EP3820981A1 - Procédé de production de polymères stables contenant du vinylimidazole - Google Patents

Procédé de production de polymères stables contenant du vinylimidazole

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Publication number
EP3820981A1
EP3820981A1 EP19735565.4A EP19735565A EP3820981A1 EP 3820981 A1 EP3820981 A1 EP 3820981A1 EP 19735565 A EP19735565 A EP 19735565A EP 3820981 A1 EP3820981 A1 EP 3820981A1
Authority
EP
European Patent Office
Prior art keywords
weight
vinylimidazole
acid
quaternary ammonium
polymers
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP19735565.4A
Other languages
German (de)
English (en)
Inventor
Stephan Hueffer
Roland Ettl
Ruediger LUKAS
Andrea SCHILLER
Frank Dietsche
Juergen Detering
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP3820981A1 publication Critical patent/EP3820981A1/fr
Pending legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L39/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions of derivatives of such polymers
    • C08L39/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
    • C08L39/06—Homopolymers or copolymers of N-vinyl-pyrrolidones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/005—Processes for mixing polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C08K5/19—Quaternary ammonium compounds
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/62—Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0021—Dye-stain or dye-transfer inhibiting compositions
    • 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
    • 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
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/12—Soft surfaces, e.g. textile

Definitions

  • the present invention relates to an aqueous mixture containing or consisting of water, 1-vinylimidazole-containing polymer (s) (P) and quaternary ammonium salts (QA), its preparation and use.
  • s 1-vinylimidazole-containing polymer
  • QA quaternary ammonium salts
  • Vinylimidazole (VI) -based polymers are known per se and are used, inter alia, in the detergent industry as color transfer inhibitors.
  • US Pat. No. 5,964,939 A describes aqueous compositions comprising color transfer inhibitors (in particular polypyrrolidone), DE 10 2006 004697 A1 detergents or cleaners comprising, inter alia, a certain ammonium salt as a color transfer inhibitor
  • US 2003/224030 A1 processes and articles for reducing particles in der Lucas and US 2013/108959 A1 the use of a composition containing vinyl monomer-containing polymers and at least one halogen-free biocide.
  • Vinylimidazole (VI) -based polymers pose special challenges to product stability beyond two to three months of storage. Product stability affects microbiological stability on the one hand and physical stability on the other.
  • VI induces the decomposition of most stabilizers or all commercially available stabilizers for the microbiological stability, which the regulatory Meet PT6 requirements of the European Chemical Agency (ECHA) for the detergent industry.
  • ECHA European Chemical Agency
  • detergent formulations usually contain (above all) anionic surfactants. It has therefore previously been assumed that cationic compounds would not be useful as stabilizers in a detergent formulation in terms of physical stability due to interactions.
  • (cationic) quaternary ammonium salts can solve the problems described above, which occur especially with polymers containing vinylimidazole.
  • the addition of at least 0.01% by weight of the salts mentioned results in a formulation which is stable in storage at room temperature for a period of 18 months (or 18 weeks at elevated temperature, 40 ° C.).
  • microbiological activity is also still present after 12 months at room temperature (or 12 weeks at elevated temperature).
  • the performance properties of the detergent formulations with vinylimidazole-containing polymers can be considerably improved.
  • the present invention therefore relates to a process for the preparation of an aqueous mixture comprising or consisting of water, at least one polymer (P) containing 1-vinylimidazole and at least one quaternary ammonium salt (QA), by adding an aqueous solution of at least one quaternary ammonium salt ( QA) to an aqueous solution of at least one 1-vinylimidazole-containing polymer (P) and subsequent mixing.
  • P polymer
  • QA quaternary ammonium salt
  • Another object of the present invention is a method for producing a liquid detergent by producing an aqueous mixture as described in the preceding claims, and adding at least one component selected from the list comprising or consisting of anionic surfactants, non-ionic surfactants, cationic surfactants , amphoteric surfactants, enzymes, optical brighteners, complexing agents, polymers, copolymers, soaps, silicone defoamers, solubilizers, short-chain alcohols, dyes, fragrances and mixtures thereof.
  • the present invention also relates to an aqueous mixture comprising or consisting of at least one 1-vinylimidazole-containing polymer (s) (P) and at least one quaternary ammonium salt (QA).
  • s 1-vinylimidazole-containing polymer
  • QA quaternary ammonium salt
  • the polymers (P) are preferably soluble in water at room temperature.
  • the water content is greater than 10% by weight, preferably greater than 20% by weight, more preferably at least 25% by weight, based on the mixture as a whole.
  • the 1-vinylimidazole-containing polymers (P) are selected from polymers with a vinylimidazole content of larger or equal to 5% by weight, more preferably greater than or equal to 10% by weight, particularly preferably greater than or equal to 15% by weight, based on the polymer (P).
  • the 1-vinylimidazole-containing polymers (P) are homopolymers of 1 -vinylimidazole.
  • the 1-vinylimidazole-containing polymers (P) are selected from copolymers of 1-vinylimidazole with at least one further monomer (A), the at least one further monomer (A) preferably being selected from the list from vinylpiperidone, vinylcaprolactam, 1-vinyloxazolidinone, 4-vinylpyridine-N-oxide, N-vinylformamide, N-vinylacetamide, N-vinyl-N-methylacetamide, acrylamide, basic monomers and their quaternized variants, isoprenol, styrene, 1-alkenes, Vinyl esters, vinyl ethers, (meth) acrylic acid alkyl esters, maleic acid alkyl esters, N, N'-dialkylacrylamides, (meth) acrylic acid, itaconic acid, maleic acid, fumaric acid and its alkali metal salts, monomers containing alkylene oxide groups, and mixtures thereof.
  • the 1-vinylimidazole-containing polymers (P) are selected from copolymers of 1 -vinylimidazole with at least one further monomer (A), the at least one further monomer (A) being 1-vinylpyrrolidone.
  • the 1-vinylimidazole-containing polymers (P) are obtained by polymerizing 1-vinylimidazole and optionally monomer (A), optionally in the presence of up to 50% by weight, preferably up to 30% by weight Polyalkylene glycols, based on the monomers used, the polyalkylene glycols preferably being polyethylene glycols.
  • the 1-vinylimidazole-containing polymers (P) which are liquid at room temperature preferably have a molecular weight Mw of from 2000 to 200,000 g / mol, more preferably 3000 to 100,000 g / mol, particularly preferably 5,000 to 80,000 g / mol (determined by SEC , ie size exclusion chromatography).
  • the quaternary ammonium salts (QA) used are preferably halide salts, particularly preferably selected from the list consisting of bromide salts and chloride salts.
  • counterions according to the invention can be selected, for example, from the list comprising (or consisting of) halides, sulfates, carbonates, tartrates, citrates, lactacte, acetates, formates, hydroxides, methanesulfonates and mono-methyl sulfate.
  • the quaternary ammonium salts (QA) contain at least one alkyl chain, preferably each containing 2 to 20, particularly preferably 4 to 18, methylene groups.
  • the quaternary ammonium salts are particularly preferably selected from the list consisting of didecyldimethylammonium chloride, benzalkonium chloride, cetylalkonium chloride, cetylpyridinium chloride and mixtures thereof.
  • the quaternary ammonium salts (QA) are, in one embodiment, in a proportion of at least 0.01% by weight to 2.0% by weight, preferably 0.01% by weight to 1.0 % By weight, more preferably 0.03 to 0.3% by weight, particularly preferably 0.05 to 0.10% by weight, based on the mixture as a whole.
  • the mixture contains polymers (P) in a proportion of 5 to 90% by weight, preferably 20 to 60% by weight, based on the total mixture.
  • the present invention also relates to a detergent or cleaning agent, preferably liquid detergent, comprising the mixture according to the invention and additionally at least one further component selected from the list comprising or consisting of anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants, enzymes , optical brighteners, complexing agents, polymers, copolymers, soaps, silicone defoamers, solubilizers, short-chain alcohols, dyes, fragrances and mixtures thereof.
  • a detergent or cleaning agent preferably liquid detergent, comprising the mixture according to the invention and additionally at least one further component selected from the list comprising or consisting of anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants, enzymes , optical brighteners, complexing agents, polymers, copolymers, soaps, silicone defoamers, solubilizers, short-chain alcohols, dyes, fragrances and mixtures thereof.
  • the washing or cleaning agent according to the invention preferably liquid detergent
  • preferably liquid detergent preferably comprises the following components:
  • enzymes preferably selected from enzymes, enzyme stabilizers, bases, corrosion inhibitors, defoamers and foam inhibitors, dyes, fragrances, fillers, tabletting aids, disintegrators, thickeners, solubilizers, organic solvents, electrolytes, pH regulators, perfumes , bitter substances
  • builder B also comprises compounds referred to as sequestering agents, builders, complexing agents, chelators, chelating agents or softeners.
  • the bleaching systems C) optionally also contain bleach activators, bleach catalysts and / or bleach stabilizers.
  • the washing and cleaning agent according to the invention particularly preferably comprises at least one enzyme as additive D).
  • the washing and cleaning agents according to the invention contain at least one surfactant as component A).
  • Suitable surfactants A) are nonionic, anionic, cationic or amphoteric surfactants.
  • nonionic surfactants can be used as surfactants A).
  • Alkoxylated alcohols are preferably used as nonionic surfactants. Alkoxylated primary alcohols are preferred. Preferred alkoxylated alcohols are ethoxylated alcohols with preferably 8 to 18 carbon atoms in the alkyl radical and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol.
  • the alcohol residue can be linear or preferably methyl-branched in the 2-position or can contain linear and methyl-branched residues in the mixture, as are usually present in oxo alcohol residues.
  • the ethoxylated alcohols are preferably selected from:
  • Ci2Ci4 alcohols with 3 EO, 5 EO, 7 EO or 9 EO,
  • Ci2Ci8 alcohols with 3 EO, 5 EO, 7 EO or 9 EO and mixtures thereof,
  • a preferred mixture of nonionic surfactants is a mixture of Ci2Ci4 alcohol (lauryl alcohol / myristyl alcohol) with 3 EO and Ci2C-i8 alcohol (lauryl alcohol / myristyl alcohol / cetyl alcohol / stearyl alcohol) with 7 EO.
  • Ci2Ci4 alcohol laauryl alcohol / myristyl alcohol
  • Ci2C-i8 alcohol laauryl alcohol / myristyl alcohol / cetyl alcohol / stearyl alcohol
  • the degrees of ethoxylation given represent statistical mean values (number average, Mn), which can be an integer or a fraction for a specific product.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • Nonionic surfactants containing ethylene oxide (EO) and propylene oxide (PO) groups together in the molecule can also be used.
  • block copolymers with EO-PO block units or PO-EO block units can be used, but also EO-PO-EO copolymers or PO-EO-PO copolymers.
  • mixed alkoxylated nonionic surfactants can also be used, in which the EO and PO units are not distributed in blocks, but are statistically distributed. Such products can be obtained by the simultaneous action of ethylene oxide and propylene oxide on fatty alcohols.
  • Surfactants suitable as component A) are also polyether, preferably with a number average molecular weight of at least 200 g / mol.
  • Suitable polyetheroies can be linear or branched, preferably linear.
  • Suitable polyetherols generally have a number average molecular weight in the range from about 200 to 100,000 g / mol, preferably 300 to 50,000 g / mol, particularly preferably 500 to 40,000 g / mol.
  • Suitable polyether materials are, for example, water-soluble or water-dispersible nonionic polymers which have alkylene oxide repeating units. The proportion of alkylene oxide repeating units is preferably at least 30% by weight, based on the total weight of the compound.
  • Suitable polyether oils are polyalkylene glycols, such as polyethylene glycols, polypropylene glycols, polytetrahydrofurans and alkylene oxide copolymers.
  • Suitable alkylene oxides for the production of alkylene oxide copolymers are e.g. B. ethylene oxide, propylene oxide, epichlorohydrin, 1, 2- and 2,3-butylene oxide.
  • copolymers of ethylene oxide and propylene oxide, copolymers of ethylene oxide and butylene oxide and copolymers of ethylene oxide, propylene oxide and at least one butylene oxide are suitable.
  • the alkylene oxide copolymers can contain the alkylene oxide units randomly distributed or copolymerized in the form of blocks.
  • the proportion of repeating units derived from ethylene oxide in the ethylene oxide / propylene oxide copolymers is preferably 40 to 99% by weight. Ethylene oxide homopolymers and ethylene oxide / propylene oxide copolymers are particularly preferred.
  • alkyl glycosides of the general formula (IV) can also be used as further nonionic surfactants.
  • R 10 represents a primary straight-chain or methyl-branched aliphatic radical having 8 to 22 C atoms
  • G stands for a glycoside unit with 5 or 6 carbon atoms, and i means any number between 1 and 10.
  • R 10 preferably represents an aliphatic radical with 8 to 22, preferably 12 to 18, carbon atoms branched in the 2-position.
  • G preferably represents glucose.
  • the degree of oligomerization i which gives the distribution of monoglycosides and oligoglycosides, is preferably in a range from 1.2 to 1.4.
  • nonionic surfactants which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain , Fatty acid methyl esters, such as are described, for example, in Japanese patent application JP 58/217598 or which are preferably prepared by the process described in international patent application WO 90/13533, are particularly preferred.
  • nonionic surfactants are amine oxides, for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and fatty acid alkanolamides. These nonionic surfactants are preferably used as a mixture with alkoxylated alcohols. The mixture with ethoxylated fatty alcohols is preferred. The amount by weight of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of them.
  • Suitable surfactants A) are polyhydroxy fatty acid amides of the formula (V)
  • R 12 represents hydrogen, an alkyl radical with 1 to 4 carbon atoms or a hydroxyalkyl radical with 1 to 4 carbon atoms
  • R 13 stands for one linear or branched polyhydroxyalkyl radical having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.
  • the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
  • the group of polyhydroxy fatty acid amides also includes compounds of the formula (VI) wherein R 14 for a linear or branched alkyl or alkenyl radical with 7 to 12 carbon atoms, R 15 for a linear, branched or cyclic alkylene radical with 2 to 8 carbon atoms or an arylene radical with 6 to 8 carbon atoms, and R 16 for a linear, is a branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, C 1 -C 4 -alkyl or phenyl radicals being preferred, and R 17 representing a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this radical.
  • R 17 is preferably obtained by reductive amination of a sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • a sugar for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • the N-alkoxy- or N-aryloxy-substituted compounds can then, for example in accordance with WO 95/07331, be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
  • Suitable surfactants A) are also anionic surfactants (anionic surfactants).
  • anionic surfactants are soaps, alkyl sulfonates, alkyl benzene sulfonates, olefin sulfonates, Methyles- tersulfonate, sulfofatty acids, alkyl sulfates, mono- and dialkyl sulfosuccinates, mono- and dialkyl kylsulfosuccinamate, sulfotriglycerides, amide soaps, ether carboxylic acids and salts thereof, fatty klaierithionate acid taurides , N-acylamino acids, such as, for example, acyl lactylates, acyl tartrates, acyl glutamates and acyl aspartates, alkyl oligoglucoside sulfates, alkyl glucose carboxylates, protein fatty acid condensates and alkyl
  • a first preferred embodiment is anionic surfactants of the sulfonate and sulfate type.
  • Preferred surfactants of the sulfonate type are C9-Ci3-alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates, and also disulfonates, such as are obtained, for example, from Ci2-Ci8 monoolefins with a terminal or internal double bond by sulfonating with gaseous sulfur trioxide and subsequent receives alkaline or acidic hydrolysis of the sulfonation products.
  • alkanesulfonates which are obtained from Ci2-Ci8-alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • the esters of a-sulfofatty acids are also suitable, for example the a-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.
  • Other suitable anionic surfactants are sulfonated fatty acid glycerol esters.
  • Fatty acid glycerol esters include the mono-, di- and triesters and their mixtures, as obtained in the production by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol be.
  • Preferred sulfonated fatty acid glycerol esters are the sulfonation products of G
  • saturated fatty acids with 6 to 22 carbon atoms for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
  • Preferred alk (en) yl sulfates are the alkali and in particular the sodium salts of the sulfuric acid semiesters of the Ci2-Ci8 fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the Cio-C2o-oxo alcohols and the half esters secondary Cio-C2o alcohols.
  • alk (en) yl sulfates which contain a synthetic, straight-chain Cio-C2o-alkyl radical produced on a petrochemical basis. These have a degradation behavior similar to that of the adequate compounds based on fatty chemical raw materials.
  • Ci2-Ci6-alkyl sulfates and C12-Ci5-alkyl sulfates as well as Ci4-Ci5-alkyl sulfates are preferred for reasons of washing technology.
  • 2,3-Alkyl sulfates which are produced, for example, according to US Pat. Nos. 3,234,258 or 5,075,041 and can be obtained as commercial products from the Shell Oil Company under the name DAN®, are also suitable anionic surfactants.
  • Ci2-Ci8 fatty alcohols with 1 to 4 EO are suitable among others. Because of their high foaming behavior, they are usually used in cleaning agents only in relatively small amounts, for example in amounts of 1 to 5% by weight.
  • Other suitable anionic surfactants in the context of the present invention are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain Ce-Ci 8 fatty alcohol residues or mixtures thereof. Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols. Again, sulfosuccinates, the fatty alcohol residues of which are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are particularly preferred. It is also possible
  • Alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the Al k (en) yl chain or salts thereof.
  • Soaps are particularly preferred anionic surfactants.
  • Saturated and unsaturated fatty acid soaps are suitable, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, (hydrogenated) erucic acid and behenic acid, and in particular soap mixtures derived from natural fatty acids, for example coconut, palm kernel, olive oil or tallow fatty acids.
  • the anionic surfactants can be in the form of their sodium, potassium or ammonium salts and also as soluble salts of organic bases, such as mono-, di- or triethanolamine.
  • the anionic surfactants are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
  • Suitable surfactants A) are also cationic surfactants. Particularly preferred cationic surfactants are: C7-C 25 alkylamines;
  • Ester quats especially quaternary esterified mono-, di- and trialkanolamines esterified with Ce-C22 carboxylic acids;
  • Imidazoline quats in particular 1 -alkylimidazolinium salts of the formulas VII or VIII
  • R 18 Ci-C25-alkyl or C2-C25-alkenyl
  • R 19 Ci-C4-alkyl or hydroxy-Ci-C4-alkyl
  • R 20 Ci-C4-alkyl, hydroxy-Ci-C4-alkyl or a radical R 21 - (CO) -R 22 - (CH2) r, where R 21 stands for H or Ci-C4-alkyl, R 22 for - O- or -NH- and r is 2 or 3, at least one radical R 18 being a C7-C22-alkyl radical.
  • the surfactants A) can also be amphoteric surfactants.
  • Suitable amphoteric surfactants are alkyl betaines, alkyl amido betaines, alkyl sulfobetaines, aminopropionates, aminoglycinates and amphoteric imidazolium compounds.
  • cocodimethylsulfopropylbetaine, laurylbetaine, cocamidopropylbetaine, sodium cocamphopropionate or tetradecyldimethylamine oxide can be used.
  • the content of surfactants in liquid and gel detergent and cleaning agent compositions is preferably 2 to 75% by weight and in particular 5 to 65% by weight, in each case based on the total composition.
  • the content of surfactants in solid detergent and cleaning agent compositions is preferably 2 to 40% by weight and in particular 5 to 35% by weight, in each case based on the total composition.
  • Builders which are sometimes also referred to as sequestering agents, builders, complexing agents, chelators, chelating agents or softeners, bind alkaline earth metals and other water-soluble metal salts without precipitating. They help break up dirt, disperse dirt, help detach dirt and sometimes have their own washing effect.
  • Suitable builders can be both organic and inorganic in nature. Examples are aluminosilicates, carbonates, phosphates and polyphosphates, polycarboxylic acids, polycarboxylates, hydroxycarboxylic acids, phosphonic acids, eg. B. hydroxyalkylphosphonic acids, phosphates, aminopolycarboxylic acids and their salts and polymeric compounds containing carboxylic acid groups and their salts.
  • Suitable inorganic builders are, for example, crystalline or amorphous aluminosilicates with ion-exchanging properties, such as zeolites.
  • zeolites Different types of zeolites are suitable, in particular zeolites A, X, B, P, MAP and HS in their Na form or in forms in which Na is partially replaced by other cations such as Li, K, Ca, Mg or ammonium.
  • Suitable zeolites are described, for example, in US-A-4604224.
  • Suitable crystalline silicates as builders are, for example, disilicates or layered silicates, e.g. B. 5-Na 2 Si 2 05 or B-Na2Si 2 05 (SKS 6 or SKS 7).
  • the silicates can be used in the form of their alkali metal, alkaline earth metal or ammonium salts, preferably as Na, Li and Mg silicates.
  • Amorphous silicates such as sodium metasilicate, which has a polymer structure, or amorphous disilicate (Britesil® H 20 manufacturer: Akzo) can also be used. Among them, sodium disilicate is preferred.
  • Suitable inorganic builders based on carbonate are carbonates and hydrogen carbonates. These can be used in the form of their alkali metal, alkaline earth metal or ammonium salts. Na, Li and Mg carbonates or bicarbonates, in particular sodium carbonate and / or sodium bicarbonate, are preferably used.
  • Common phosphates used as inorganic builders are alkali metal orthophosphates and / or polyphosphates such as. B. pentasodium triphosphate.
  • Suitable organic builders are, for example, C4-C3o-di-, tri- and tetracarboxylic acids, such as. B. Bernstein acid, propane tricarboxylic acid, butanetetracarboxylic acid, cyclopentanetetracarbon acid and alkyl and alkenyl succinic acids with C2-C2o-alkyl or alkenyl radicals.
  • Suitable organic builders are also hydroxycarboxylic acids and polyhydroxycarboxylic acids (sugar acids). These include C4-C 2 o-hydroxycarboxylic acids such as. As malic acid, tartaric acid, gluconic acid, mucic acid, lactic acid, glutaric acid, citric acid, tartronic acid, glucoheptonic acid, lactobionic acid and sucrose mono -, - di- and tricarboxylic acid.
  • Suitable organic builders are also phosphonic acids, such as. B. hydroxyalkylphosphonic acids, aminophosphonic acids and the salts thereof. These include e.g. B. phosphonobutane tricarboxylic acid, aminotris methylenephosphonic acid, ethylenediaminetetraethylenephosphonic acid, hexamethylenediaminetetramethylenephosphonic acid, diethylenetriamine-pentamethylenephosphonic acid, morpholino-methanediphosphonic acid, 1-hydroxy-ci- to C10-alkyl-1, 1-diphyphosphonic acid such as 1-1-phosphonophosphonic acid. Preferred among these is 1-hydroxyethane-1,1-diphosphonic acid and its salts.
  • Suitable organic builders are also aminopolycarboxylic acids, such as nitrilotriacetic acid (NTA), nitrilomonoacetic dipropionic acid, nitrilotripropionic acid, ß-alanine diacetic acid (ß-ADA), ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid, 1, 3-propylenediamine, 1, 3-propylenediamine, 1, 3-propylenediamine, 1, 3-propylenediamine, 1, 3-propylenediamine, 1, 3-propylenediamine, 1, 3-propylenediamine, 1, 3-propylenediamine, 1, 3-propylenediamine, 1, 3-propylenediamine, 1, 3-propylenediamine, 1, 3-propylenediamine, 1, 3-propylenediamine, 1, 3-propylenediamine, 1, 3-propylenediamine, 1, 3-propylenediamine, 1-3-propylenediamine and
  • Glutamic acid diacetic acid methylglycinediacetic acid (MGDA) and the salts of the aforementioned aminopolycarboxylic acids.
  • Methylglycinediacetic acid, glutamic acid diacetic acid and their salts are preferred.
  • the salts of methylglycinediacetic acid can be present as a racemate, i. H. D and L enantiomers are in an equimolar mixture, or an enantiomer, e.g. B. the L-enantiomer, may be in excess.
  • Suitable organic builders are also polymeric compounds containing carboxylic acid groups, such as acrylic acid homopolymers. These preferably have a number average molecular weight in the range from 800 to 70,000 g / mol, particularly preferably from 900 to 50,000 g / mol, in particular from 1000 to 20,000 g / mol, especially 1000 to 10,000 g / mol.
  • the term acrylic acid homopolymer also includes polymers in which the carboxylic acid groups are partially or completely neutralized. These include acrylic acid homopolymers in which the carboxylic acid groups are partially or completely in the form of alkali metal salts or ammonium salts. Acrylic acid homopolymers in which the carboxylic acid groups are protonated or in which the carboxylic acid groups are partially or completely in the form of sodium salts are preferred.
  • Suitable polymeric compounds containing carboxylic acid groups are also oligomaleic acids, as described, for example, in EP-A 451 508 and EP-A 396 303.
  • Suitable polymeric compounds containing carboxylic acid groups are also terpolymers of unsaturated C4-Ce dicarboxylic acids, the comonomers being monoethylenically unsaturated monomers from group (i) given below in amounts of up to 95% by weight and from group (ii) in amounts of up to 60% by weight and from group (iii) in amounts of up to 20% by weight.
  • suitable unsaturated C4-C8 dicarboxylic acids are maleic acid, fumaric acid, itaconic acid and citraconic acid. Maleic acid is preferred.
  • Group (i) includes monoethylenically unsaturated Ca-Cs monocarboxylic acids such as B.
  • Acrylic acid, methacrylic acid, crotonic acid and vinyl acetic acid From group (i), preference is given to using acrylic acid and methacrylic acid.
  • Group (ii) includes monoethylenically unsaturated C2-C22 olefins, vinyl alkyl ethers with Ci-Ce alkyl groups, styrene, vinyl esters of Ci-Ce carboxylic acids, (meth) acrylamide and vinyl pyrrolidone. From group (ii), preference is given to using C2-C6 olefins, vinyl alkyl ethers with C 1 -C 4 -alkyl groups, vinyl acetate and vinyl propionate.
  • group (ii) contains vinyl esters in copolymerized form, these can also be partially or completely hydrolyzed to vinyl alcohol structural units.
  • Suitable copolymers and terpolymers are known, for example, from US-A 3887806 and DE-A 4313909.
  • Group (iii) includes (meth) acrylic esters of Ci-Cs alcohols, (meth) acrylonitrile,
  • Suitable polymeric compounds containing carboxylic acid groups are also homopolymers of monoethylenically unsaturated C3-Cs-monocarboxylic acids such as.
  • acrylic acid, methacrylic acid, crotonic acid and vinyl acetic acid especially acrylic acid and methacrylic acid, copolymers of dicarboxylic acids, such as. B.
  • Suitable polymeric compounds containing carboxylic acid groups are also copolymers of 50 to 98% by weight of ethylenically unsaturated weak carboxylic acids with 2 to 50% by weight of ethylenically unsaturated sulfonic acids, as are described, for example, in EP-A-0877002.
  • Suitable weak ethylenically unsaturated carboxylic acids are especially C3- C 6 monocarboxylic acids, such as acrylic acid and methacrylic acid.
  • Suitable ethylenically unsaturated sulfonic acids are 2-acetylamidomethyl-1-propanesulfonic acid, 2-methacrylic acid amido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxy-2-benzene sulfonic acid, propenyloxy) propanesulfonic acid, 2-methyl-2-propene-1 sulfonic acid, styrene sulfonic acid, vinyl sulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate, sulfomethylacrylamide, sulfomethyl methacrylamide and salts of these acids.
  • the copolymers may further contain 0 to 30% by weight of ethylenically unsaturated C4-C8 dicarboxylic acids, such as maleic acid, and 0 to 30% by weight of at least one monomer which is copolymerizable with the aforementioned monomers.
  • the latter is, for example, Ci-C4-alkyl ester of (meth) acrylic acid, Ci-C4-hydroxyalkyl ester of (meth) acrylic acid, acrylamide, alkyl-substituted acrylamide, N, N-dialkyl-substituted acrylamide, vinylphosphonic acid, vinyl acetate, allyl alcohols , sulfonated allyl alcohols, styrene and other vinyl aromatics, acrylonitrile, N-vinylpyrrolidone, N-vinylformamide, N-vinylimidazole or N-vinylpyridine.
  • the weight average molecular weight of these copolymers is in the range of 3000 to 50,000 Daltons. Copoly- with about 77% by weight of at least one ethylenically unsaturated C3-C6 monocarboxylic acid and about 23% by weight of at least one ethylenically unsaturated sulfonic acid.
  • Graft polymers of unsaturated carboxylic acids on low molecular weight carbohydrates or hydrogenated carbohydrates are also suitable.
  • Suitable unsaturated carboxylic acids are, for example, maleic acid, fumaric acid, itaconic acid, citraconic acid, acrylic acid, methacrylic acid, crotonic acid and vinyl acetic acid and mixtures of acrylic acid and maleic acid, which are grafted on in amounts of 40 to 95% by weight, based on the component to be grafted.
  • up to 30% by weight, based on the component to be grafted, of additional monoethylenically unsaturated monomers may be present in copolymerized form.
  • Suitable modifying monomers are the above-mentioned monomers of groups (ii) and (iii).
  • polyglyoxylic acids as are described, for example, in EP-B-001004, US-A-5399286, DE-A-4106355 and EP-A-656914.
  • the end groups of the polyglyoxylic acids can have different structures.
  • Polyamidocarboxylic acids and modified polyamidocarboxylic acids are also suitable; these are known for example from EP-A-454126, EP-B-511037, WO-A94 / 01486 and EP-A-581452.
  • Polyaspartic acids and their alkali salts or cocondensates of aspartic acid with other amino acids for example with glycine, glutamic acid or lysine, C4-C 2 5 -mono- or - dicarboxylic acids and / or C4-C25-mono- or -diamines can also be used as polymeric groups containing carboxylic acids Connections are used.
  • polyacrylic acids in partially or completely neutralized form are also preferred.
  • organic builders are iminodisuccinic acid, oxydisuccinic acid, amino polycarboxylates, alkyl polyaminocarboxylates, amino polyalkylene phosphonates, polyglutamates, hydrophobically modified citric acid such as, for example, B. agaricinic acid, poly- [alpha] -hydroxyacrylic acid, N-acylethylenediamine triacetates such as lauroylethylenediamine triacetate and alkylamides of ethylenediaminetetraacetic acid such as EDTA-tallow amide.
  • Oxidized starches can also be used as organic builders.
  • the bleaching systems C) contain at least one bleaching agent and optionally at least one further component, selected from bleach activators, bleach catalysts and bleach stabilizers.
  • Suitable bleaching agents are, for example, percarboxylic acids, e.g. B. Diper-oxododecane dicarboxylic acid, phthalimidopercaproic acid or monoperoxophthalic acid or
  • salts of percarboxylic acids e.g. As sodium percarbonate, adducts of water peroxide with inorganic salts, for. As sodium perborate monohydrate, sodium perborate tetrahydrate, sodium carbonate perhydrate or sodium phosphate perhydrate, adducts of what peroxide to organic compounds, for. B. urea perhydrate, or of inorganic peroxo salts, e.g. B. alkali metal persulfates, or -peroxodisulfates.
  • bleach activators are polyacylated sugars, e.g. B. Pentaacetylglucose; Acyloxybenzenesulfonic acids and their alkali and alkaline earth metal salts, e.g. B. sodium p-nonanoyloxybenzenesulfonate or sodium p-benzoyloxybenzenesulfonate; - N, N-diacylated and N, N, N ', N'-tetraacylated amines, e.g. B.
  • N, N, N ', N'-tetraacetylmethylene diamine and ethylenediamine TAED
  • N, N-diacetylaniline N, N-diacetyl-ptoluidine or 1,3-diacylated hydantoins such as 1,3-diacetyl-5,5 dimethylhydantoin
  • N-alkyl-N-sulfonylcarbonamides e.g. B. N-methyl-N-mesylacetamide or N-methylN-mesylbenzamide
  • N-acylated cyclic hydrazides acylated triazoles or urazoles, e.g. B.
  • monoacetyl maleic acid hydrazide O, N, N-trisubstituted hydroxylamines, e.g. B. 0-benzoyl-N, N-succinylhydroxylamine, 0-acetyl-N, N-succinylhydroxylamine or O, N, N-triacetylhydroxylamine; N, N'-diacylsulfurylamides, e.g. B.
  • O-acetylacetone oxime or bisisopropyliminocarbonate O-acetylacetone oxime or bisisopropyliminocarbonate; Carboxylic anhydrides, e.g. B. acetic anhydride, benzoic anhydride, m-chlorobenzoic anhydride or phthalic anhydride; Enolesters such as B. isopropenyl acetate; 1,3-diacyl-4,5-diacyloxy imidazolines, e.g. B. 1,3-diacetyl-4,5-diacetoxyimidazoline; Tetraacetylglycoluril and tetrapropionylglycoluril; diacylated 2,5-diketopiperazines, e.g. B.
  • Carboxylic anhydrides e.g. B. acetic anhydride, benzoic anhydride, m-chlorobenzoic anhydride or phthalic anhydr
  • 1,4-diacetyl-2,5-diketopiperazine ammonium substituted nitriles such as N-Methylmorpholiniumacetonitrilmethylsulfat; Acylation products of propylene diurea and 2,2-dimethyl-propylene diurea, e.g. B. tetraacetylpropylene diurea; a- acyloxypolyacylmalonamides, e.g. B. a-acetoxy-N, N'-diacetylmalonamide; Diacyl-dioxohexahydro-1, 3,5-triazines, e.g. B.
  • a bleaching system consisting of bleaching agents and bleach activators can optionally also contain bleaching catalysts.
  • Suitable bleaching catalysts are, for example, quaternized imines and sulfonimines, which are described, for example, in US Pat. No. 5,360,569 and EP-A 453 003.
  • Be particularly effective bleaching catalysts are manganese complexes, for example in WO-A 94/21777 are described.
  • detergents and cleaning agents such compounds are used in amounts of up to 1.5% by weight, in particular up to 0.5% by weight, and in the case of very active manganese complexes in amounts of up to 0.1% by weight. -%, incorporated.
  • the detergents and cleaning agents according to the invention can also use systems with enzymatic peroxide release or photoactivated fourth bleaching systems.
  • component D1 Suitable enzymes are those which are usually used as industrial enzymes. This includes both enzymes with optimal activity in the neutral to alkaline pH range, as well as enzymes with optimal activity in the acidic pH range.
  • component D1) additionally comprises at least one enzyme stabilizer. Suitable enzyme stabilizers D1) are those as are usually used.
  • the enzymes are preferably selected from aminopeptidases, amylases, arabinases, carbohydrases, carboxypeptidases, catalases, cellulases, chitinases, cutinases, cyclodextrin glycosyltransferases, deoxyribonucleases, esterases, galactanases, alpha-galactosidases, beta-galactosidases, glucamosases, glucamases, glucamases, Beta glucosidases, haloperoxidases, hydrolase invertases, isomerases, keratinases, laccases, lipases, mannanases, mannosidases, oxidases, pectinolytic enzymes, peptidoglutaminases, peroxidases, peroxygenases, phytases, polyphenol oxidases, proteolytic enzymes, transonglutases, ribonu
  • the enzymes are specifically selected from hydrolases, such as proteases, esterases, glucosidases, lipases, amylases, cellulases, mannanases, other glycosyl hydrolases and mixtures of the aforementioned enzymes. All of these hydrolases contribute to the dissolving and removal of dirt containing protein, fat or starch. Oxireductases can also be used for bleaching. Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus and Humicola insolens are particularly suitable.
  • Suitable proteolytic enzymes can in principle be of animal, vegetable or microbial origin. Proteolytic enzymes of microbial origin are preferred. This also includes chemically or genetically modified mutants.
  • Suitable lipases can generally come from bacteria or fungi. This also includes chemically or genetically modified mutants.
  • a- and / or ⁇ -amylases are suitable.
  • Suitable amylases can generally come from bacteria or fungi. This also includes chemically or genetically modified mutants.
  • Suitable cellulases can generally come from bacteria or fungi. This also includes chemically or genetically modified mutants.
  • Suitable peroxidases / oxidases can in principle come from plants, bacteria or fungi. This also includes chemically or genetically modified mutants.
  • lyases are suitable. Suitable lyases can in principle originate from bacteria or fungi. This also includes chemically or genetically modified mutants.
  • the washing or cleaning agent according to the invention preferably contains at least one enzyme which is selected from proteases, amylases, mannanases, cellulases, lipases, pectin lyases and mixtures thereof.
  • the washing or cleaning agent according to the invention preferably contains at least one protease and / or amylase.
  • the washing, cleaning and dishwashing detergent according to the invention preferably contains an enzyme mixture.
  • enzyme mixtures which contain or consist of the following enzymes are preferred:
  • Amylase, cellulase and lipase or lipolytic enzymes
  • Protease protease
  • lipase or lipolytic enzymes
  • cellulase cellulase
  • the enzymes can be adsorbed on carriers in order to protect them against premature decomposition.
  • the washing or cleaning agent according to the invention can also contain enzyme stabilizers D1).
  • enzyme stabilizers D1 include e.g. As calcium propionate, sodium formate, boric acids, boronic acids and their salts, such as 4-formylphenylboronic acid, peptides and peptide derivatives, such as. B. peptide aldehydes, polyols such as 1, 2-propanediol, and mixtures thereof.
  • the washing or cleaning agents according to the invention preferably contain the enzymes in an amount of 0.1 to 5% by weight, particularly preferably 0.12 to 2.5% by weight, based on the total weight of the washing or cleaning agents.
  • any known thickener rheology modifier
  • Suitable thickeners can be of natural origin as well as synthetic.
  • thickeners of natural origin are xanthan, locust bean gum, guar flour, carrageenan, agar, tragacanth, gum arabic, alginates, modified starches, such as hydroxyethyl starch, starch phosphate esters or starch acetates, dextrins, pectins and cellulose derivatives, such as carboxymethyl cellulose, hydroxylethyl cellulose, hydroxylethyl cellulose, cellulose, methyl cellulose and the like.
  • Thickeners of natural origin are also inorganic thickeners, such as polysilicic acids and clay minerals, e.g. B. layered silicates, as well as the silicates mentioned in the builders.
  • synthetic thickeners are polyacrylic and polymethacrylic compounds, such as (partially) crosslinked homopolymers of acrylic acid, for example with an allyl ether of saccharose or pentaerythritol or with propylene crosslinked homopolymers of acrylic acid (carbomer), for. B. the Carbopol® brands from BF Goodridge (e.g. Carbopol® 676, 940, 941, 934 and the like) or the Polygel® brands from 3V Sigma (e.g.
  • Polygel® DA copolymers of ethylenically unsaturated saturated mono- or dicarboxylic acids, for example terpolymers of acrylic acid, methacrylic acid or maleic acid with methyl or ethyl acrylate and a (meth) acrylate, which is derived from long-chain ethoxylated alcohols, for example the Acusol® brands from Rohm & Haas (e.g. Acusol® 820 or 1206A), copolymers of two or more monomers, which are selected from acrylic acid, methacrylic acid and their Ci-C4-alkyl esters, e.g. B.
  • copolymers of methacrylic acid, butyl acrylate and methyl methacrylate or of butyl acrylate and methyl methacrylate e.g. B. the Aculyn® and Acusol® brands from Rohm & Haas (e.g. Aculyn® 22, 28 or 33 and Acusol® 810, 823 and 830), or crosslinked high molecular acrylic copolymers, for example with an allyl ether from Sucrose or pentaerythritol cross-linked copolymers of C10-C30-alkyl acrylates with one or more comonomers, which are selected from acrylic acid, methacrylic acid and their Ci-C4-alkyl esters (e.g. Carbopol® ETD 2623, Carbopol® 1382 or Carbopol® AQUA 30 from Rohm & Haas).
  • Ci-C4-alkyl esters e.g. Carbopol® ETD 2623, Carb
  • Examples of synthetic thickeners are furthermore reaction products of maleic acid polymers with ethoxylated long-chain alcohols, e.g. B. the Surfonic L series from Texaco Chemical Co. or Gantrez AN-1 19 from ISP; Polyethylene glycols, polyamides, polyimines and polycarbon acids.
  • Preferred thickeners are xanthans and the above-mentioned polyacrylics and poly
  • Suitable organic solvents are selected from monohydric or polyhydric alcohols, alkanolamines or glycol ethers. They are preferably selected from ethanol, n- or i-propanol, butanols, glycol, propane or butanediol, glycerol, diglycol, propyl or butyl diglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol methyl ether, Diethyl englycol ethyl ether, propylene glycol methyl, ethyl or propyl ether, dipropylene glycol monomethyl or ethyl ether, di-isopropylene glycol monomethyl or ethyl ether, methoxy, ethoxy or butoxytriglycol, i-butoxyeth
  • Suitable foam inhibitors or defoamers are, for example, soaps, paraffins or silicone oils, which can optionally be applied to carrier materials.
  • Suitable bases are alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal carbonates, alkaline earth metal carbonates, ammonium carbonate, alkali metal hydrogen carbonates, alkaline earth metal hydrogen carbonates, ammonium hydrogen carbonate and mixtures thereof. Na, Li and Mg carbonates or
  • Hydrogen carbonates in particular sodium carbonate and / or sodium hydrogen carbonate, are used.
  • washing or cleaning agents according to the invention can contain further additives D6) which further improve the application technology and / or aesthetic properties.
  • preferred agents contain, in addition to the components mentioned above, at least one further additive which is selected from electrolytes, pH regulators, perfume carriers, bitter substances, fluorescent agents, hydrotropes, anti-redeposition agents, optical brighteners, graying inhibitors, anti-shrink agents, anti-crease agents, (if appropriate, further ) Color transfer inhibitors, antimicrobial agents, antioxidants, anti-yellowing agents, corrosion inhibitors, antistatic agents, ironing aids, phobing and impregnating agents, swelling and anti-slip agents and UV absorbers.
  • suitable color transfer inhibitors are, in particular, homopolymers or copolymers which contain at least one copolymerized copolymer which is selected from N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylimidazole, 2-vinylpyridine, 4-vinylpyridine, salts of the three the latter monomers, 4-vinylpyridine-N-oxide, N-carboxymethyl-4-vinylpyridinium halides and mixtures thereof.
  • graying inhibitors and / or detergency boosters carboxymethyl cellulose
  • Graft polymers of vinyl acetate on carbohydrates e.g. B. on degraded starch
  • Alkoxylated oligo- and polyamines e.g. B. ethoxylated hexamethylenediamine, which may also be present in quaternized and / or sulfated form, or alkoxylated polyethyleneimine with 16 to 24 EO per NH,
  • Copolymers based on styrene and maleic acid which may also be modified with end-capped polyethylene glycol,
  • Copolymers based on styrene and acrylic acid are Copolymers based on styrene and acrylic acid.
  • washing, cleaning or dishwashing detergents In order to improve the aesthetic impression of the washing, cleaning or dishwashing detergents according to the invention, they can be colored with suitable dyes.
  • Preferred dyes the selection of which is not difficult for the person skilled in the art, have a high storage stability and insensitivity to the other ingredients of the compositions and to light, and no pronounced substantivity towards textile fibers in order not to dye them.
  • the washing, cleaning or dishwashing agents according to the invention can contain at least one bitter substance.
  • Bitter substances are used specifically to prevent accidental ingestion of the agents, for example by small children. Suitable bitter substances are known to the person skilled in the art.
  • an unmodified polyethyleneimine can also be added to the detergents, cleaning agents or dishwashing agents according to the invention (preferably liquid detergents).
  • Modified polyethyleneimine preferably in an amount of up to 5% by weight, can also be added to the washing, cleaning or dishwashing agents (preferably liquid detergents) according to the invention (based on the overall formulation).
  • washing, cleaning or dishwashing agents preferably liquid detergents
  • the polyethyleneimine polymer has a polyethyleneimine backbone with a molecular weight of about 300 to about 10,000, a weight average molecular weight, preferably from about 400 to about 7500, a weight average molecular weight and preferably about 500 to about 5000, preferably from about 500 to 2500 weight average molecular weights with a distribution Q in the range of 1.0 to 4.5.
  • the modification of the polyethyleneimine backbone comprises one or two alkoxylation modifications per nitrogen atom, depending on whether the modification takes place on an internal nitrogen atom or on a terminal nitrogen atom in the polyethyleneimine backbone, the alkoxylation modification consisting of the replacement of a hydrogen atom on a polyalkoxylene chain with an average of about 1 to about 40 ethylene oxide (EO), propylene oxide (PO), butylene oxide (BuO). EO and / or PO are preferably used.
  • Another object of the present invention is also a process for the preparation of a mixture according to the invention by adding an aqueous solution of at least one quaternary ammonium salt (QA) to an aqueous solution of at least one 1-vinylimidazole-containing polymer (P) and subsequent mixing.
  • QA quaternary ammonium salt
  • P 1-vinylimidazole-containing polymer
  • the aqueous solution of at least one quaternary ammonium salt (QA) can be added in the cooling phase after the polymerization.
  • the aqueous solution of at least one quaternary ammonium salt (QA) can also be added during the dilution of the mixture (to adjust the solids content).
  • the aqueous solution of at least one quaternary ammonium salt (QA) can also be added later in the storage or transport tank, for example by online metering. Combinations of these variants are also conceivable, e.g. B.
  • the present invention also relates to a process for stabilizing polymers (P) containing 1-vinylimidazole (P) by adding at least one quaternary ammonium salt (QA) and the use of at least one quaternary ammonium salt (QA) for stabilizing 1 -vinylimidazole- containing polymers (P).
  • Another object of the present invention is the use of at least one quaternary ammonium salt (QA) for stabilizing liquid detergent formulations containing 1-vinylimidazole-containing polymers (P).
  • QA quaternary ammonium salt
  • the mixture according to the invention can moreover also be used for textile finishing (finishing and textile care) and for the treatment of cellulose and cotton fibers (including non-wovens).
  • the mixtures according to the invention are also suitable, inter alia, for textile dyeing (for example as a constituent of a leveling agent or stripping agent or aftersoap agent) and for textile printing.
  • the polymerization of the monomers usually takes place in an inert gas atmosphere, e.g. B. nitrogen, argon or helium. Good mixing of the reactants is generally ensured during the polymerization.
  • the polymerization is carried out in particular in water or mixtures of water and at least one C1 to C4 alcohol (in any ratio as solvent). Suitable alcohols are methanol, ethanol, n-propanol, isopropanol, n-butanol, tert. -Butanol and isobutanol. Of the alcohols, isopropanol is preferably used.
  • the monomers are polymerized in the presence of up to 50% by weight of polyalkylene glycols (based on the mass of the monomers used), in particular in the presence of up to 50% by weight of polyethylene glycols (based on the mass of the monomers used) , Polyethylene glycols with a molar mass of 200 g / mol up to 10000 g / mol are preferably used.
  • the polymerization temperature is preferably in the range from 50 to 100 ° C. If the polymerization is carried out at higher temperatures, e.g. at temperatures up to 150 ° C, it is carried out in pressure-tight sealed apparatus.
  • the monomers are polymerized by free radicals, ie to initiate the homo- and copoly merization, compounds are required which form free radicals under the polymerization conditions.
  • radical initiators are all the usual peroxy and azo compounds, for example peroxides, hydroperoxides and peroxyesters such as hydrogen peroxide, dibenzoyl peroxide, di-t-butyl peroxide, t-butyl hydroperoxide, t-butyl peroxypivalate and t-butyl peroxy-2-ethylhexanoate and azo compounds such as 2 , 2'-Azobis (2-amidinopropane) dihydrochloride, 2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, 2,2'-azobisisobutyronitrile, 2,2'-azobis ( 2-methylbutyronitrile) and dimethyl 2,2'-azo-bis (2-methylpropionate).
  • initiator mixtures or the known redox initiators (for example t-butyl hydroperoxide / sodium bisulfite).
  • the initiators are used in the usual amounts, e.g. B. in amounts of 0.2 to 6 wt .-%, based on the monomers to be polymerized. If the Po- If the polymerization is carried out in water or in mixtures of water and at least one of the abovementioned alcohols as solvents, water-soluble azo initiators are preferably used.
  • the polymerization is preferably carried out in the presence of polymerization regulators which preferably contain sulfur in bound form.
  • polymerization regulators which preferably contain sulfur in bound form.
  • Compounds of this type are, for example, inorganic hydrogen sulfites, disulfites and dithionites or organic sulfides, disulfides, polysulfides, sulfoxides, sulfones and mercapto compounds.
  • polymerization regulators are mentioned by way of example: di-n-butyl sulfide, di-n-octyl sulfide, diphenyl sulfide, thiodiglycol, ethylthioethanol, diisopropyl disulfide, di-n-butyl disulfide, di-n-hexyl disulfide, di-acetyl disulfide, diethanol butyl sulfide, di-sulfide and dimethyl sulfoxide.
  • Compounds preferably used as polymerization regulators are mercapto compounds, dialkyl sulfides, dialkyl disulfides and / or diaryl sulfides.
  • Examples of these compounds are ethyl thioglycolate, cysteine, 2-mercaptoethanol, 1, 3-mercaptopropanol, 3-mercaptopropan-1, 2-diol, 1, 4-mercaptobutanol, mercaptoacetic acid, 3-mercaptopropionic acid, mercapto-succinic acid, thioglycerin, thioohanoic acid, thioglycerin, and thiooganoic acid such as n-butyl mercaptan, n-hexyl mercaptan or n-dodecyl mercaptan.
  • Polymerization regulators used with particular preference are mercapto alcohols and mercaptocarboxylic acids.
  • the polymerization regulators which contain sulfur in bound form are used in amounts of 0.1 to 15, preferably 0.3 to 10% by weight, based on the monomers used in the polymerization. Mixtures of the polymerization regulators to be used can of course also be used in the polymerization.
  • the monomers can be polymerized by the usual process techniques, e.g.
  • the reaction mixture is stirred at the polymerization temperature until the conversion is more than 99%.
  • the initiator can optionally also be added only after the polymerization temperature has been reached.
  • the feed methods represent further process variants for the polymerization.
  • a solution of the preferred sulfur contained in bound form of polymerization regulator and an initiator solution are added continuously or in portions to the mixture of monomers and a solvent at the polymerization temperature at a particular time.
  • Another method is to add the initiator below or at the polymerization temperature to the template and only the regulator or a solution of the regulator after reaching the polymerization temperature within a predetermined period of time to the reaction mixture.
  • the template is heated to a temperature at which the polymerization takes place and then regulator, initiator and monomers are added in separate runs or added together.
  • water or a mixture of water, monomer and / or initiator and / or regulator is preferably used as a template.
  • the polymerization regulators which preferably contain sulfur in bound form, are added continuously or in portions during the polymerization of the monomers. If the monomers are polymerized in the presence of polyalkylene glycols, the polyalkylene glycols are preferably submitted, so they are part of the template.
  • the solutions formed during the polymerization can be subjected to a physical or chemical deodorization after the polymerization process.
  • chemical aftertreatment polymerization initiators or mixtures of several polymerization initiators are added and the polymer solution is heated to temperatures which are above the polymerization temperature, if appropriate. Polymer solutions low in residual monomers are obtained in particular by chemical aftertreatment.
  • the polymers can be isolated from the aqueous polymerization medium, for example by spray drying or spray granulation. Other drying processes, for example evaporating the polymer solution and grinding the residue or freeze-drying, are also possible.
  • the polymers (P) can contain vinyl esters as co-monomers (A) in addition to vinylimidazole.
  • Preferred vinyl esters are selected from the list consisting of vinyl acetate, vinyl propionate, vinyl laurate and mixtures thereof.
  • the polymers (P) can contain vinyl ethers as co-monomers (A) in addition to vinylimidazole.
  • Preferred vinyl ethers are selected from the list consisting of methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, 2-ethylhexyl vinyl ether and mixtures thereof.
  • the polymers (P) can contain 1-alkenes as co-monomers (A) in addition to vinylimidazole.
  • Preferred 1-alkenes are selected from the list consisting of isobutene, 1-hexene, 2-methyl-1-pentene, 1-octene, 2,4,4-trimethylpentene, C18-alkene and mixtures thereof.
  • the polymers (P) can contain N, N-dialkylacrylamides as co-monomers (A) in addition to vinylimidazole.
  • N, N-dialkylacrylamides are selected from the list consisting of N, N-dimethyllacrylamide, N, N-diethylacrylamide and mixtures thereof.
  • the polymers (P) can contain, in addition to vinylimidazole (meth) acrylic acid esters, as co-monomers (A).
  • Preferred (meth) acrylic acid esters are selected from the list consisting of (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester and mixtures thereof.
  • the polymers (P) can contain basic co-monomers (A) in addition to vinylimidazole.
  • Suitable monomers of this type are, for example, N, N'-dialkylaminoalkyl (meth) acrylates, e.g. Dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, diethylaminopropyl (meth) acrylate, dimethylaminobutyl (meth) acrylate, dimethylaminoneopentyl (meth) acrylate.
  • Other suitable basic monomers of this group are N, N'-dialkylaminoalkyl (meth) acrylamides, e.g.
  • N, N'-Di-Ci-to C3-alkylamino-C2-C6-alkyl (meth) acrylamides such as dimethylaminoethyl (meth) acrylamide, diethylaminoethyl (meth) acrylamide, dipropylaminoethyl (meth) acrylamide, dimethylaminopropyl (meth ) acrylamide, diethylaminopropyl (meth) acrylamide, dimethylaminoneopentyl- (meth) acrylamide and dialkylaminobutylacrylamide.
  • alkylvinylimidazoles such as 2-methyl-1-vinylimidazole, 4-vinylpyridine, 2-vinylpyridine, 1-vinyltriazole and diallyl (di) alkylamines in which the alkyl group has 1 to 12 carbon atoms.
  • the above-mentioned basic monomers are used in the copolymerization in the form of the free bases, the salts with organic or inorganic acids or in quaternized form.
  • carboxylic acids with 1 to 7 carbon atoms e.g.
  • Formic acid acetic acid or propionic acid, benzenesulfonic acid, p-toluenesulfonic acid, methanesulfonic acid or inorganic acids such as hydrohalic acids, for example hydrochloric acid.
  • the basic monomers exemplified above can also be used in quaternized form.
  • alkyl halides with 1 to 18 carbon atoms in the alkyl group are suitable, e.g. Methyl chloride, methyl bromide, methyl iodide, ethyl chloride, propyl chloride, hexyl chloride, dodecyl chloride, lauryl chloride and benzyl halides, in particular benzyl chloride.
  • the quaternization of the nitrogen-containing basic monomers can also be carried out by reacting these compounds with dialkyl sulfates, in particular diethyl sulfate or dimethyl sulfate.
  • Examples of quaternized monomers in this group are trimethylammoniumethyl methacrylate chloride, dimethylethylammoniumethyl methacrylate ethyl sulfate and dimethylethylammonium ethyl methacrylamide ethyl sulfate.
  • quaternized monomers are 1-vinylimidazolium compounds.
  • quaternized 1-vinylimidazoles are 3-methyl-1-vinylimidazolium chloride, 3-methyl-1-vinylimidazolium methyl sulfate, 3-benzyl-1-vinyl-imidazalium chloride, 3-n-dodecyl-1 - vinylimidazolium chloride and 3-n-octadecyl-1 -vinylimidazoliumchlorid.
  • the quaternization can also be polymer-analogous by reaction of the basic monomers. polymers with the alkylating agents listed above, for example.
  • the polymers (P) can contain, besides vinylimidazole, alkylene oxide-containing co-monomers (A).
  • X 0, 1 or 2
  • K and I are independent integers from 0 to 100, the sum of k and I being at least 2, preferably at least 5,
  • R 1 is hydrogen or Ci-Ce-alkyl
  • R 2 is hydrogen, C 1 -C 30 alkyl, C 2 -C 30 alkenyl or C 5 -Ce cycloalkyl, and
  • XO is or a group of the formula NR 3 , where R 3 is H, alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl or hetaryl.
  • a mixture of 15 g of 1-vinylpyrrolidone, 5 g of 1-vinylimidazole, 0.3 g of mercaptoethanol and 85 g of water is heated to a temperature of 62 ° C. with stirring and nitrogen gas. After this temperature has been reached, a mixture of 258 g of 1-vinylpyrrolidone, 12 g of 1-vinylimidazole, 2.9 g of mercaptoethanol and 485 g of water is added as feed 1 and a solution of 5.8 g of 2,2'- azobis [2- (2-imidazolin-2- yl) propane] dihydrochloride in 100 g of water metered in over 3 hours.
  • reaction mixture is then stirred at 62 ° C. for 30 minutes and then with an aqueous solution of 1.5 g of 2,2'-azobis [2- (2-imidazolin-2-yl-) propane] dihydrochloride in 10 g of water were added within 5 minutes and the mixture was stirred at 62 ° C. for 2.5 hours. 980.5 g of a yellow, clear aqueous polymer solution are obtained. The solids content of the polymer solution is 30.3%.
  • a mixture of 15 g of 1-vinylpyrrolidone, 5 g of 1-vinylimidazole, 0.3 g of mercaptoethanol and 85 g of water is heated to a temperature of 62 ° C. with stirring and nitrogen gas.
  • a mixture of 10 g of 1-vinylpyrrolidone, 10 g of 1-vinylimidazole, 0.3 g of mercaptoethanol and 85 g of water is heated to a temperature of 62 ° C. with stirring and nitrogen gas in a 1.5 liter polymerization apparatus.
  • a mixture of 10 g of 1-vinyl pyrrolidone, 10 g of 1-vinyl imidazole, 0.3 g of mercaptoethanol and 85 g of water is heated to a temperature of 62 ° C. with stirring and nitrogen gas.
  • Example P5 125 g of 1-vinylpyrrolidone, 125 g of 1-vinylimidzole and 500 g of water are placed in a 1.51 stirring apparatus and heated to 75 ° C. with nitrogen purging and stirring. As soon as the reaction mixture has reached a temperature of 75 ° C., a solution of 5.0 g of 2,2'-azobis (2-amidinopropane) dihydrochloride in 50 ml of water is metered in as feed 1 over the course of 120 minutes and as feed 2, a solution of 6.0 g of mercaptoethanol in 50 ml of water within 100 minutes.
  • the reaction mixture is stirred for 30 minutes at a temperature of 75 ° C., then 1.0 g of 2,2′-azobis (2-amidinopropane) dihydrochloride is added, and the mixture is stirred at 75 ° for a further 2 hours C stirred. 860.5 g of a yellow, clear aqueous polymer solution are obtained. The solids content of the polymer solution is 30.4%.
  • Example P5 is repeated with the exception that, as feed 1, a solution of 5.0 g of 2,2'-azobis- (2-amidinopropane) dihydrochloride in 50 ml of water within 90 minutes and as feed 2, a solution of 10, 0 g of mercaptoethanol in 50 ml of water is metered in over 60 minutes. This gives 861.1 g of a yellow polymer solution. The solids content of the polymer solution is 30.5%.
  • reaction mixture is then stirred for a further 30 minutes at 85 ° C., followed by 1.51 of a 10% strength solution of 2,2′-azobis- (2-amidinopropane) dihydrochloride and a 2-hour stirring time at 75 ° C. 131.1 kg of yellow, clear aqueous polymer solution are obtained.
  • the solids content of the polymer solution is 30.5%.
  • a mixture of 16 kg of polyethylene glycol with a molar mass of 600 g / mol and 80 kg of water is heated to a temperature of 80 ° C. with stirring and nitrogen gas. After this temperature has been reached, feed 1 is started with 40 kg of 1-vinylpyrrolidone, the metering rate for a metering in 3 hours being selected. With an offset of 20 minutes, feed 2 consisting of 20 kg of 1-vinylimidzole (metered in 3 hours) and feed 3 consisting of a solution of 1200 g of 2,2'-azo-bis- (2-amidinopropane) dihydrochloride are run in parallel in 22 kg of water which is dosed within 3.5 hours.
  • reaction mixture is then stirred at 80 ° C. for 30 minutes and then added over the course of 5 minutes with an aqueous solution of 120 g of 2,2'-azobis- (2-amidinopropane) di-hydrochloride in 2.2 kg of water, and 2 Stirred at 80 ° C for 5 hours. After cooling, a yellow, clear and low-odor aqueous polymer solution is obtained. The solid content of the polymer solution is 40.7%.
  • a mixture of 300 g of 1-vinylimidazole and 400 g of water is heated to a temperature of 80 ° C. in a nitrogen atmosphere with stirring. After this temperature has been reached, a solution of 9 g of mercaptoethanol in 50 g of water is metered in as feed 1 within 2 hours and a feed of 7.5 g of azobis (2-methylbutyronitrile) in 70 g of isopropanol is metered in as feed 2 within 3 hours.
  • the reaction mixture is then stirred for 1 hour at a temperature of 80 ° C., then a solution of 1.5 g of azobis (2-methylbutyronitrile) in a little isopropanol is added, and the reaction mixture is stirred for a further 3 hours at 80 ° C.
  • the isopropanol is then removed from the reaction mixture using steam distillation. A yellow, clear and low-odor aqueous polymer solution is obtained.
  • the homopolymer of 1-vinylimidazole has a molecular weight of 25300 g / mol.
  • the solids content of the polymer solution is 41.6%.
  • the column (NOVEMA Max Ultrahigh) had a length of 30 cm with a diameter of 8 mm.
  • a modified acrylate copolymer network was used as the separating material.
  • the following stabilizers for VI-containing polymers (here: aqueous solution of a copolymer of vinylpyrrolidone and vinylimidazole) were investigated.
  • MIT, BIT, CMIT, OIT, DCOIT and iodopropynyl butyl carbamate were determined by RP chromatography with UV detection after dilution of the sample to be examined. An RP18 column with an eluent made from acid-methanol was used. Mixture under isocratic conditions.
  • Quaternary ammonium salts ie DDAC, BAC, 16-BAC and CPC, were determined by LC chromatography with an eluent water / formic acid / ammonium formate. iodine color number according to DIN 6162: 2014-09)
  • Microbiological results to freshly formulated, i.e. test series of 4 weeks is started immediately) and after 60d storage at 40 ° C (i.e. the 4 week microbial test is started with the sample stored at 40 ° C for 60 days)
  • the test described below is carried out to determine the preservative effect of chemical preservatives in water-containing products and systems, the principle of the method described reflecting the effectiveness of chemical preservatives with regard to the pot keeping of water-containing products / systems under the conditions of the use of Correspond to laundry products / consumer products by the consumer.
  • the preservatives to be investigated are added in concentrations that correspond to those of the suppliers (e.g. Thor, Speyer) from the literature or the manufacturer's information. In this study, we focused on the upper range, which had always led to excellent results for aqueous polymers for laundry with the exception of the Vl-containing polymer.
  • a constant microorganism load is achieved by periodic inoculation of the test batches before the smears of each batch are immediately made in parallel with the vaccination.
  • the assessment is based on the microbial growth of the strips. The longer the time until microbial growth first appears, the more effective a preservative is.
  • test organisms for the preservation test are the following microorganisms:
  • Alcaligenes faecalis Yeast Alcaligenes faecalis Yeast:
  • test batches are inoculated a total of four times and once a week and streaked once a week on an agar plate, the first streak is carried out immediately before the new vaccination.
  • the preservative effect takes place in a semi-quantitative method via the growth of the individual strips after the evaluation of - over + to +++. The result of the preservative is repeatedly proven to be solid, ie +++ - determines the microbial growth.
  • the test for ten weeks shows the surprising increase in activity of the preparations according to the invention, i. H. extended ten vaccination cycles.
  • the mixtures according to the invention were tested in model liquid detergent formulations. As can be seen from the data below, there was no deterioration in the (physical) stability when using the mixtures according to the invention containing VI polymers and quaternary ammonium salts compared to the use of the VI polymers without stabilizer.
  • composition of the detergent formulations :
  • WM1 5.5 g linear alkylbenzenesulfonic acid, 2.4 g coconut fatty acid K12-18, 7.7 g C12-C14 alcohol + 2 mol EO + sulfate, Na salt (C12-C14 ether sulfate), 2.2 g KOH, 5.4 g C13-C15 oxo alcohol + 7 mol EO, 6.0 g 1, 2-propylene glycol, 2.0 g ethanol and water to 90g
  • WM2 6.6 g linear alkylbenzenesulfonic acid, 2.4 g coconut fatty acid K12-18, 9.3 g C12-C14 alcohol + 2 mol EO + sulfate, Na salt (C12-C14 ether sulfate), 2.5 g KOH, 3.3 g C13-C15 oxo alcohol + 7 mol EO, 6.0 g 1, 2-propylene glycol, 2.0 g ethanol and water to 90g
  • the VI polymers without and with the quaternary ammonium salt preservative were mixed into the detergent WM1 or WM2 with stirring (room temperature, 60 min). The stability and the appearance of the detergents were assessed immediately, after 7d and after 28d (storage at 25 ° C.).
  • Aqueous mixture containing or consisting of water, at least one 1-vinylimidazole-containing polymer (P) and at least one quaternary ammonium salt (QA).
  • P 1-vinylimidazole-containing polymer
  • QA quaternary ammonium salt
  • the 1-vinylimidazole-containing polymers (P) being selected from polymers with a vinylimidazole content of greater than or equal to 5% by weight, preferably greater than or equal to 10% by weight preferably greater than or equal to 15% by weight, based on the polymer (P).
  • the 1-vinylimidazole-containing polymers (P) being homopolymers of 1 -vinylimidazole.
  • the 1-vinylimidazole-containing polymers (P) are selected from copolymers of 1-vinylimidazole with at least one further monomer (A).
  • the 1-vinylimidazole-containing polymers (P) being selected from copolymers of 1 -vinylimidazole with at least one further monomer (A), and the at least one further monomer (A) being selected from the list consisting of vinylpiperidone, vinylcaprolactam, 1-vinyloxazolidinone, 4-vinylpyridine-N-oxide, N-vinylformamide, N-vinylacetamide, N-vinyl-N-methylacetamide, acrylamide, basic monomers and their quaternized variants, isoprenol, styrene, 1-alkenes , Vinyl esters, vinyl ethers, (meth) acrylic acid alkyl esters, maleic acid alkyl esters, N, N'-dialkylacrylamides, (meth) acrylic acid, itaconic acid, maleic acid, fumaric acid and its alkali metal salts, monomers containing alkylene oxide groups, and mixtures thereof.
  • the 1-vinylimidazole-containing polymers (P) being obtained by polymerizing 1 -vinylimidazole and optionally monomer (A), optionally in the presence of up to 50% by weight, preferably up to 30 % By weight of polyalkylene glycols, based on the monomers used.
  • the quaternary ammonium salts being halide salts, preferably selected from the list consisting of bromide salts and chloride salts.
  • the quaternary ammonium salts being selected from the list consisting of didecyldimethylammonium chloride. rid, benzalkonium chloride, cetylalkonium chloride, cetylpyridinium chloride and mixtures thereof.
  • Liquid detergent containing the mixture according to one of the preceding variants and additionally at least one component selected from the list comprising or consisting of anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants, enzymes, optical brighteners, complexing agents, polymers , Copolymers, soaps, silicone defoamers, solubilizers, short-chain alcohols, dyes, fragrances and mixtures thereof.
  • QA quaternary ammonium salt
  • P 1-vinylimidazole-containing polymer
  • Process for stabilizing 1-vinylimidazole-containing polymers by adding at least one quaternary ammonium salt (QA).

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Abstract

La présente invention concerne des mélanges aqueux à base ou constitués d'eau, d'un ou de plusieurs polymères (P) contenant du 1-vinylimidazole et de sels ammoniacaux quaternaires (QA), ainsi que la production et l'utilisation de ces mélanges.
EP19735565.4A 2018-07-11 2019-07-03 Procédé de production de polymères stables contenant du vinylimidazole Pending EP3820981A1 (fr)

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WO2023242276A1 (fr) 2022-06-15 2023-12-21 Omya International Ag Agent de stabilisation au stockage pour formulations aqueuses d'entretien ménager
CN115057965B (zh) * 2022-07-01 2023-08-01 漳州华福化工有限公司 一种n-乙烯吡咯烷酮/1-乙烯基咪唑共聚物的制备方法

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