polymerization can be carried out as a block copolymerization or as a random copolymerization. Preferably it is carried out as a random copolymerization. Alternatively, it can be carried out as a block copolymerization, in which N-vinylpyrrolidone oligomer blocks are first produced and the other monomers are polymerized onto them.
  • copolymers obtainable from the monomers mentioned leads to a significantly better detachment of, in particular, bleach-sensitive or enzyme-sensitive soiling on hard surfaces and on textiles, including those made of cotton or with a percentage of cotton, than when using compounds previously known for this purpose the case is.
  • significant amounts of surfactants can be saved while maintaining the same dirt-releasing properties.
  • a further advantage of the copolymers used in accordance with the invention is that they can easily be incorporated in a stable manner into liquid water-containing detergents and cleaning agents without this leading to phase separations.
  • the invention therefore also relates to detergents and cleaning agents, in particular liquid, water-containing washing and cleaning agents which contain a named copolymer.
  • the use according to the invention can take place in the context of a washing or cleaning process in such a way that the active ingredient is added to a detergent or cleaning agent-containing liquor or, preferably, the active ingredient is introduced into the liquor as a component of a washing or cleaning agent, the concentration of active ingredient in the liquor preferably is 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.
  • Detergents or cleaning agents which contain an active ingredient to be used according to the invention or are used together with this or are used in the method according to the invention can contain all the usual other constituents of such agents which do not interact in an undesirable manner with the active ingredient essential to the invention.
  • An above-defined polymeric active ingredient is preferably incorporated into washing or cleaning agents in amounts of 0.1% by weight to 10% by weight, in particular 0.2% by weight to 5% by weight.
  • An agent which contains an active ingredient to be used according to the invention or is used together with it or is used in the method according to the invention can preferably be peroxygen-based bleaching agents, in particular in amounts in the range of 5% by weight up to 70% by weight, and optionally bleach activator, in particular in amounts in the range from 2% by weight to 10% by weight.
  • the bleaching agents which can be considered are preferably the peroxygen compounds usually used in detergents, such as percarboxylic acids, for example dodecanediperic acid or phthaloylaminoperoxicaproic acid, hydrogen peroxide, alkali perborate, which can be present as tetra- or monohydrate, percarbonate, perpyrophosphate and persilicate, which are usually as alkali salts, in particular as sodium salts.
  • Such bleaches are in detergents which contain 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 particularly preferably from 5% by weight to 15% by weight, in each case on the entire medium, with percarbonate in particular being used.
  • the optionally present component of the bleach activators comprises the commonly used N- or O-acyl compounds, for example poly-acylated alkylenediamines, in particular tetraacetylethylenediamine, acylated glycolurils, in particular tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, urazoles, diketopiperazines and carboxylic acid anurylamides , in particular phthalic anhydride, carboxylic acid esters, in particular sodium isononanoyl phenolsulfonate, and acylated sugar derivatives, in particular pentaacetyl glucose, and cationic nitrile derivatives such as trimethylammonium acetonitrile salts.
  • N- or O-acyl compounds for example poly-acylated alkylenediamines, in particular tetraacetylethylenediamine, acylated glycolurils,
  • the bleach activators can be coated with coating substances and / or granulated in a known manner in order to avoid interaction with the per compounds during storage, whereby with the help of carboxymethyl cellulose, granulated tetraacetylethylenediamine with mean particle sizes of 0.01 mm to 0.8 mm, granulated 1, 5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine, and / or trialkylammonium acetonitrile made up in particulate form is particularly preferred.
  • Such bleach activators are preferably contained in detergents in amounts of up to 8% by weight, in particular from 2% by weight to 6% by weight, in each case based on the total detergent.
  • an agent according to the invention or used within the scope of the use according to the invention contains synthetic anionic surfactant of the sulfate and / or sulfonate type, in particular alkylbenzenesulfonate, fatty alkyl sulfate, fatty alkyl ether sulfate, alkyl and / or dialkyl sulfosuccinate, sulfofatty acid esters and / or sulfofatty acid disalts, in particular in an amount equal to Range from 2 wt% to 25 wt%.
  • synthetic anionic surfactant of the sulfate and / or sulfonate type in particular alkylbenzenesulfonate, fatty alkyl sulfate, fatty alkyl ether sulfate, alkyl and / or dialkyl sulfosuccinate, sulfofatty acid esters and / or sulfofatty acid disalts, in
  • 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 with longer-chain radicals in the range from 16 to 18 carbon atoms is more than 20% by weight.
  • Another embodiment of such agents comprises the presence of nonionic surfactant selected from fatty alkyl polyglycosides, fatty alkyl polyalkoxylates, in particular ethoxylates and / or propoxylates, fatty acid polyhydroxyamides and / or ethoxylation and / or propoxylation products of fatty alkylamines, vicinal diols, fatty acid alkyl esters and / or fatty acid amides and mixtures thereof, in particular in an amount in the range from 2% by weight to 25% by weight.
  • nonionic surfactant selected from fatty alkyl polyglycosides, fatty alkyl polyalkoxylates, in particular ethoxylates and / or propoxylates, fatty acid polyhydroxyamides and / or ethoxylation and / or propoxylation products of fatty alkylamines, vicinal diols, fatty acid alkyl esters and / or fatty acid amides and mixtures thereof
  • the nonionic surfactants in question include the alkoxylates, in particular the ethoxylates and / or propoxylates, of saturated or mono- to polyunsaturated linear or branched-chain alcohols having 10 to 22 carbon atoms, preferably 12 to 18 carbon atoms.
  • the degree of alkoxylation of the alcohols is generally between 1 and 20, preferably between 3 and 10. They can be prepared in a known manner by reacting the corresponding alcohols with the corresponding alkylene oxides.
  • the derivatives of fatty alcohols are particularly suitable, although their branched-chain isomers, in particular so-called oxo alcohols, can also be used to prepare usable alkoxylates.
  • the alkoxylates especially the ethoxylates, of primary alcohols with linear, especially dodecyl, tetradecyl, hexadecyl or octadecyl radicals and mixtures thereof can be used.
  • Corresponding alkoxylation products of alkylamines, vicinal diols and carboxamides which correspond to the alcohols mentioned with regard to the alkyl moiety can also be used.
  • the ethylene oxide and / or propylene oxide insertion products of fatty acid alkyl esters and fatty acid polyhydroxyamides are also suitable.
  • alkyl polyglycosides suitable for incorporation into the agents according to the invention are compounds of the general formula (G) n -OR 12 , in which R 12 is an alkyl or alkenyl radical having 8 to 22 carbon atoms, G is a glycose unit and n is a number between 1 and 10 mean.
  • the glycoside component (G) n is oligo- or polymers from naturally occurring aldose or ketose monomers, to which in particular glucose, mannose, fructose, galactose, talose, gulose, altrose, allose, idose, ribose, arabinose, Include xylose and lyxosis.
  • the oligomers consisting of such glycosidically linked monomers are characterized not only by the type of sugars they contain but also by their number, the so-called degree of oligomerization.
  • the degree of oligomerization n generally assumes fractional numerical values as a variable to be determined analytically; it has values between 1 and 10, in the case of the glycosides preferably used below a value of 1.5, in particular between 1.2 and 1.4.
  • the preferred monomer building block is glucose because of its ready availability.
  • Nonionic surfactant is in agents 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 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 more likely to be found in liquid detergents and particulate detergents preferably rather smaller amounts of contain up to 5% by weight.
  • the agents can contain further surfactants, preferably synthetic anionic surfactants of the sulfate or sulfonate type, including, for example, the aforementioned alkylbenzenesulfonates, in amounts of preferably not more than 20% by weight, in particular from 0.1% by weight to 18% by weight, each based on the total agent.
  • Particularly suitable synthetic anionic surfactants for use in such agents are the alkyl and / or alkenyl sulfates with 8 to 22 carbon atoms which have an alkali, ammonium or alkyl or hydroxyalkyl-substituted ammonium ion as a counter cation.
  • the derivatives of fatty alcohols having in particular 12 to 18 carbon atoms and their branched-chain analogs, the so-called oxo alcohols, are preferred.
  • the alkyl and alkenyl sulfates can be prepared in a known manner by reacting the corresponding alcohol component with a customary sulfating reagent, in particular sulfur trioxide or chlorosulfonic acid, and subsequent neutralization with alkali, ammonium or alkyl or hydroxyalkyl-substituted ammonium bases.
  • a customary sulfating reagent in particular sulfur trioxide or chlorosulfonic acid
  • the sulfate-type surfactants that can be used also include the sulfated alkoxylation products of the alcohols mentioned, so-called ether sulfates.
  • Such ether sulfates preferably contain 2 to 30, in particular 4 to 10, ethylene glycol groups per molecule.
  • Suitable anionic surfactants of the sulfonate type include the ⁇ -sulfoesters obtainable by reacting fatty acid esters with sulfur trioxide and subsequent neutralization, in particular those derived from fatty acids with 8 to 22 carbon atoms, preferably 12 to 18 carbon atoms, and linear alcohols with 1 up to 6 carbon atoms, preferably 1 to 4 carbon atoms, derived sulfonation products, as well as the sulfo fatty acids resulting from these by formal saponification.
  • Preferred anionic surfactants are also the salts of sulfosuccinic acid esters, which are also referred to as alkyl sulfosuccinates or dialkyl sulfosuccinates, and the monoesters or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain C 8 to C 18 fatty alcohol radicals or mixtures of these.
  • Particularly preferred sulfosuccinates contain an ethoxylated fatty alcohol residue which, considered in itself, represents a nonionic surfactant.
  • Sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution are particularly preferred.
  • soaps 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, being suitable.
  • soap mixtures which are composed of 50% by weight to 100% by weight of saturated C 12 -C 18 fatty acid soaps and up to 50% by weight of oleic acid soap. Soap is preferably contained in amounts of 0.1% by weight to 5% by weight. In particular in liquid agents which contain an active ingredient used according to the invention, however, higher amounts of soap of generally up to 20% by weight can also be included.
  • the agents can also contain betaines and / or cationic surfactants, which - if present - are preferably used in amounts of 0.5% by weight to 7% by weight.
  • the agent contains water-soluble and / or water-insoluble builders, in particular selected from alkali aluminosilicate, crystalline alkali silicate with a module greater than 1, monomeric polycarboxylate, polymeric polycarboxylate and mixtures thereof, in particular in amounts in the range from 2.5% by weight to 60 Wt%.
  • water-soluble and / or water-insoluble builders in particular selected from alkali aluminosilicate, crystalline alkali silicate with a module greater than 1, monomeric polycarboxylate, polymeric polycarboxylate and mixtures thereof, in particular in amounts in the range from 2.5% by weight to 60 Wt%.
  • the agent preferably contains 20% by weight to 55% by weight of water-soluble and / or water-insoluble, organic and / or inorganic builders.
  • the water-soluble organic builder substances include, in particular, those from the class of polycarboxylic acids, in particular citric acid and sugar acids, and polymeric (poly) carboxylic acids, in particular the polycarboxylates, polymeric acrylic acids, methacrylic acids, maleic acids and copolymers of these which are also accessible by oxidation of polysaccharides may contain small amounts of polymerizable substances without carboxylic acid functionality polymerized.
  • the relative molecular weight 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 relative molecular weight of 50,000 g / mol to 100,000 g / mol.
  • Suitable, albeit less preferred, compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinyl methyl ethers, vinyl esters, ethylene, propylene and styrene, in which the acid makes up at least 50% by weight.
  • vinyl ethers such as vinyl methyl ethers, vinyl esters, ethylene, propylene and styrene
  • the acid makes up at least 50% by weight.
  • Terpolymers which contain two carboxylic acids and / or their salts as monomers and vinyl alcohol and / or a vinyl alcohol derivative or a carbohydrate as a third monomer can 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 can be a derivative of a C 4 -C 8 dicarboxylic acid, maleic acid being particularly preferred.
  • the third monomeric unit is formed by vinyl alcohol and / or preferably an esterified vinyl alcohol. Vinyl alcohol derivatives which represent an ester of short-chain carboxylic acids, for example of C 1 -C 4 carboxylic acids, with vinyl alcohol are particularly preferred.
  • Preferred terpolymers here contain 60% by weight to 95% by weight, in particular 70% by weight to 90% by weight (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, vinyl alcohol and / or vinyl acetate.
  • Terpolymers in which the weight ratio (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 can also be a derivative of an allylsulfonic acid which is in the 2-position with an alkyl radical, preferably with a C 1 -C 4 -alkyl radical, or an aromatic radical, which is preferably derived from benzene or benzene derivatives , is substituted.
  • Preferred terpolymers contain 40% by weight to 60% by weight, in particular 45 to 55% by weight (meth) acrylic acid and / or (meth) acrylate, particularly preferably acrylic acid and / or acrylate, up to 10% by weight 30% by weight, preferably 15% by weight to 25% by weight methallylsulfonic acid and / or methallylsulfonate and, as the third monomer, 15% by weight to 40% by weight, preferably 20% by weight to 40% by weight % of a carbohydrate.
  • This carbohydrate can be, for example, a mono-, di-, oligo- or polysaccharide, mono-, di- or oligosaccharides being preferred, sucrose being particularly preferred.
  • terpolymers generally have a relative molecular weight between 1000 g / mol and 200,000 g / mol, preferably between 2000 g / mol and 50,000 g / mol and in particular between 3000 g / mol and 10,000 g / mol.
  • terpolymers can be used 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 upper limit mentioned are preferably used in paste-like or liquid, in particular water-containing, agents.
  • the water-insoluble, water-dispersible inorganic builder materials used are in particular 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, used.
  • the crystalline aluminosilicates in detergent quality in particular zeolite NaA and optionally NaX, are preferred.
  • Quantities close to the upper limit mentioned are preferably used in solid, particulate compositions.
  • Suitable aluminosilicates in particular have no particles with a particle size greater than 30 ⁇ m and preferably consist of at least 80% by weight of particles with a size less than 10 ⁇ m.
  • Suitable substitutes or partial substitutes for the said aluminosilicate are crystalline alkali metal silicates, which can be present alone or in a mixture with amorphous silicates.
  • the alkali silicates which can be used as builders in the agents preferably have a molar ratio of alkali oxide to SiO 2 below 0.95, in particular from 1: 1.1 to 1:12, and can amorphous or crystalline.
  • Preferred alkali silicates are the sodium silicates, in particular the amorphous sodium silicates, with a molar ratio Na 2 O: SiO 2 of 1: 2 to 1: 2.8.
  • Such amorphous alkali silicates are commercially available, for example, under the name Portil®.
  • Those with a molar ratio of Na 2 O: SiO 2 of 1: 1.9 to 1: 2.8 are preferably added as a solid and not in the form of a solution in the course of production.
  • the crystalline silicates used alone or in a mixture with amorphous silicates are preferably crystalline sheet silicates of the general formula Na 2 Si x O 2x + 1 ⁇ yH 2 O, in which x, the so-called module, is a number of 1.9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4.
  • Crystalline sheet silicates that come under this general formula are, for example, in the European patent application EP 0 164 514 described.
  • Preferred crystalline sheet silicates are those in which x in the general formula mentioned assumes the values 2 or 3. In particular, both ß- and ⁇ -sodium disitics (Na 2 Si 2 O 5 ⁇ yH 2 O) are preferred.
  • Virtually anhydrous crystalline alkali silicates of the abovementioned general formula, in which x is a number from 1.9 to 2.1, prepared from amorphous alkali silicates, can also be used in agents which contain an active ingredient to be used according to the invention.
  • agents according to the invention a crystalline layered sodium silicate with a module of 2 to 3, as can be produced from sand and soda, is used.
  • Crystalline sodium silicates with a modulus in the range from 1.9 to 3.5 are used in a further preferred embodiment of detergents which contain an active ingredient used according to the invention.
  • alkali metal silicates are preferably 1% by weight to 50% by weight and in particular 5% by weight to 35% by weight, based on anhydrous active substance. If alkali aluminosilicate, in particular zeolite, is also present as an additional builder substance, the alkali silicate content is preferably 1% by weight to 15% by weight and in particular 2% by weight to 8% by weight, based on anhydrous active substance.
  • the weight ratio of aluminosilicate to silicate, based in each case on anhydrous active substances is then preferably 4: 1 to 10: 1.
  • the weight ratio of amorphous alkali silicate to crystalline alkali silicate is preferably 1: 2 to 2: 1 and in particular 1: 1 to 2: 1.
  • water-soluble or water-insoluble inorganic substances can be contained in the agents which contain an active ingredient to be used according to the invention, used together with this or used in the process according to the invention.
  • the alkali metal carbonates, alkali metal hydrogen carbonates and alkali metal sulfates and mixtures thereof are suitable.
  • Such additional inorganic material can be present in amounts up to 70% by weight.
  • the agents can contain other constituents that are customary in detergents or cleaning agents.
  • These optional components 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.
  • optical brighteners in particular compounds from the class of substituted 4,4 '
  • optical brighteners are in agents which contain an active ingredient used according to the invention -Bis- (2,4,6-tri-amino-s-triazinyl) -stilbene-2,2'-disulfonic acids, up to 5% by weight, in particular 0.1% by weight to 2% by weight
  • an agent according to the invention is liquid and contains 1% by weight to 90% by weight, in particular 10% by weight to 85% by weight, preferably 25% by weight to 75% by weight, and particularly preferably 35% by weight to 65% by weight of water, water-miscible solvent or a mixture of water and water-miscible solvent.
  • Water-miscible solvents include, for example, monohydric alcohols with 1 to 4 carbon atoms, in particular methanol, ethanol, isopropanol and tert-butanol, diols and triols with 2 to 4 carbon atoms, in particular ethylene glycol, propylene glycol and glycerol, and mixtures thereof and the ethers derived from the named classes of compounds.
  • Such water-miscible solvents are preferably present in the agents according to the invention in amounts not exceeding 30% by weight, in particular from 2% by weight to 20% by weight.
  • the active ingredients used according to the invention are generally dissolved or in suspended form.
  • the enzymes preferably present are selected in particular from the group comprising protease, amylase, lipase, cellulase, hemicellulase, oxidase, peroxidase, pectinase and mixtures of these.
  • Protease obtained from microorganisms such as bacteria or fungi, is primarily considered. It can be obtained in a known manner from suitable microorganisms by fermentation processes.
  • 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 cellulase that can be used can be an enzyme which can be obtained from bacteria or fungi and which has a pH optimum, preferably in the weakly acidic to weakly alkaline range 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 names Rohapect UF®, Rohapect TPL®, Rohapect PTE100®, Rohapect MPE®, Rohapect MA plus HC, Rohapect DA12L®, Rohapect 10L®, Rohapect B1L® from AB Enzymes and available under the name Pyrolase® from Diversa Corp., San Diego, CA, USA.
  • customary enzyme stabilizers that may be present, especially 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 behen soap, fatty acid amides, paraffins, waxes, microcrystalline waxes, organopolysiloxanes and mixtures thereof, which can also contain microfine, optionally silanized or otherwise hydrophobized silica.
  • foam inhibitors are preferably bound to granular, water-soluble carrier substances.
  • dicarboxylic acids for example adipic acid, phthalic acid or terephthalic acid
  • diols for example ethylene glycol or propylene glycol
  • polydiols for example polyethylene glycol or polypropylene glycol.
  • dirt-releasing polyesters include those compounds which are formally accessible by esterification of two monomer parts, the first monomer being a dicarboxylic acid HOOC-Ph-COOH and the second monomer being a diol HO- (CHR 11 -) a OH, which is also called polymeric Diol H- (O- (CHR 11 -) a ) b OH may be present.
  • Ph therein denotes an o-, m- or p-phenylene radical which can carry 1 to 4 substituents selected from alkyl radicals with 1 to 22 carbon atoms, sulfonic acid groups, carboxyl groups and mixtures thereof
  • R 11 is hydrogen, an alkyl radical with 1 to 22 carbon atoms and their mixtures
  • a is a number from 2 to 6
  • b is a number from 1 to 300.
  • the polyesters obtainable from these preferably contain both monomer diol units - O - (CHR 11 -) a O - and polymer diol units - ( O- (CHR 11 -) a ) b O- before.
  • the molar ratio of monomer diol units to polymer diol units is preferably 100: 1 to 1: 100, in particular 10: 1 to 1:10.
  • the degree of polymerization b is preferably in the range from 4 to 200, in particular from 12 to 140.
  • the molecular weight or the average molecular weight or the maximum molecular weight distribution of preferred soil-releasing polyesters is in the range from 250 to 100,000, in particular from 500 to 50,000
  • the acid on which the remainder Ph is based is preferably selected from terephthalic acid, isophthalic acid, phthalic acid, trimellitic acid, mellitic acid, the isomers of sulfophthalic acid, sulfoisophthalic acid and sulfoterephthalic acid and mixtures thereof. If their acid groups are not part of the ester bonds in the polymer, they are preferably in salt form, in particular as an alkali metal or ammonium salt. Among these are the Sodium and potassium salts are particularly preferred.
  • small proportions, in particular not more than 10 mol% based on the proportion of Ph with the meaning given above, of other acids which have at least two carboxyl groups can be contained in the soil-releasing polyester instead of the HOOC-Ph-COOH monomer.
  • these include, for example, alkylene and alkenylene dicarboxylic acids such as malonic acid, succinic acid, fumaric acid, maleic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid.
  • the preferred diols HO- (CHR 11 -) a OH include those in which R 11 is hydrogen and a is a number from 2 to 6, and those in which a has the value 2 and R 11 is hydrogen and the alkyl radicals with 1 to 10, in particular 1 to 3, carbon atoms is selected.
  • those of the formula HO-CH 2 -CHR 11 -OH, in which R 11 has the abovementioned meaning are particularly preferred.
  • diol components are ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,2-decanediol, 1, 2-dodecanediol and neopentyl glycol.
  • Particularly preferred among the polymeric diols is polyethylene glycol with an average molar mass in the range from 1000 g / mol to 6000 g / mol.
  • these polyesters composed as described above can also be end group-capped, with possible end groups being alkyl groups with 1 to 22 carbon atoms and esters of monocarboxylic acids.
  • the end groups bonded via ester bonds can be based on alkyl, alkenyl and aryl monocarboxylic acids having 5 to 32 carbon atoms, in particular 5 to 18 carbon atoms.
  • valeric acid caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, undecenoic acid, lauric acid, lauroleic acid, tridecanoic acid, myristic acid, myristoleic acid, pentadecanoic acid, palmitic acid, stearic acid, linroselic acid, eloic acidic acid, petroselic acid, linoleumic acid, arsenicic acid, petroselic acid , Gadoleic acid, arachidonic acid, behenic acid, erucic acid, brassidic acid, clupanodonic acid, lignoceric acid, cerotic acid, melissic acid, benzoic acid, which can carry 1 to 5 substituents with a total of up to 25 carbon atoms, in particular 1 to 12 carbon atoms, for example tert-butylbenzoic acid .
  • the end groups can also be based on hydroxymonocarboxylic acids having 5 to 22 carbon atoms, which include, for example, hydroxyvaleric acid, hydroxycaproic acid, ricinoleic acid, their hydrogenation product hydroxystearic acid and o-, and p-hydroxybenzoic acid.
  • the hydroxymonocarboxylic acids can for their part be linked to one another via their hydroxyl group and their carboxyl group and can thus be present several times in an end group.
  • the number of hydroxymonocarboxylic acid units per end group is preferably in the range from 1 to 50, in particular from 1 to 10.
  • the soil-releasing 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.
  • polymers used with preference have a solubility of at least 1 g per liter, in particular at least 10 g per liter, under these conditions.
  • solid agents according to the invention does not present any difficulties and can be carried out in a known manner, for example by spray drying or granulation, enzymes and any other thermally sensitive ingredients such as bleaching agents being added later if necessary.
  • a method having an extrusion step is preferred.
  • the procedure is preferably such that all constituents - optionally one layer each - are in one Mixers are mixed with one another and the mixture is pressed by means of conventional tablet presses, for example eccentric presses or rotary presses, with pressing forces in the range from about 50 to 100 kN, preferably at 60 to 70 kN.
  • unbreakable tablets which dissolve sufficiently quickly under the conditions of use and have breaking and flexural strengths of normally 100 to 200 N, but preferably more than 150 N, are obtained without any problems up to 40 g.
  • the three-dimensional shape of the tablets is arbitrary and can be round, oval or angular, with intermediate shapes also being possible. Corners and edges are advantageously rounded. Round tablets preferably have a diameter of 30 mm to 40 mm.
  • the size of angular or cuboid tablets which are introduced predominantly via the dosing device, for example the dishwasher, depends on the geometry and the volume of this dosing device.
  • Exemplary preferred embodiments have a base area of (20 to 30 mm) ⁇ (34 to 40 mm), in particular of 26 ⁇ 36 mm or of 24 ⁇ 38 mm.
  • Liquid or pasty agents according to the invention in the form of solutions containing customary solvents, in particular water, are generally produced by simply mixing the ingredients, which can be added in bulk or as a solution to an automatic mixer.
  • an agent into which the active ingredient to be used according to the invention is incorporated is liquid and contains 1% by weight to 15% by weight, in particular 2% by weight to 10% by weight nonionic surfactant, 2% by weight. -% to 30 wt .-%, in particular 5 wt .-% to 20 wt .-% synthetic anionic surfactant, up to 15 wt .-%, in particular 2 wt .-% to 12.5 wt .-% soap, 0, 5% by weight to 5% by weight, in particular 1% by weight to 4% by weight, organic builder, in particular polycarboxylate such as citrate, up to 1.5% by weight, in particular 0.1% by weight up to 1% by weight complexing agent for heavy metals, such as phosphonate, and in addition to any enzyme, enzyme stabilizer, color and / or fragrance contained, water and / or water-miscible solvent.
  • an agent into which the active ingredient to be used according to the invention is incorporated is particulate and contains up to 25% by weight, in particular 5% by weight to 20% by weight of bleach, in particular alkali percarbonate, up to 15% by weight %, in particular 1% by weight to 10% by weight bleach activator, 20% by weight to 55% by weight inorganic builder, up to 10% by weight, in particular 2% by weight to 8% by weight.
  • water-soluble organic builder 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 .-% up to 25% by weight of inorganic salts, in particular alkali metal carbonate and / or hydrogen carbonate.
  • THF tetrahydrofuran
  • Example 1 The performance of the polymers produced in Example 1 was tested in washing tests at a washing temperature of 20 ° C. under European conditions (16 ° dH) in Miele washing machines.
  • the polymers were each incorporated in amounts of 2% by weight, based on the detergent, into a commercially available liquid detergent and this was then used in the washing of textiles provided with 111 standardized soils.
  • the liquid detergent free of the respective polymers was also used under the same conditions.
  • the agent with polymer A showed a significantly better washing performance on 14 of the soils compared to the liquid detergent free from the polymer, the agent with polymer B on 23 soils, the agent with polymer C on 22 soils, and the agent with polymer C on 21 Soiling.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)

Claims (10)

  1. Utilisation de polymères pouvant être obtenus par copolymérisation de N-vinylpyrrolidone, de N-vinylcaprolactame et d'un autre composé à insaturation éthylénique, choisi parmi le (méth)acrylate d'alkyle en C1-C24 éventuellement alcoxylé, le (méth)acrylate de polyalkylène glycol, le (méth)acrylamide à substitution N-alkyle, l'acrylonitrile et leurs mélanges, pour renforcer la performance de lavage primaire d'agents de lavage ou de nettoyage lors du lavage de textiles ou lors du nettoyage de surfaces dures contre des salissures.
  2. Utilisation selon la revendication 1, caractérisée en ce que les salissures sont des salissures sensibles au blanchiment ou aux enzymes.
  3. Utilisation selon la revendication 1 ou 2, caractérisée en ce que l'autre composé à insaturation éthylénique est choisi parmi les méthacrylates de polyalkylène glycol, en particulier les méthacrylates de polyéthylène glycol, les (méth)acrylates d'alkyle en C1-C24 dans lesquels le groupe alkyle peut être linéaire ou ramifié, en particulier le (méth)acrylate de méthyle, le (méth)acrylate d'éthyle, le (méth)acrylate de butyle, le (méth)acrylate d'éthylhexyle, le (méth)acrylate d'octyle, le (méth)acrylate de décyle, le (méth)acrylate de dodécyle, seuls ou en mélanges.
  4. Utilisation selon l'une des revendications 1 à 3, caractérisée en ce que le polymère peut être obtenu par copolymérisation de 60 à 98 % en poids de N-vinylpyrrolidone, de 1 à 39 % en poids de N-vinylcaprolactame et de 1 à 20 % en poids de l'autre composé à insaturation éthylénique, les pourcentages en poids étant basés sur la quantité totale de monomères présents dans la copolymérisation.
  5. Utilisation selon l'une des revendications 1 à 4, caractérisée en ce que le polymère présente un poids moléculaire moyen (en nombre) compris entre 1 000 et 500 000 g/mol, en particulier entre 1 100 et 150 000 g/mol.
  6. Utilisation selon l'une des revendications 1 à 5, caractérisée en ce que le polymère est ajouté à un bain contenant un agent de lavage ou de nettoyage ou est introduit dans le bain en tant que constituant d'un agent de lavage ou de nettoyage.
  7. Procédé d'élimination en particulier de salissures sensibles au blanchiment ou aux enzymes de textiles ou de surfaces dures, lequel procédé met en œuvre un agent de lavage ou de nettoyage et un polymère pouvant être obtenu par copolymérisation de N-vinylpyrrolidone, de N-vinylcaprolactame et d'un autre composé à insaturation éthylénique, choisi parmi le (méth)acrylate d'alkyle en C1-C24 éventuellement alcoxylé, le (méth)acrylate de polyalkylène glycol, le (méth)acrylamide à substitution N-alkyle, l'acrylonitrile et leurs mélanges.
  8. Agent de lavage ou de nettoyage contenant un polymère pouvant être obtenu par copolymérisation de N-vinylpyrrolidone, de N-vinylcaprolactame et d'un autre composé à insaturation éthylénique, choisi parmi le (méth)acrylate d'alkyle en C1-C24 éventuellement alcoxylé, le (méth)acrylate de polyalkylène glycol, le (méth)acrylamide à substitution N-alkyle, l'acrylonitrile et leurs mélanges.
  9. Agent selon la revendication 8, caractérisé en ce qu'il contient le polymère en des quantités de 0,1 à 10 % en poids, en particulier de 0,2 à 5 % en poids.
  10. Agent selon la revendication 8 ou 9, caractérisé en ce qu'il est liquide et en ce qu'il contient 1 à 90 % en poids, en particulier 10 à 85 % en poids d'eau, d'un solvant hydromiscible ou d'un mélange d'eau et d'un solvant hydromiscible.
EP16732315.3A 2015-07-10 2016-06-28 Principes actifs polymères améliorant le pouvoir détergent Active EP3320073B1 (fr)

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DE102015212963.2A DE102015212963A1 (de) 2015-07-10 2015-07-10 Die Primärwaschkraft verbessernde polymere Wirkstoffe
PCT/EP2016/064904 WO2017009030A1 (fr) 2015-07-10 2016-06-28 Principes actifs polymères améliorant le pouvoir détergent

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AT330930B (de) 1973-04-13 1976-07-26 Henkel & Cie Gmbh Verfahren zur herstellung von festen, schuttfahigen wasch- oder reinigungsmitteln mit einem gehalt an calcium bindenden substanzen
DE3413571A1 (de) 1984-04-11 1985-10-24 Hoechst Ag, 6230 Frankfurt Verwendung von kristallinen schichtfoermigen natriumsilikaten zur wasserenthaertung und verfahren zur wasserenthaertung
US4579681A (en) 1984-11-08 1986-04-01 Gaf Corporation Laundry detergent composition
US4614519A (en) 1984-11-08 1986-09-30 Gaf Corporation Soil release agent for textiles
US5567786A (en) 1996-02-06 1996-10-22 Isp Investments Inc. Polymerizable composition of vinylpyrrolidone and vinyl caprolactam
JP4147067B2 (ja) 2002-08-09 2008-09-10 花王株式会社 洗浄剤組成物
GB0229146D0 (en) * 2002-12-13 2003-01-15 Unilever Plc Polymers and laundry detergent compositions containing them
GB0911294D0 (en) 2009-06-30 2009-08-12 Reckitt Benckiser Nv Composition
DE102011112777A1 (de) 2011-09-09 2013-03-14 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Die Primärwaschkraft verbessernde polymere Wirkstoffe
DE102011112778A1 (de) * 2011-09-09 2013-03-14 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Die Primärwaschkraft verbessernde polymere Wirkstoffe
DE102012024440A1 (de) * 2012-12-14 2014-06-18 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Die Primärwaschkraft verbessernde polymere Wirkstoffe

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EP3320073A1 (fr) 2018-05-16
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