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WO2024213278A1 - Détergents et produits de nettoyage comprenant des adjuvants de détergence polymères - Google Patents

Détergents et produits de nettoyage comprenant des adjuvants de détergence polymères Download PDF

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Publication number
WO2024213278A1
WO2024213278A1 PCT/EP2024/050838 EP2024050838W WO2024213278A1 WO 2024213278 A1 WO2024213278 A1 WO 2024213278A1 EP 2024050838 W EP2024050838 W EP 2024050838W WO 2024213278 A1 WO2024213278 A1 WO 2024213278A1
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Prior art keywords
acid
mol
alkali
mixtures
diols
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PCT/EP2024/050838
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German (de)
English (en)
Inventor
Kira NEUBAUER
Christian Kropf
Janice Mahnke
Benjamin ORGIS
Bernhard PUTZ
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Publication of WO2024213278A1 publication Critical patent/WO2024213278A1/fr
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Classifications

    • 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
    • C11D3/3788—Graft polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/01—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to unsaturated polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
    • 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
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • 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
    • C11D2111/14—Hard surfaces

Definitions

  • the present invention relates to the use of certain polyester derivatives for washing textiles or cleaning hard surfaces as well as to washing or cleaning agents which contain such polyester derivatives.
  • washing and cleaning agents In addition to surfactants, which are primarily responsible for removing soiling from the objects to be washed or cleaned, washing and cleaning agents usually contain a not inconsiderable number of auxiliary substances that contribute to the washing or cleaning result, such as bleaching agents, enzymes or antiredeposition agents, and probably first and foremost among these are so-called builder materials.
  • Builder materials are responsible for removing or rendering harmless metal ions such as calcium and magnesium from the aqueous washing or cleaning liquor and from soiling on the objects to be washed or cleaned. This can be done by detrimental precipitation or, preferably, by exchanging or complexing the metal ions and keeping them in solution.
  • Complexing builders are, for example, tripolyphosphate, ethylenediaminetetraacetic acid, aminotrismethylenephosphonic acid, but also polymeric organic polycarboxylic acids such as polyacrylic acid and acrylic acid-maleic acid copolymers.
  • the present invention makes a contribution to the field of polymeric organic builder substances.
  • the invention relates to washing or cleaning agents containing the polymers specified below which can be obtained by polycondensation and subsequent radical polymerization.
  • the polymers essential to the invention are obtainable from a) the polycondensation of diols A with dicarboxylic acids B, where the diols or the dicarboxylic acids or both are monoethylenically unsaturated, and b) the subsequent radical copolymerization of the unsaturated polyesters obtainable in step a) with monoethylenically unsaturated monomers C, which are different from the monoethylenically unsaturated diols and the monoethylenically unsaturated dicarboxylic acids of step a).
  • the polymer contains no further structural elements than those resulting from the above-mentioned monomers A, B and C, with the ends of the polymer consisting of alcohol functions from the diol A, carboxymethyl ester, carboxylic acid groups from the dicarboxylic acid B, functional groups originating from monomer C, and residues originating from polymerization initiators and mixtures thereof.
  • diols A examples include 1,2-propanediol, 1,3-propanediol, 3-ethoxy-1,2-propanediol, 3-dimethylamino-1,2-propanediol, 2,2-diethyl-1,3-propanediol, 1,5-propanediol, 1,6-hexanediol, 1,2-butanediol, 2,3-butanediol, 1,4-butanediol, 1,3-butanediol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, polypropylene glycol (M n 200 to 2 000), polyether polyol (M n 200 to 4 000), poly(tetrahydrofuran) (M n 200 to 2 000), Poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) (M n 200 to
  • dicarboxylic acids B are maleic acid, itaconic acid, fumaric acid, muconic acid, propanedioic acid, butanedioic acid, pentanedioic acid, hexanedioic acid, 3,6,9-trioxaundecanedioic acid and poly(ethylene glycol) bis(carboxymethyl) ether.
  • Particularly preferred dicarboxylic acids B are selected from maleic acid, itaconic acid, fumaric acid and mixtures thereof.
  • the polyester of step a) is accessible from monoethylenically unsaturated dicarboxylic acids B, wherein the diols A are also monoethylenically unsaturated or particularly preferably saturated.
  • the polyester of step a) is obtainable from the polycondensation of the diols A and the dicarboxylic acids B in molar ratios of 0.9:1.1 to 1.1:0.9, particularly preferably in a molar ratio of 1:1.
  • Preferred polyesters obtainable by polycondensation of step a) have a number-average molecular weight M n in the range from 500 g/mol to 20,000 g/mol, in particular in the range from 700 g/mol to 10,000 g/mol.
  • Preferred monoethylenically unsaturated monomers C are selected from acrylic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, their alkali and ammonium salts, and mixtures thereof. They can be radically polymerized with the polyesters obtainable in step a) using known radical initiators, for example azo-bis-(isobutylonitrile).
  • Preferred polymers obtainable by polycondensation of step a) and subsequent radical polymerization of step b) have a number-average molecular weight M n in the range from 1 000 g/mol to 150 000 g/mol, in particular in the range from 1 100 g/mol to 50 000 g/mol.
  • the invention further relates to the use of such polymers for washing textiles or for cleaning hard surfaces, in which they are used together with water and generally other usual ingredients of washing or cleaning agents.
  • This use can be carried out manually or, if necessary, with the aid of a conventional household washing machine or dishwasher. It is possible to use the washing or cleaning agent and the polymeric active ingredient simultaneously or one after the other. Simultaneous use can be carried out particularly advantageously by using a washing or cleaning agent that contains the active ingredient.
  • a textile washing process preferably takes place at a temperature of 15 °C to 60 °C, particularly preferably at a temperature of 20 °C to 40 °C.
  • the textile washing process also preferably takes place at a pH of 6 to 11, particularly preferably at a pH of 7.5 to 9.5.
  • the use concentration of the polymer defined above in the washing liquor is preferably in the range from 0.001 g/l to 5 g/l, in particular from 0.01 g/l to 0.5 g/l.
  • Agents which contain a polymer essential to the invention or are used together with it can contain all other usual constituents of such agents which do not interact in an undesirable manner with the active ingredient essential to the invention, in particular surfactant.
  • the agent preferably contains the active ingredient defined above in amounts of 0.1% by weight to 15% by weight, in particular from 0.5% by weight to 10% by weight, whereby this and the following data of % by weight refer to the entire agent, unless otherwise stated.
  • Detergents that can be used in connection with the present invention which can be present in particular as powdered solids, in post-compacted particle form, as solutions, dispersions or suspensions, can contain all known ingredients that are usual in such agents.
  • the agents can in particular contain further builder substances, surface-active surfactants, water-miscible organic solvents, enzymes, sequestering agents, electrolytes, pH regulators, polymers with special effects, such as soil release polymers, color transfer inhibitors, graying inhibitors, crease-reducing and shape-retaining polymeric active ingredients, and further auxiliary substances, such as optical brighteners, foam regulators, dyes and fragrances.
  • the agents may contain one or more surfactants, particularly anionic surfactants, non-ionic surfactants and mixtures thereof, but may also contain cationic and/or amphoteric surfactants.
  • nonionic surfactants known to the person skilled in the art can be used as nonionic surfactants.
  • alkoxylated, advantageously ethoxylated, in particular primary alcohols with preferably 8 to 18 C atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol are used as nonionic surfactants, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or can contain linear and methyl-branched radicals in the mixture, as is usually the case in oxo alcohol radicals.
  • alcohol ethoxylates with linear radicals from alcohols of native origin with 12 to 18 C atoms e.g.
  • the preferred ethoxylated alcohols include, for example, C12-14 alcohols with 3 EO or 4 EO, C8-n alcohol with 7 EO, C12-18 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C12-14 alcohol with 3 EO and C12-18 alcohol with 5 EO.
  • the stated degrees of ethoxylation represent statistical averages which can correspond to a whole or a fractional number 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 of these are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • alkyl glycosides of the general formula R 5 O(G) X can also be used as further non-ionic surfactants, in which R 5 corresponds to a primary straight-chain or methyl-branched, in particular methyl-branched in the 2-position, aliphatic radical with 8 to 22, preferably 12 to 18 C atoms and G is the symbol that stands for a glycose unit with 5 or 6 C atoms, preferably glucose.
  • the degree of oligomerization x, which determines the distribution of monoglycosyl alcohols, den and oligoglycosides is any number between 1 and 10; preferably x is between 1.2 and 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.
  • Non-ionic surfactants of the amine oxide type for example N-cocoalkyl-N,N-dimethylamine oxide and N-tallowalkyl-N,N-dihydroxyethylamine oxide, and fatty acid alkanolamides can also be used.
  • the amount of these non-ionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of that.
  • Suitable surfactants are polyhydroxy fatty acid amides of the formula
  • R- CO- N- [Z] in which R is an aliphatic acyl radical having 6 to 22 carbon atoms, R 1 is hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl radical having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.
  • 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
  • R- CO- N- [Z] in which R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R 1 is a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R 2 is a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, with C 1-4 alkyl or phenyl radicals being preferred and [Z] is 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.
  • [Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • a reduced sugar for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • the N-alkoxy- or N-aryloxy-substituted compounds can be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as a catalyst.
  • anionic surfactants used are sulfonates and sulfates.
  • sulfonate-type surfactants are Cg-alkylbenzenesulfonates, olefinsulfonates, i.e.
  • alkene and hydroxyalkanesulfonates, and disulfonates such as those obtained from C12-18 monoolefins with a terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products.
  • alkanesulfonates obtained from C12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • esters of ⁇ -sulfofatty acids esters of ⁇ -sulfofatty acids (estersulfonates), for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.
  • sulfated fatty acid glycerol esters are sulfated fatty acid glycerol esters.
  • Fatty acid glycerol esters are understood to mean the mono-, di- and triesters as well as mixtures thereof, as obtained in the production by esterification of glycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol.
  • Preferred sulfated fatty acid glycerol esters are the sulfonation products of 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.
  • alkyl sulfates of the general formula
  • RO-SO3M in which R is a linear, branched-chain or cyclic saturated hydrocarbon radical having 12 to 18, in particular 12 to 14 C atoms and M is a counter cation leading to the charge neutralization of the sulfuric acid semiester, in particular a sodium or potassium ion or an ammonium ion of the general formula R 1 R 2 R 3 R 4 N + , in which R 1 , R 2 , R 3 , and R 4 independently of one another are hydrogen, an alkyl group having 1 to 4 C atoms or a hydroxyalkyl group having 2 to 3 C atoms.
  • Preferred R radicals are derived from native Ci2-Cis fatty alcohols, such as coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or the Cio-C2o oxo alcohols or secondary alcohols of these chain lengths.
  • alkyl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical produced on a petrochemical basis, which have a degradation behavior analogous to the corresponding compounds based on oleochemical raw materials. Ci2-Ci6-alkyl sulfates and Ci2-Ci4-alkyl sulfates are particularly preferred.
  • sulfuric acid monoesters of straight-chain or branched C7-2i-alcohols ethoxylated with 1 to 6 moles of ethylene oxide such as 2-methyl-branched Cg-n-alcohols with an average of 3.5 moles of ethylene oxide (EO) or Ci2-is-fatty alcohols with 1 to 4 EO.
  • suitable anionic surfactants are the salts of alkyl sulfosuccinic acid, which are also referred to as sulfosuccinates or sulfosuccinic acid esters and are the monoesters and/or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain Cs-is fatty alcohol residues or mixtures of these. Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants. Sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution are particularly preferred. It is also possible to use alk(en)ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk(en)yl chain or its salts.
  • soaps Suitable are saturated fatty acid soaps, 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, e.g. coconut, palm kernel or tallow fatty acids.
  • the anionic surfactants can be in the form of their sodium, potassium or ammonium salts and 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.
  • cationic and/or amphoteric surfactants can also be used.
  • Cationic compounds of the following formulas can be used as cationic active substances:
  • Surfactants are contained in detergents in amounts of preferably 5 wt.% to 50 wt.%, in particular 8 wt.% to 30 wt.%.
  • Textile softening compounds can be used to care for textiles and improve textile properties such as a softer feel (finishing) and reduced electrostatic charge (increased wearing comfort).
  • the active ingredients in these formulations are quaternary ammonium compounds with two hydrophobic residues, such as disteraryldimethylammonium chloride, which, however, due to its insufficient biodegradability, is increasingly being replaced by quaternary ammonium compounds that contain ester groups in their hydrophobic residues as predetermined breaking points for biodegradation.
  • esters with improved biodegradability can be obtained, for example, by esterifying mixtures of methyldiethanolamine and/or triethanolamine with fatty acids and then quaternizing the reaction products with alkylating agents in a manner known per se.
  • Dimethylolethyleneurea is suitable as a finishing agent.
  • a washing or cleaning agent can contain one or more other water-soluble and/or water-insoluble, organic and/or inorganic builders.
  • the water-soluble organic builder substances include monomeric polycarboxylic acids, in particular citric acid and sugar acids, monomeric and polymeric aminopolycarboxylic acids, in particular methylglycinediacetic acid, nitrilotriacetic acid and ethylenediaminetetraacetic acid as well as polyaspartic acid, polyphosphonic acids, in particular aminotris-(methylenephosphonic acid), ethylenediaminetetrakis(methylenephosphonic acid) and 1-hydroxyethane-1,1-diphosphonic acid, polymeric hydroxy compounds such as dextrin and polymeric (poly)carboxylic acids, in particular polycarboxylates accessible by oxidation of polysaccharides or dextrins, and/or polymeric acrylic acids, methacrylic acids, maleic acids and copolymers thereof, which
  • the relative molecular mass of the homopolymers of unsaturated carboxylic acids is generally between 5 000 g/mol and 200 000 g/mol, that of the copolymers between 2 000 g/mol and 200 000 g/mol, preferably 50 000 g/mol to 120 000 g/mol, based in each case on the free acid.
  • Suitable, although 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 proportion of acid is at least 50% by weight.
  • Terpolymers which contain two unsaturated acids and/or their salts as monomers and vinyl alcohol and/or an esterified vinyl alcohol or a carbohydrate as the 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 Cs-Cs-carboxylic acid and preferably from a C3-C4-monocarboxylic acid, in particular from (meth)acrylic acid.
  • the second acidic monomer or its salt can be a derivative of a C4-C8 dicarboxylic acid, with maleic acid being particularly preferred, and/or a derivative of an allylsulfonic acid which is substituted in the 2-position with an alkyl or aryl radical.
  • Such polymers generally have a relative molecular mass of between 1,000 g/mol and 200,000 g/mol.
  • Other possible copolymers are those which have acrolein and acrylic acid/acrylic acid salts or vinyl acetate as monomers.
  • Such organic builder substances can be used additionally, if desired in amounts of up to 40% by weight, in particular up to 25% by weight and preferably up to 8% by weight, but are preferably completely replaced by the polymers essential to the invention.
  • Water-insoluble, water-dispersible inorganic builder materials used are in particular crystalline or amorphous alkali 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.
  • crystalline sodium aluminosilicates in detergent quality in particular zeolite A, P and optionally X, are preferred.
  • Amounts close to the upper limit mentioned are preferably used in solid, particulate agents.
  • Suitable aluminosilicates in particular have no particles with a grain size of more than 30 pm and preferably consist of at least 80% by weight of particles with a size of less than 10 pm.
  • Their calcium binding capacity is generally in the range from 100 mg to 200 mg CaO per gram.
  • Suitable substitutes or partial substitutes for the aluminosilicate mentioned are crystalline alkali silicates, which can be present alone or in a mixture with amorphous silicates.
  • the alkali silicates which can be used as builders preferably have a molar ratio of alkali oxide to SiO2 of less than 0.95, in particular from 1:1.1 to 1:12, and can be amorphous or crystalline.
  • Preferred alkali silicates are the sodium silicates, in particular the amorphous sodium silicates, with a molar ratio Na2O:SiO2 of 1:2 to 1:2.8.
  • Crystalline silicates which can be present alone or in a mixture with amorphous silicates are preferably crystalline layered silicates of the general formula Na2Si x O2x+iy H2O, in which x, the so-called modulus, is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4.
  • Preferred crystalline layered silicates are those in which x in the general formula mentioned assumes the values 2 or 3.
  • both ß- and 8-sodium disilicates Na2Si2Os y H2O are preferred.
  • crystalline alkali silicates made from amorphous alkali silicates of the above general formula, in which x is a number from 1.9 to 2.1.
  • a crystalline sodium layer silicate with a modulus of 2 to 3 is used, as can be made from sand and soda. Crystalline sodium silicates with a modulus in the range from 1.9 to 3.5 are used in a further preferred embodiment.
  • a granular compound of alkali silicate and alkali carbonate is used, as is commercially available, for example, under the name Nabion® 15.
  • the weight ratio of aluminosilicate to silicate is preferably 1:10 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.
  • Inorganic builder substances are preferably contained in detergents in amounts of up to 60 wt.%, in particular from 5 wt.% to 40 wt.%.
  • the agent has a water-soluble builder block.
  • builder block is intended to express that the agent does not contain any builder substances other than those that are water-soluble, i.e. all builder substances contained in the agent are combined in the "block” characterized in this way, with the exception of the amounts of substances that may be commercially present in small quantities as impurities or stabilizing additives in the other ingredients of the agent.
  • water-soluble is to be understood to mean that the builder block dissolves without residue at the concentration that results from the amount of the agent containing it used under normal conditions.
  • at least 15% by weight and up to 55% by weight, in particular 25% by weight to 50% by weight, of water-soluble builder block are contained in the agents.
  • This is preferably composed of the components a) 5% to 35% by weight of citric acid, alkali citrate and/or alkali carbonate, which can also be at least partially replaced by alkali hydrogen carbonate, b) up to 10% by weight of alkali silicate with a modulus in the range from 1.8 to 2.5, c) up to 2% by weight of phosphonic acid and/or alkali phosphonate, d) up to 50% by weight of alkali phosphate, and e) 1% to 10% by weight of the polymer essential to the invention, the amounts given referring to the entire detergent.
  • the water-soluble builder block contains, in addition to component e), at least 1 of components a) and b) in amounts greater than 0% by weight.
  • component a) in a preferred embodiment, 15% to 25% by weight of alkali carbonate, which can be at least partially replaced by alkali hydrogen carbonate, and up to 5% by weight, in particular 0.5% to 2.5% by weight of citric acid and/or alkali citrate are included.
  • component a) contains 5% to 25% by weight, in particular 5% to 15% by weight of citric acid and/or alkali citrate and up to 5% by weight, in particular 1% to 5% by weight of alkali carbonate, which can be at least partially replaced by alkali hydrogen carbonate. If both alkali carbonate and alkali hydrogen carbonate are present, component a) preferably contains alkali carbonate and alkali hydrogen carbonate in a weight ratio of 10:1 to 1:1.
  • a preferred embodiment contains 1 wt.% to 5 wt.% alkali silicate with a modulus in the range of 1.8 to 2.5.
  • preferred embodiments contain up to 1% by weight of phosphonic acid and/or alkali phosphonate.
  • Phosphonic acids are also understood to mean optionally substituted alkylphosphonic acids, which can also have several phosphonic acid groups (so-called polyphosphonic acids).
  • hydroxy and/or aminoalkylphosphonic acids and/or their alkali salts such as dimethylaminomethanediphosphonic acid, 3-aminopropane-1-hydroxy-1,1-diphosphonic acid, 1-amino-1-phenylmethanediphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid, amino-tris-(methylenephosphonic acid), N,N,N',N'-ethylenediamine-tetrakis(methylenephosphonic acid) and acylated derivatives of phosphorous acid, which can also be used in any mixtures.
  • hydroxy and/or aminoalkylphosphonic acids and/or their alkali salts such as dimethylaminomethanediphosphonic acid, 3-aminopropane-1-hydroxy-1,1-diphosphonic acid, 1-amino-1-phenylmethanediphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid, amino-tris-(methylenephosphonic acid),
  • alkali phosphate in particular trisodium polyphosphate
  • alkali phosphate is the collective name for the alkali metal (in particular sodium and potassium) salts of the various phosphoric acids, among which metaphosphoric acids (HPO3)n and orthophosphoric acid H3PO4 can be distinguished alongside higher molecular weight representatives.
  • the phosphates combine several advantages: They act as alkali carriers, prevent limescale deposits on machine parts or limescale incrustations in fabrics and also contribute to the cleaning performance.
  • Sodium dihydrogen phosphate NaH2PÜ4 exists as a dihydrate (density 1.91 g/ cm3 , melting point 60°) and as a monohydrate (density 2.04 g/ cm3 ). Both salts are white powders that are very easily soluble in water. When heated, they lose their water of crystallization and turn into the weakly acidic diphosphate (disodium hydrogen diphosphate, Na2H2P2O?) at 200°C, and into sodium trimetaphosphate (NasPsOg) and Madrell's salt at higher temperatures. NaH2PÜ4 reacts acidically; it is formed when phosphoric acid is adjusted to a pH of 4.5 with sodium hydroxide solution and the mash is sprayed.
  • Potassium dihydrogen phosphate (primary or monobasic potassium phosphate, potassium biphosphate, KDP), KH2PO4, is a white salt with a density of 2.33 g 3 , has a melting point of 253° (decomposition to form (KPO3)x, potassium polyphosphate) and is easily soluble in water.
  • Disodium hydrogen phosphate (secondary sodium phosphate), Na2HPO4, is a colorless, highly water-soluble crystalline salt.
  • Disodium hydrogen phosphate is produced by neutralizing phosphoric acid with soda solution using phenolphthalein as an indicator.
  • Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K2HPO4, is an amorphous, white salt that is easily soluble in water.
  • Trisodium phosphate, tertiary sodium phosphate, NasPC are colorless crystals which, as dodecahydrate, have a density of 1.62% 3 and a melting point of 73-76°C (decomposition), as decahydrate (corresponding to 19-20% P2O5) a melting point of 100°C and in anhydrous form (corresponding to 39-40% P2O5) a density of 2.536% 3.
  • Trisodium phosphate is easily soluble in water under alkaline reaction and is prepared by evaporating a solution of exactly 1 mol disodium phosphate and 1 mol NaOH.
  • Tripotassium phosphate (tertiary or tribasic potassium phosphate), K3PO4, is a white, deliquescent, granular powder with a density of 2.56% 3 , has a melting point of 1340° and is easily soluble in water with alkaline reaction. It is formed, for example, when Thomas slag is heated with coal and potassium sulfate. Despite the higher price, the more easily soluble and therefore highly effective potassium phosphates are often preferred over the corresponding sodium compounds.
  • Tetrasodium diphosphate (sodium pyrophosphate), Na 4 P2O7, exists in anhydrous form (density 2.534 g 3 , melting point 988°, also given as 880°) and as a decahydrate (density 1.815-1.836 g -3 , melting point 94° with loss of water). Substances are colorless crystals that are soluble in water with an alkaline reaction. Na4P 2 O 7 is formed when disodium phosphate is heated to >200° or by reacting phosphoric acid with soda in a stoichiometric ratio and dewatering the solution by spraying. The decahydrate complexes heavy metal salts and hardness-forming agents and therefore reduces the hardness of the water.
  • Potassium diphosphate (potassium pyrophosphate), K4P2O7, exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33 to 3 , which is soluble in water, with the pH value of the 1% solution at 25° being 10.4.
  • Condensation of NaH2PC or KH2PO4 produces higher molecular weight sodium and potassium phosphates, of which one can distinguish between cyclic representatives, the sodium or potassium metaphosphates, and chain-shaped types, the sodium or potassium polyphosphates.
  • a variety of names are used, especially for the latter: melt or calcined phosphates, Graham's salt, Kurrol's and Madrell's salt.
  • All higher sodium and potassium phosphates are collectively referred to as condensed phosphates.
  • About 17 g of the water-free salt dissolve in 100 g of water at room temperature, about 20 g at 60°, and about 32 g at 100°; after heating the solution at 100° for two hours, hydrolysis produces about 8% orthophosphate and 15% diphosphate.
  • pentasodium triphosphate In the production of pentasodium triphosphate, phosphoric acid is reacted with soda solution or sodium hydroxide in a stoichiometric ratio and the solution is dehydrated by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentaka- Potassium triphosphate, K5P3O10 (potassium tripolyphosphate), is available in the form of a 50% by weight solution (> 23% P2O5, 25% K2O). There are also sodium potassium tripolyphosphates, which can also be used in the context of the present invention. These are formed, for example, when sodium trimetaphosphate is hydrolyzed with KOH:
  • sodium tripolyphosphate, potassium tripolyphosphate or mixtures of the two can be used in the same way as sodium tripolyphosphate, potassium tripolyphosphate or mixtures of the two; mixtures of sodium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of potassium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of sodium tripolyphosphate and potassium tripolyphosphate and sodium potassium tripolyphosphate can also be used.
  • Enzymes that can be used in the products are those from the class of lipases, cutinases, amylases, pullulanases, mannanases, cellulases, hemicellulases, xylanases and peroxidases as well as mixtures thereof, for example amylases such as Termamyl®, Amylase-LT®, Maxamyl®, Duramyl® and/or Purafect® OxAm, lipases such as Lipolase®, Lipomax®, Lumafast®, Lipozym® and/or Lipex®, cellulases such as Celluzyme® and/or Carezyme®.
  • amylases such as Termamyl®, Amylase-LT®, Maxamyl®, Duramyl® and/or Purafect® OxAm
  • lipases such as Lipolase®, Lipomax®, Lumafast®, Lipozym® and/or Lipex®
  • cellulases such as Celluzyme® and
  • Enzymatic active ingredients obtained from fungi or bacteria such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus, Humicola lanuginosa, Humicola insolens, Pseudomonas pseudoalcaligenes or Pseudomonas cepacia are particularly suitable.
  • the enzymes used, if any, can be adsorbed on carriers and/or embedded in coating substances in order to protect them against premature inactivation. They are preferably contained in detergents in amounts of up to 10% by weight, in particular from 0.2% by weight to 2% by weight.
  • the agent contains 5 wt.% to 50 wt.%, in particular 8 to 30 wt.% anionic and/or nonionic surfactant, up to 60 wt.%, in particular 5 to 40 wt.% builder substance and 0.2 wt.% to 2 wt.% enzyme selected from lipases, cutinases, amylases, pullulanases, mannanases, cellulases, oxidases and peroxidases and mixtures thereof.
  • the organic solvents that can be used in the detergents include alcohols with 1 to 4 carbon atoms, particularly methanol, ethanol, isopropanol and tert-butanol, diols with 2 to 4 carbon atoms, particularly ethylene glycol and propylene glycol, and mixtures thereof and the ethers that can be derived from the above-mentioned classes of compounds.
  • Such water-miscible solvents are preferably present in the detergents in amounts not exceeding 30% by weight, particularly from 6% by weight to 20% by weight.
  • Naturally derived polymers that can be used as thickeners in aqueous liquid agents include agar-agar, carrageenan, tragacanth, gum arabic, AI- ginates, pectins, polyoses, guar flour, locust bean gum, starch, dextrins, gelatin and casein, cellulose derivatives such as carboxymethylcellulose, hydroxyethyl and propylcellulose, and polymeric polysaccharide thickeners such as xanthan; in addition, fully synthetic polymers such as polyacrylic and polymethacrylic compounds, vinyl polymers, polycarboxylic acids, polyethers, polyimines, polyamides and polyurethanes can also be used as thickeners.
  • the agents can contain system- and environmentally-compatible acids, in particular citric acid, acetic acid, tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid and/or adipic acid, but also mineral acids, in particular sulfuric acid, or bases, in particular ammonium or alkali hydroxides.
  • Such pH regulators are preferably contained in the agents in amounts of no more than 20% by weight, in particular from 1.2% by weight to 17% by weight.
  • soil-removing polymers which are often referred to as “soil release” agents or as “soil repellents” because of their ability to make the treated surface, for example the fiber, dirt-repellent, are non-ionic or cationic cellulose derivatives.
  • the particularly polyester-active soil-removing polymers include copolyesters of dicarboxylic acids, for example adipic acid, phthalic acid or terephthalic acid, diols, for example ethylene glycol or propylene glycol, and polydiols, for example polyethylene glycol or polypropylene glycol.
  • the preferably used soil-removing polyesters include those compounds which are formally accessible by esterification of two monomer parts, where the first monomer is a dicarboxylic acid HOOC-Ph-COOH and the second monomer is a diol HO-(CHR 11 -) a OH, which can also be present as a polymeric diol H-(O-(CHR 11 -) a )bOH.
  • Ph is an o-, m- or p-phenylene radical which can carry 1 to 4 substituents selected from alkyl radicals having 1 to 22 C atoms, sulfonic acid groups, carboxyl groups and mixtures thereof
  • R 11 is hydrogen, an alkyl radical having 1 to 22 C atoms and mixtures thereof
  • a is a number from 2 to 6
  • b is a number from 1 to 300.
  • the polyesters obtainable from these contain both monomer diol units -O-(CHR 11 -) a O- and polymer diol units -(O-(CHR 11 -
  • 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 of the 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 underlying the residue Ph is preferably selected from terephthalic acid, isophthalic acid, phthalic acid, trimellitic acid, mellitic acid, the isomers of sulfophthalic acid, sulfoisophthalic acid and sulfoterephthalic acid and mixtures thereof. If their acid groups are not part of the ester bonds in the polymer, they are preferably present in salt form, in particular as alkali or ammonium salts. Of these, the sodium and potassium salts are particularly preferred.
  • the monomer HOOC-Ph-COOH small amounts, in particular not more than 10 mol% based on the amount of Ph with the meaning given above, of other acids which have at least two carboxyl groups may be present in the soil-releasing polyester.
  • these include, for example, alkylene and alkenylene dicarboxylic acids such as malonic acid, succinic acid, fumaric acid, maleic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid.
  • the preferred diols HO-(CHR 11 -) a OH include those in which R 11 is hydrogen and a is a number from 2 to 6, and those in which a has the value 2 and R 11 is selected from hydrogen and the alkyl radicals with 1 to 10, in particular 1 to 3, C atoms.
  • R 11 is hydrogen and a is a number from 2 to 6
  • R 11 is selected from hydrogen and the alkyl radicals with 1 to 10, in particular 1 to 3, C atoms.
  • those of the formula HO-CH2-CHR 11 -OH, in which R 11 has the meaning given above 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 molecular weight in the range from 1000 to 6000.
  • these polyesters can also be end-capped, with alkyl groups having 1 to 22 carbon atoms and esters of monocarboxylic acids being suitable as end groups.
  • the end groups bound via ester bonds can be based on alkyl, alkenyl and arylmonocarboxylic acids with 5 to 32 C atoms, in particular 5 to 18 C atoms. These include 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, petroselinic acid, petroselaidic acid, oleic acid, linoleic acid, linolaidic acid, linolenic acid, eleostearic acid, arachidic acid, gadoleic acid, arachidonic acid, behenic acid, erucic acid, brassidic acid, clupanodonic acid, lignoceric acid, cerotic acid,
  • the end groups can also be based on hydroxymonocarboxylic acids with 5 to 22 carbon atoms, which include, for example, hydroxyvaleric acid, hydroxycaproic acid, ricinoleic acid, its hydrogenation product hydroxystearic acid, and o-, m- and p-hydroxybenzoic acid.
  • the hydroxymonocarboxylic acids can in turn be linked to one another via their hydroxyl group and their carboxyl group and thus be present multiple times in one end group.
  • the number of hydroxymonocarboxylic acid units per end group i.e. their degree of oligomerization, is in the range from 1 to 50, in particular from 1 to 10.
  • polymers of ethylene terephthalate and polyethylene oxide terephthalate in which the polyethylene glycol units have molecular weights of 750 to 5000 and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate is 50:50 to 90:10, are used alone or in combination with cellulose derivatives.
  • the color transfer inhibitors suitable for use in textile washing agents include in particular polyvinylpyrrolidones, polyvinylimidazoles, polymeric N-oxides such as poly(vinylpyridine-N-oxide) and copolymers of vinylpyrrolidone with vinylimidazole and optionally other monomers.
  • the products may contain anti-crease agents, as textile fabrics, particularly those made of rayon, wool, cotton and their blends, can tend to crease because the individual fibers are sensitive to bending, kinking, pressing and squeezing across the fiber direction.
  • graying inhibitors The purpose of graying inhibitors is to keep the dirt that has been detached from the hard surface and in particular from the textile fiber suspended in the liquor.
  • Water-soluble colloids usually of an organic nature, are suitable for this purpose, for example starch, glue, gelatin, salts of ethercarboxylic acids or ethersulfonic acids of starch or cellulose, or salts of acidic sulfuric acid esters of cellulose or starch.
  • Water-soluble polyamides containing acidic groups are also suitable for this purpose.
  • Starch derivatives other than those mentioned above can also be used, for example aldehyde starches.
  • Cellulose ethers such as carboxymethylcellulose (Na salt), methylcellulose, hydroxyalkylcellulose and mixed ethers such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof are preferred, for example in amounts of 0.1 to 5% by weight, based on the agent.
  • the agents can contain optical brighteners, among these in particular derivatives of diaminostilbene disulfonic acid or its alkali metal salts. Suitable examples are salts of 4,4'-bis(2-anilino-4-morpholino-1,3,5-triazinyl-6-amino)stilbene-2,2'-disulfonic acid or similarly constructed compounds which carry a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group instead of the morpholino group.
  • Brighteners of the substituted diphenylstyryl type can also be present, for example the alkali salts of 4,4'-bis(2-sulfostyryl)-diphenyl, 4,4'-bis(4-chloro-3-sulfostyryl)-diphenyl, or 4-(4-chlorostyryl)-4'-(2-sulfostyryl)-diphenyl. Mixtures of the above-mentioned optical brighteners can also be used.
  • Suitable foam inhibitors include, for example, soaps of natural or synthetic origin that have a high proportion of cis-C24 fatty acids.
  • Suitable non-surfactant-type foam inhibitors include, for example, organopolysiloxanes and mixtures thereof with microfine, optionally silanized silica, as well as paraffins, waxes, microcrystalline waxes and mixtures thereof with silanized silica or bis-fatty acid alkylenediamides. Mixtures of different foam inhibitors are also advantageously used, for example those made from silicones, paraffins or waxes.
  • the foam inhibitors in particular silicone and/or paraffin-containing foam inhibitors, are preferably bound to a granular, water-soluble or water-dispersible carrier substance. Mixtures of paraffins and bis-stearylethylenediamide are particularly preferred.
  • Peroxygen compounds that may be present in the agents, particularly those in solid form, are particularly organic peracids or peracidic salts of organic acids, such as phthalimidopercaproic acid, perbenzoic acid or salts of diperdodecanedioic acid, hydrogen peroxide and inorganic salts that release hydrogen peroxide under the washing conditions, such as perborate, percarbonate and/or persilicate.
  • Hydrogen peroxide can also be produced with the aid of an enzymatic system, i.e. an oxidase and its substrate.
  • solid peroxygen compounds i.e. an oxidase and its substrate.
  • solid peroxygen compounds can be used in the form of powders or granules, which can also be coated in a manner known in principle.
  • peroxygen compounds are present in detergents in amounts of up to 50 wt.%, in particular from 5 wt.% to 30 wt.%.
  • bleach activators which form peroxocarboxylic acids or peroxoimidic acids under perhydrolysis conditions and/or conventional bleach-activating transition metal complexes can be used.
  • the optional component of the bleach activators which is present in particular in amounts of 0.5% by weight to 6% by weight, comprises the N- or O-acyl compounds commonly used, for example multiply acylated alkylenediamines, in particular tetraacetylethylenediamine, acylated glycolurils, in particular tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, urazoles, diketopiperazines, sulfurylamides and cyanurates, as well as carboxylic acid anhydrides, in particular phthalic acid anhydride, carboxylic acid esters, in particular sodium isononanoylphenolsulfonate, and acylated sugar derivatives, in particular pentaacetylglucos
  • the bleach activators can be coated with coating substances or granulated in a known manner, with tetraacetylethylenediamine granulated with the aid of carboxymethylcellulose with average grain sizes of 0.01 mm to 0.8 mm, granulated 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine, and/or trialkylammonium acetonitrile prepared in particle form being particularly preferred.
  • such bleach activators are preferably contained in amounts of up to 8% by weight, in particular from 2% by weight to 6% by weight, in each case based on the entire detergent.
  • solid agents does not present any difficulties and can be carried out in a manner known in principle, for example by spray drying or granulation.
  • a process comprising an extrusion step is preferred.
  • Detergents in the form of aqueous solutions or solutions containing other conventional solvents are particularly advantageously produced by simply mixing the ingredients, which can be added in bulk or as a solution to an automatic mixer.
  • the agents, particularly in concentrated liquid form are present as a portion in a completely or partially water-soluble coating. The portioning makes it easier for the consumer to dose.
  • the products can be packed in foil bags, for example. Bags made of water-soluble foil make it unnecessary for the consumer to tear open the packaging. This makes it easy to dispense a single portion for one wash cycle by placing the bag directly in the washing machine or by throwing the bag into a certain amount of water, for example in a bucket, bowl or hand basin.
  • the foil bag surrounding the wash portion dissolves without leaving any residue when a certain temperature is reached.
  • water-soluble detergent portions which are basically also suitable for producing agents that can be used in the context of the present invention.
  • the best known processes are the tubular film process with horizontal and vertical sealing seams.
  • the thermoforming process deep-drawing process
  • the water-soluble casings do not necessarily have to consist of a film material, however, but can also be dimensionally stable containers that can be obtained, for example, by means of an injection molding process.
  • processes for producing water-soluble capsules from polyvinyl alcohol or gelatin which in principle offer the possibility of providing capsules with a high degree of filling.
  • the processes are based on the water-soluble polymer being introduced into a forming cavity.
  • the capsules are filled and sealed either synchronously or in successive steps, with the latter case being filled through a small opening.
  • the capsules are filled, for example, by a filling wedge arranged above two counter-rotating drums that have spherical half-shells on their surface.
  • the drums guide polymer bands that cover the spherical half-shell cavities. Sealing takes place at the positions where the polymer band of one drum meets the polymer band of the opposite drum.
  • the filling material is injected into the capsule being formed, with the injection pressure of the filling liquid pressing the polymer bands into the spherical half-shell cavities.
  • a process for producing water-soluble capsules, in which the capsules are filled first and then sealed, is based on the so-called Bottle-Pack® process.
  • a tube-like preform is fed into a two-part cavity. The cavity is closed, sealing the lower tube section, then the tube is inflated to form the capsule shape in the cavity, filled and finally sealed.
  • the shell material used to produce the water-soluble portion is preferably a water-soluble polymeric thermoplastic, particularly preferably selected from the group (optionally partially acetalized) polyvinyl alcohol, polyvinyl alcohol copolymers, polyvinylpyrrolidone, polyethylene oxide, gelatin, cellulose and derivatives thereof, starch and derivatives thereof, blends and composites, inorganic salts and mixtures of the materials mentioned, preferably hydroxypropylmethylcellulose and/or polyvinyl alcohol blends.
  • Polyvinyl alcohols are commercially available, for example under the trademark Mowiol® (Clariant).
  • Polyvinyl alcohols that are particularly suitable in the context of the present invention are, for example, Mowiol® 3-83, Mowiol® 4-88, Mowiol® 5-88, Mowiol® 8-88 and Clariant L648.
  • the water-soluble thermoplastic used to produce the portion can optionally additionally comprise polymers selected from the group comprising acrylic acid-containing polymers, polyacrylamides, oxazoline polymers, polystyrene sulfonates, polyurethanes, polyesters, polyethers and/or mixtures of the above polymers.
  • the water-soluble thermoplastic used comprises a polyvinyl alcohol whose degree of hydrolysis is 70 mol% to 100 mol%, preferably 80 mol% to 90 mol%, particularly preferably 81 mol% to 89 mol% and in particular 82 mol% to 88 mol%. It is further preferred that the water-soluble thermoplastic used comprises a polyvinyl alcohol whose molecular weight is in the range from 10,000 g/mol to 100,000 g/mol, preferably from 11,000 g/mol to 90,000 g/mol, particularly preferably from 12,000 g/mol to 80,000 g/mol and in particular from 13,000 g/mol to 70,000 g/mol.
  • thermoplastics are present in amounts of at least 50% by weight, preferably at least 70% by weight, particularly preferably at least 80% by weight and in particular at least 90% by weight, in each case based on the weight of the water-soluble polymeric thermoplastic.
  • a mixture of 6.97 g of maleic acid, 11.55 g of tetraethylene glycol, 30 mg of p-toluenesulfonic acid and 15 mg of hydroquinone was heated to 170°C. After 50 minutes, a vacuum of 50 mbar was applied and the mixture was stirred for a further 5 hours at 170°C. The water formed during the reaction was removed using a distillation bridge. This gave 17.4 g of a maleic acid-ethylene glycol polyester PE2 with M n 2,000 g/mol and M w 16,000 g/mol, determined by GPC in THF.
  • the polymers P1 to P5 prevent the precipitation of calcium and magnesium carbonate, silicate and sulfate as well as mixed precipitates up to much higher degrees of hardness and thus the solution is less turbid than without its use.

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Abstract

L'invention concerne des polymères pouvant être obtenus à partir de a) la polycondensation de diols A avec des acides dicarboxyliques B, les diols ou les acides dicarboxyliques ou les deux étant monoéthyléniquement insaturés, et b) la copolymérisation radicalaire consécutive des polyesters insaturés pouvant être obtenus à l'étape a) avec des monomères C monoéthyléniquement insaturés, qui sont différents des diols monoéthyléniquement insaturés et des acides dicarboxyliques monoéthyléniquement insaturés de l'étape a). Les polymères de l'invention conviennent comme adjuvants de détergence pour détergents et produits de nettoyage.
PCT/EP2024/050838 2023-04-11 2024-01-16 Détergents et produits de nettoyage comprenant des adjuvants de détergence polymères Pending WO2024213278A1 (fr)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0430574A2 (fr) * 1989-11-22 1991-06-05 Rohm And Haas Company Copolymères d'acides polycarboxyliques biodégradables, solubles dans l'eau, compositions contenant de tels copolymères, méthodes d'utilisation de tels copolymères
WO2023008367A1 (fr) * 2021-07-27 2023-02-02 株式会社日本触媒 Acide polycarboxylique contenant une liaison ester (sel) et son procédé de production

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Publication number Priority date Publication date Assignee Title
DE4244386A1 (de) 1992-12-29 1994-06-30 Basf Ag Vinylpyrrolidon- und Vinylimidazol-Copolymerisate, Verfahren zur ihrer Herstellung und ihre Verwendung in Waschmitteln

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0430574A2 (fr) * 1989-11-22 1991-06-05 Rohm And Haas Company Copolymères d'acides polycarboxyliques biodégradables, solubles dans l'eau, compositions contenant de tels copolymères, méthodes d'utilisation de tels copolymères
WO2023008367A1 (fr) * 2021-07-27 2023-02-02 株式会社日本触媒 Acide polycarboxylique contenant une liaison ester (sel) et son procédé de production

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Title
BURKEYEV M.ZH. ET AL: "Properties of cross-linked copolymers of polypropylene glycol maleate with acrylic acid obtained at various concentrations of the RAFT agent", BULLETIN OF THE KARAGANDA UNIVERSITY. "CHEMISTRY" SERIES, vol. 105, no. 1, 30 March 2022 (2022-03-30), pages 15 - 24, XP093144645, ISSN: 2518-718X, Retrieved from the Internet <URL:https://chemistry-vestnik.ksu.kz/apart/2022-105-1/02.pdf> DOI: 10.31489/2022Ch1/15-24 *

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