EP3617299B1 - Polymeric agents improving primary washing power - Google Patents

Description

The present invention relates to the use of certain polymers to enhance the primary detergency of detergents when washing textiles against surfactant- or enzyme-sensitive soiling.

In addition to the ingredients that are essential for the washing process, such as surfactants and builder materials, detergents usually contain other components that can be summarized under the term washing auxiliaries and that include such different groups of active ingredients as foam regulators, graying inhibitors, bleaching agents, bleach activators and color transfer inhibitors. Such auxiliaries also include substances whose presence enhances the detergency of surfactants without generally having to exhibit pronounced surfactant behavior themselves. Such substances are often referred to as detergency boosters.

From the international patent application WO 2014/154508 A1 It is known that the application of block copolymers of polyether alcohol (meth)acrylic esters and amino alcohol or ammonium alcohol (meth)acrylic esters to textiles facilitates the detachment of soiling subsequently deposited on the textiles. From the international patent application WO 2017/005793 A1 It is known that poly-alkoxylated poly -alkanolamines and poly-alkoxylated poly -alkyleneimines show advantages in the reduction of fatty residues. In DE 10 2011 089 948 A1 ethoxylated and propoxylated polyethyleneimines are used to increase the primary detergency in laundry washing. Surprisingly, it has now been found that certain lower molecular weight polymers also have particularly good primary detergency-enhancing properties.

The polymers are (mono)amino-based alkoxylates, preferably propoxylates, with an average molecular weight M _w of 600-10000 g/mol, preferably 1300-6000 g/mol, particularly preferably 1400-4500 g/mol. The polymers according to the invention contain only one amino group, ie only one nitrogen atom per molecule.

Particularly suitable are alkoxylated amino alcohols with a molecular weight M _w of more than 600 g/mol after alkoxylation, the amino nucleus having a molecular weight of less than 200 g/mol and containing only one amino group, and the amino nucleus having a Alkylene oxide selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide and mixtures thereof is alkoxylated, preferably with a mixture containing propylene oxide, particularly preferably with propylene oxide. The alkoxylated amino alcohols can have block or random structures.

Particular preference is given, inter alia, to an alkoxylated amino alcohol, obtainable starting from triethanolamine (TEA) by propoxylation, preferably with a length of the three side arms of 15 propylene oxide (PO) units each.

Also preferred is an alkoxylated amino alcohol, obtainable starting from triisopropanolamine (TIPA) by propoxylation, preferably with a length of the three side arms of 15 propylene oxide (PO) units each.

Also suitable are alkoxylated alkyl monoamines with a linear, branched or cyclic alkyl group, alkoxylation being carried out with an alkylene oxide selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide and mixtures thereof, preferably with a mixture containing propylene oxide, particularly preferably with propylene oxide.

The alkoxylated alkyl monoamines can have block or random structures.

Preference is also given to an alkoxylated alkyl monoamine obtainable starting from tert-butylamine (tBA) by propoxylation, preferably with a length of the two side arms of 12 propylene oxide (PO) units each.

R =

C1-C12 linear, zyklisch oder verzweigt, (CH₂-CHR'O)_n-(CH₂CHR"O)_m-H

R' =

H, CH₃, CH₂CH₃

R" =

H, CH₃, CH₂CH₃

n =

0-30, bevorzugt: 0-10, am meisten bevorzugt: 0-5

m =

0-30, bevorzugt 5-20, am meisten bevorzugt: 12-16

Suitable compounds are also defined by the generic structural formula below.

R =

C1-C12 linear, cyclic or branched, (CH ₂ -CHR'O) _n -(CH ₂ CHR"O) _m -H

R' =

H, _{CH3 , CH2CH3}

R" =

H, _{CH3 , CH2CH3}

n =

0-30, preferred: 0-10, most preferred: 0-5

m =

0-30, preferably 5-20, most preferred: 12-16

The invention therefore relates to the use of polymers consisting of (mono)amino-based alkoxylates with an average molecular weight M _w of 600-10000 g/mol, preferably 1300-6000 g/mol, particularly preferably 1400-4500 g/mol, to increase the primary detergency of detergents when washing textiles in particular aqueous and surfactant-containing washing liquid against surfactant- or enzyme-sensitive soiling, wherein the polymer contains two or three chains of alkylene oxide units per nitrogen atom, and wherein the polymer contains more than 90 mol% propylene oxide units, based on the sum of all alkylene oxide units, and 10 to 18 alkylene oxide units per alkylene oxide chain.

Another subject of the invention is a process for removing surfactant- or enzyme-sensitive soiling from textiles, in which a detergent and a polymeric active ingredient mentioned are brought into contact with soiled textiles in a particularly aqueous and surfactant-containing washing liquor. This procedure can be carried out manually or by machine, for example using a domestic washing machine. It is possible in particular for liquid agents and the polymeric active substance to be used at the same time or apply sequentially. Simultaneous use can be carried out particularly advantageously by using a detergent which contains the polymeric active substance. Surfactant- or enzyme-sensitive soiling is understood to mean that which can usually be at least partially removed by surfactants or with the aid of enzymes, such as soiling from oil, grease, make-up or grass, mousse au chocolat, or egg. The polymers used according to the invention also contribute to the removability of such stains in the absence of enzymes or in particular in the absence of bleaches. The use according to the invention and the method according to the invention are preferably realized by adding the polymer, consisting of (mono)amino-based alkoxylate, to an agent free of the corresponding polymer or to a wash liquor which contains an agent free of the corresponding polymer, the amount added of polymer, based on the total weight of the agent free of the corresponding polymer, is preferably in the range from 0.01% by weight to 20% by weight, in particular from 1% by weight to 15% by weight. The polymer which is essential to the invention is particularly preferably used together with liquid detergents in particular which, based on the total weight of the detergent, have a surfactant concentration of at least 30% by weight, preferably in the range from 30% by weight to 65% by weight and in particular 50% by weight wt .-% up to 58 wt .-%. It is preferred that the wash liquor is produced by adding 7 ml to 100 ml, in particular 10 ml to 75 ml, preferably 20 ml to 50 ml, of a liquid aqueous detergent to 12 liters to 60 liters, in particular 15 liters to 20 liters of water .

The polymers essential to the invention can be obtained by processes which are known in principle. The starter molecules, especially amino-containing compounds, with alkylene oxides, such as. B. ethylene oxide (EO), propylene oxide (PO) and / or butylene oxide (BO), preferably reacted under alkaline catalysis, wherein the polymer contains two or three chains of alkylene oxide units per nitrogen atom, and wherein the polymer contains more than 90 mol% propylene oxide units, based on the sum of all alkylene oxide units, and 10 to 18 alkylene oxide units per alkylene oxide chain.

The starter molecule is presented and drained. The epoxides are then metered in in the desired order and quantity under alkaline catalysis, for example using KOH.

Suitable procedures and reaction conditions for the alkoxylation are generally known to those skilled in the art and are described, for example, in Standard work M. Ionescu, "Chemistry and technology of polyols for polyurethanes", Rapra Technology, Shrewsbury, UK, page 60 ff .

Preferred polymers used according to the invention, or their starting materials, are described in the following paragraphs.

According to the invention, the following groups of compounds, inter alia, can serve as starters for the polymers consisting of certain alkoxylates described.

(Mono)amino alcohols, e.g., triethanolamine, alkyl diethanolamine, alkyl diisopropanolamine, trialkylamino alcohols such as triisopropanolamine, N,N-di-(2-hydroxyethyl)cyclohexylamine, N,N-di-(2-hydroxypropyl)cyclohexylamine .

In one embodiment, triethanolamine (TEA) is preferred as a starter. In another preferred embodiment, triisopropanolamine (TIPA) is used as the starter.

Alkyl monoamines such as n-butylamine, n-hexylamine, n-octylamine, isopropylamine, sec-butylamine, tert-butylamine, cyclohexylamine, 2-ethylhexylamine, 2-phenylethylamine.

In one embodiment, the initiator is preferably tert -butylamine (tBA).

Preferred polymers used according to the invention have a weight-average molecular weight of 1300-6000 g/mol, and very particularly preferably 1400-4500 g/mol.

The starter is reacted with an alkylene oxide consisting of propylene oxide or mixtures containing propylene oxide. In particularly preferred embodiments, only propylene oxide is used for the alkoxylation.

According to the invention, two chains of alkylene oxide units are preferably attached on each nitrogen atom of the starter.

In another preferred embodiment, according to the invention, three chains of alkylene oxide units are attached per nitrogen atom of the starter.

In preferred embodiments of the invention, there are 12 to 16 alkylene oxide units and particularly preferably 12 to 15 alkylene oxide units per alkylene oxide chain.

In the context of the use according to the invention and the method according to the invention, it is preferred if the concentration of the polymer defined above in the aqueous washing liquor, such as that used in washing machines but also in hand washing, is 0.001 g/l to 5 g/l, in particular 0 .01 g/l to 2 g/l. The process according to the invention and the use according to the invention are preferably carried out at temperatures in the range from 10.degree. C. to 95.degree. C., in particular in the range from 20.degree. C. to 40.degree. The process according to the invention and the use according to the invention are preferably carried out at pH values in the range from pH 5 to pH 12, in particular from pH 7 to pH 11.

Detergents which can be used in connection with the use according to the invention or in the process according to the invention in addition to the polymer and which, in particular, are pulverulent solids, in post-compacted particle form, as solutions or suspensions, can contain all known ingredients customary in such agents. The funds can in particular 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, wrinkle-reducing and shape-retaining polymeric active ingredients, and other auxiliaries, such as optical brighteners , foam regulators, colorants and fragrances.

The agents can contain one or more surfactants, with anionic surfactants, nonionic surfactants and mixtures thereof being particularly suitable, but cationic and/or amphoteric surfactants can also be present.

All nonionic surfactants known to those skilled in the art can be used as nonionic surfactants. The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols preferably having 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, such as are usually present in oxo alcohol radicals. In particular, however, alcohol ethoxylates with linear radicals from alcohols of natural origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 moles of EO per mole of alcohol are preferred. Preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 EO or 4 EO, C _9-11 alcohol with 7 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C C _12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C _12-14 alcohol with 3 EO and C _12-18 alcohol with 5 EO. The degrees of ethoxylation given represent statistical mean values 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).

As an alternative or in addition to these nonionic surfactants, it is also possible to use fatty alcohols with more than 12 EO. Examples of this are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO. In addition, alkyl glycosides of the general formula R ⁵ O(G) _x can also be used as further nonionic surfactants, in which R ⁵ is a primary straight-chain or methyl-branched, in particular methyl-branched in the 2-position, aliphatic radical having 8 to 22, preferably 12 to 18 C- corresponds to atoms and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is from 1.2 to 1.4.

Another class of preferably used 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 having 1 to 4 carbon atoms in the alkyl chain.

Nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N,N-dimethylamine oxide and N-tallowalkyl-N,N-dihydroxyethylamine oxide, and the fatty acid alkanolamide type can also be used. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of it.

in der R für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen, R¹ für Wasserstoff, einen Alkyl- oder Hydroxyalkylrest mit 1 bis 4 Kohlenstoffatomen und [Z] für einen linearen oder verzweigten Polyhydroxyalkylrest mit 3 bis 10 Kohlenstoffatomen und 3 bis 10 Hydroxylgruppen steht. Bei den Polyhydroxyfettsäureamiden handelt es sich um bekannte Stoffe, die üblicherweise durch reduktive Aminierung eines reduzierenden Zuckers mit Ammoniak, einem Alkylamin oder einem Alkanolamin und nachfolgender Acylierung mit einer Fettsäure, einem Fettsäurealkylester oder einem Fettsäurechlorid erhalten werden können. Zur Gruppe der Polyhydroxyfettsäureamide gehören auch Verbindungen der Formel

in der R für einen linearen oder verzweigten Alkyl- oder Alkenylrest mit 7 bis 12 Kohlenstoffatomen, R¹ für einen linearen, verzweigten oder zyklischen Alkylrest oder einen Arylrest mit 2 bis 8 Kohlenstoffatomen und R² für einen linearen, verzweigten oder zyklischen Alkylrest oder einen Arylrest oder einen Oxy-Alkylrest mit 1 bis 8 Kohlenstoffatomen steht, wobei C_1-4-Alkyl- oder Phenylreste bevorzugt sind und [Z] für einen linearen Polyhydroxyalkylrest steht, dessen Alkylkette mit mindestens zwei Hydroxylgruppen substituiert ist, oder alkoxylierte, vorzugsweise ethoxylierte oder propoxylierte Derivate dieses Restes. [Z] wird vorzugsweise durch reduktive Aminierung eines reduzierten Zuckers erhalten, beispielsweise Glucose, Fructose, Maltose, Lactose, Galactose, Mannose oder Xylose. Die N-Alkoxy- oder N-Aryloxy-substituierten Verbindungen können durch Umsetzung mit Fettsäuremethylestern in Gegenwart eines Alkoxids als Katalysator in die gewünschten Polyhydroxyfettsäureamide überführt werden.Other suitable surfactants are polyhydroxy fatty acid amides of the formula

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. 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

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 oxy-alkyl radical having 1 to 8 carbon atoms, with C _1-4 -alkyl or phenyl radicals being preferred and [Z] representing a linear polyhydroxyalkyl radical whose alkyl chain is substituted with at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated Derivatives of this residue. [Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy- or N-aryloxy-substituted compounds can be converted to the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide catalyst.

Examples of anionic surfactants used are those of the sulfonate and sulfate type. Surfactants of the sulfonate type are preferably C _9-13 -alkylbenzene sulfonates, olefin sulfonates, i.e. mixtures of alkene and hydroxyalkane sulfonates and disulfonates, such as those obtained, for example, from C _12-18 -monoolefins with a terminal or internal double bond by sulfonation with gaseous Sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products. Also suitable are alkanesulfonates obtained from C _12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. Also suitable are the esters of α-sulfofatty acids (ester sulfonates), for example the α-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 are to be understood as meaning the mono-, di- and triesters and mixtures thereof as are 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 sulfonated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 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 are also suitable

RO-SO _3M ,

in which R is a linear, branched-chain or cyclic saturated hydrocarbon radical having 12 to 18, in particular 12 to 14, carbon atoms and M is a counter-cation leading to charge neutralization of the sulfuric acid monoester, in particular a sodium or potassium ion or an ammonium ion of the general formula

^{R1R2R3R4N + , _ _}

in which R ¹ , R ² , R ³ and R ⁴ independently represent hydrogen, an alkyl group having 1 to 4 carbon atoms or a hydroxyalkyl group having 2 to 3 carbon atoms. Preferred radicals R are derived from native C ₁₂ -C ₁₈ fatty alcohols, such as coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or the C ₁₀ -C ₂₀ oxo alcohols or secondary alcohols of these chain lengths. Also preferred are alkyl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical produced on a petrochemical basis, which have a similar degradation behavior as the appropriate compounds based on oleochemical raw materials. C ₁₂ -C ₁₆ alkyl sulfates and C ₁₂ -C ₁₄ alkyl sulfates are particularly preferred.

The sulfuric acid monoesters of the straight-chain or branched C _7-21 alcohols ethoxylated with 1 to 6 moles of ethylene oxide, such as 2-methyl-branched C _9-11 alcohols with an average of 3.5 moles of ethylene oxide (EO) or C _12-18 - Fatty alcohols with 1 to 4 EO are suitable.

Other suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters, and the monoesters and/or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contain C _8-18 fatty alcohol residues or mixtures thereof. Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols which, considered in themselves, represent nonionic surfactants. In this context, sulfosuccinates whose fatty alcohol radicals are derived from ethoxylated fatty alcohols with a narrow homolog distribution are particularly preferred. It is also possible to use alk(en)ylsuccinic acid preferably having 8 to 18 carbon atoms in the alk(en)yl chain or salts thereof.

Soaps, in particular, come into consideration as further anionic surfactants. 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, are suitable.

The anionic surfactants, including soaps, can be in the form of their sodium, potassium or ammonium salts, as well 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.

Instead of the surfactants mentioned or in combination with them, cationic and/or amphoteric surfactants can also be used.

worin jede Gruppe R¹ unabhängig voneinander ausgewählt ist aus C_1-6-Alkyl-, -Alkenyl- oder -Hydroxyalkylgruppen; jede Gruppe R² unabhängig voneinander ausgewählt ist aus C_8-28-Alkyl- oder -Alkenylgruppen; R³ = R¹ oder (CH₂)_n-T-R²; R⁴ = R¹ oder R² oder (CH₂)_n-T-R²; T = -CH₂-, - O-CO- oder -CO-O- und n eine ganze Zahl von 0 bis 5 ist.For example, cationic compounds of the following formulas can be used as cationic active substances:

wherein each R ¹ group is independently selected from C _1-6 alkyl, alkenyl or hydroxyalkyl groups; each R ² group is independently selected from C _8-28 alkyl or alkenyl groups; R ³ = R ¹ or (CH ₂ ) _n -TR ² ; R ⁴ = R ¹ or R ² or (CH ₂ ) _n -TR ² ; T = -CH ₂ -, -O-CO- or -CO-O- and n is an integer from 0 to 5.

Surfactants of this type are contained in detergents in amounts of preferably 5% by weight to 65% by weight. As stated above, particularly preferred detergents are liquid and have surfactant contents of at least 30% by weight, preferably in the range from 30% by weight to 60% by weight and in particular from 50% by weight to 58% by weight. Such concentrated liquid detergents are advantageous because they use fewer resources, which is due in particular to the lower transport weight and reduced consumption size. In comparison to detergents with a lower concentration, for example, you need a smaller bottle size and therefore less packaging material to achieve the same application performance . In addition, such highly concentrated agents are preferred by consumers because they take up little storage space in the household.

Textile-softening compounds can be used to care for the textiles and to improve the textile properties, such as a softer "handle" (finish) and reduced electrostatic charging (increased wearing comfort). The active ingredients of these formulations are quaternary ammonium compounds with two hydrophobic residues, such as disteraryldimethylammonium chloride, which, however, is increasingly being replaced by quaternary ammonium compounds that contain ester groups in their hydrophobic residues as predetermined breaking points for biodegradation because of its insufficient biodegradability.

Such “esterquats” 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. Dimethylolethylene urea is suitable as a finishing agent.

A detergent preferably contains at least one water-soluble and/or water-insoluble, organic and/or inorganic builder. The water-soluble organic builder substances include polycarboxylic acids, especially citric acid and sugar acids, monomeric and polymeric aminopolycarboxylic acids, especially methylglycinediacetic acid, nitrilotriacetic acid and ethylenediaminetetraacetic acid, and polyaspartic acid, polyphosphonic acids, especially 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 mixed polymers of these, which can also contain small amounts of polymerizable substances without carboxylic acid functionality as polymerized units. 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. mol, in each case based on the free acid. A particularly preferred acrylic acid-maleic acid copolymer has a relative molecular weight of 50,000 g/mol to 100,000 g/mol. Suitable, 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 the 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 C ₃ -C ₈ -carboxylic acid and preferably from a C ₃ -C ₄ -monocarboxylic acid, in particular from (meth)acrylic acid. The second acidic monomer or its salt can be a derivative of a C ₄ -C ₈ -dicarboxylic acid, maleic acid being particularly preferred, 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 weight of between 1000 g/mol and 200,000 g/mol. Further preferred copolymers are those which contain acrolein and acrylic acid/acrylic acid salts or vinyl acetate as monomers. The organic builder substances can be used in the form of aqueous solutions, preferably in the form of 30 to 50 percent by weight aqueous solutions, particularly for the production of liquid agents. All of the acids mentioned are generally used in the form of their water-soluble salts, in particular their alkali metal salts.

Such organic builder substances can, if desired, be present in amounts of up to 40% by weight, in particular up to 25% by weight and preferably from 0.5% by weight to 8% by weight. Amounts in the upper half of the ranges mentioned are preferably used in paste-like or liquid, in particular aqueous, agents.

Particularly suitable as water-soluble inorganic builder materials are polymeric alkali metal phosphates, which can be present in the form of their alkaline, neutral or acidic sodium or potassium salts. Examples of these are tetrasodium diphosphate, disodium dihydrogen diphosphate, pentasodium triphosphate, so-called sodium hexametaphosphate and the corresponding potassium salts or mixtures of sodium and potassium salts. In particular, crystalline or amorphous alkali metal aluminosilicates, in amounts of up to 50% by weight, preferably not more than 40% by weight and in liquid compositions, in particular from 1% by weight to 5% by weight, are used as water-insoluble, water-dispersible inorganic builder materials. deployed. Among these, the crystalline detergent grade sodium aluminosilicates, particularly zeolite A, P and optionally X, are preferred. Amounts close to the upper limit mentioned are preferably used in solid, particulate compositions. In particular, suitable aluminosilicates do not have any particles with a particle size of more than 30 μm and preferably consist of at least 80% by weight of particles with a size of less than 10 μm. Their calcium binding capacity is usually in the range of 100 mg to 200 mg CaO per gram.

Suitable substitutes or partial substitutes for the aluminosilicate mentioned are crystalline alkali metal silicates, which can be present alone or in a mixture with amorphous silicates. The alkali metal silicates which can be used as builders preferably have a molar ratio of alkali metal oxide to SiO ₂ below 0.95, in particular from 1:1.1 to 1:12, and can be amorphous or crystalline. Preferred alkali silicates are the sodium silicates, in particular the amorphous sodium silicates, with a molar ratio Na ₂ O:SiO ₂ of 1:2 to 1:2.8. Crystalline phyllosilicates of the general formula Na ₂ Si _x O _2x+1 y H ₂ O are preferably used as crystalline silicates, which can be present alone or in a mixture with amorphous silicates, 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 has the value 2 or 3 in the general formula mentioned. In particular, both β- and δ-sodium disilicates (Na ₂ Si ₂ O ₅ .yH ₂ O) are preferred. Practically anhydrous crystalline alkali metal silicates of the abovementioned general formula in which x is a number from 1.9 to 2.1 and produced from amorphous alkali metal silicates can also be used. In a further preferred embodiment, a crystalline layered sodium silicate with a modulus of 2 to 3 is used, such as can be produced from sand and soda. In a further preferred embodiment, crystalline sodium silicates with a modulus in the range from 1.9 to 3.5 are used. In a preferred embodiment, a granular compound of alkali metal silicate and alkali metal carbonate is used, as is commercially available, for example, under the name ^Nabion® 15. If alkali metal aluminosilicate, in particular zeolite, is also present as an additional builder substance, the weight ratio of aluminosilicate to silicate, based in each case on anhydrous active substances, is preferably 1:10 to 10:1. In compositions containing both amorphous and crystalline alkali metal silicates, the weight ratio of amorphous alkali metal silicate to crystalline alkali metal silicate is preferably 1:2 to 2:1 and in particular 1:1 to 2:1.

Detergents preferably contain builder substances in amounts of up to 60% by weight, in particular from 0.5% by weight to 40% by weight.

1. a) 5 Gew.-% bis 35 Gew.-% Citronensäure, Alkalicitrat und/oder Alkalicarbonat, welches auch zumindest anteilig durch Alkalihydrogencarbonat ersetzt sein kann,
2. b) bis zu 10 Gew.-% Alkalisilikat mit einem Modul im Bereich von 1,8 bis 2,5,
3. c) bis zu 2 Gew.-% Phosphonsäure und/oder Alkaliphosphonat,
4. d) bis zu 50 Gew.-% Alkaliphosphat, und
5. e) bis zu 10 Gew.-% polymerem Polycarboxylat,

• wobei die Mengenangaben sich auf das gesamte Waschmittel beziehen. Dies gilt auch für alle folgenden Mengenangaben, sofern nicht ausdrücklich anders angegeben.
• In einer bevorzugten Ausführungsform enthält der wasserlösliche Builderblock mindestens 2 der Komponenten b), c), d) und e) in Mengen größer 0 Gew.-%.

In a preferred embodiment, the agent has a water-soluble builder block. The use of the term "builder block" is intended to express that the agent does not contain any other builder substances 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 at most the amounts of Substances are excluded, which can be contained as impurities or stabilizing additives in small amounts in the other ingredients of the agent in a commercial manner. The term “water-soluble” should be understood to mean that the builder block dissolves without residue at the concentration that results from the amount of agent containing it under the usual conditions. The detergents preferably contain 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. This is preferably composed of the components

1. a) 5% by weight to 35% by weight of citric acid, alkali metal citrate and/or alkali metal carbonate, which can also be replaced at least partially by alkali metal bicarbonate,
2. b) up to 10% by weight of alkali silicate with a modulus in the range from 1.8 to 2.5,
3. c) up to 2% by weight of phosphonic acid and/or alkali metal phosphonate,
4. d) up to 50% by weight alkali metal phosphate, and
5. e) up to 10% by weight polymeric polycarboxylate,

• where the quantities are based on the entire detergent. This also applies to all the following quantities, unless expressly stated otherwise.
• In a preferred embodiment, the water-soluble builder block contains at least 2 of components b), c), d) and e) in amounts greater than 0% by weight.

With regard to component a), in a preferred embodiment, 15% by weight to 25% by weight alkali metal carbonate, which can be replaced at least partially by alkali metal bicarbonate, and up to 5% by weight, in particular 0.5% by weight 2.5% by weight of citric acid and/or alkali citrate. In an alternative embodiment, component a) contains 5% by weight to 25% by weight, in particular 5% by weight to 15% by weight, of citric acid and/or alkali metal citrate and up to 5% by weight, in particular 1% by weight .-% to 5 wt .-% alkali metal carbonate, which can be replaced at least partially by alkali metal bicarbonate included. If both alkali metal carbonate and alkali metal bicarbonate are present, component a) preferably has alkali metal carbonate and alkali metal bicarbonate in a weight ratio of from 10:1 to 1:1.

With regard to component b), a preferred embodiment contains 1% by weight to 5% by weight of alkali metal silicate with a modulus in the range from 1.8 to 2.5.

With regard to component c), a preferred embodiment contains 0.05% by weight to 1% by weight of phosphonic acid and/or alkali metal phosphonate. Phosphonic acids are also understood as meaning optionally substituted alkyl phosphonic acids which can also have several phosphonic acid groups (so-called polyphosphonic acids). They are preferably selected from the hydroxy and/or aminoalkylphosphonic acids and/or their alkali metal 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.

With regard to component d), a preferred embodiment contains 15% by weight to 35% by weight of alkali metal phosphate, in particular trisodium polyphosphate. Alkaline phosphate is the general term for the alkali metal (especially sodium and potassium) salts of the various phosphoric acids, in which metaphosphoric acids (HPO ₃ ) _n and orthophosphoric acid H ₃ PO ₄ can be distinguished in addition to higher-molecular representatives. The phosphates combine several advantages: they act as alkali carriers, prevent lime deposits on machine parts and lime incrustations in fabrics and also contribute to the cleaning performance. Sodium dihydrogen phosphate, NaH ₂ PO ₄ , exists as a dihydrate (density 1.91 gcm ^-3 , melting point 60°) and as a monohydrate (density 2.04 gcm ^-3 ). Both salts are white powders, very easily soluble in water, which lose the water of crystallization when heated and are converted into the weakly acidic diphosphate (disodium hydrogen diphosphate, Na ₂ H ₂ P ₂ O ₇ ) at 200°C and into sodium trimetaphosphate (Na ₃ P ₃ O ₉ ) and Madrell's salt. NaH ₂ PO ₄ is acidic; it is formed when phosphoric acid with caustic soda to a pH of 4.5 adjusted and the mash is sprayed. Potassium dihydrogen phosphate (potassium phosphate primary or monobasic, potassium biphosphate, KDP), KH ₂ PO ₄ , is a white salt with a density of 2.33 gcm ^-3 , a melting point of 253° (decomposes to form (KPO ₃ ) _x , potassium polyphosphate) and is easily soluble in water. Disodium hydrogen phosphate (secondary sodium phosphate), Na ₂ HPO ₄ , is a colourless, very easily water-soluble crystalline salt. It exists anhydrous and with 2 moles (density 2.066 gcm ^-3 , loss of water at 95°), 7 moles (density 1.68 gcm ^-3 , melting point 48° with loss of 5 H ₂ O) and 12 moles of water (density 1, 52 gcm ^-3 , melting point 35° with loss of 5 H ₂ O), becomes anhydrous at 100° and converts to the diphosphate Na ₄ P ₂ O ₇ when heated more intensely. 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), K ₂ HPO ₄ , is an amorphous, white salt that is readily soluble in water. Trisodium phosphate, tertiary sodium phosphate, Na ₃ PO ₄ , are colorless crystals which, as dodecahydrate, have a density of 1.62 gcm ^-3 and a melting point of 73-76°C (decomposition), as decahydrate (equivalent to 19-20% P ₂ O ₅ ) have a melting point of 100°C and in anhydrous form (corresponding to 39-40% P ₂ O ₅ ) a density of 2.536 gcm ^-3 . Trisodium phosphate is easily soluble in water with an alkaline reaction and is prepared by evaporating a solution of exactly 1 mole of disodium phosphate and 1 mole of NaOH. Tripotassium phosphate (potassium tertiary or tribasic phosphate), K ₃ PO ₄ , is a white, deliquescent, granular powder with a density of 2.56 gcm ^-3 , has a melting point of 1340° and is readily soluble in water with an alkaline reaction. It is formed, for example, when Thomas slag is heated with coal and potassium sulphate. 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 P ₂ O ₇ , exists in anhydrous form (density 2.534 gcm ^-3 , melting point 988°, also given as 880°) and as decahydrate (density 1.815-1.836 gcm ^-3 , melting point 94° with loss of water) . Substances are colorless crystals that are soluble in water with an alkaline reaction. Na ₄ P ₂ O ₇ is formed when disodium phosphate is heated to >200°C or by reacting phosphoric acid with soda in a stoichiometric ratio and dewatering the solution by spraying. The decahydrate complexes heavy metal salts and hardeners and therefore reduces the hardness of the water. Potassium diphosphate (potassium pyrophosphate), K ₄ P ₂ O ₇ , exists in the form of the trihydrate and is a colourless, hygroscopic powder with a density of 2.33 gcm ^-3 , which is soluble in water at a pH of 1% solution at 25° is 10.4. Condensation of the NaH ₂ PO ₄ or the KH ₂ PO ₄ results in higher molecular weight sodium and potassium phosphates, in which one can distinguish between cyclic representatives, the sodium or potassium metaphosphates, and chain-type types, the sodium or potassium polyphosphates. A large number of terms are used for the latter in particular: melted 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. The technically important pentasodium triphosphate, Na ₅ P ₃ O ₁₀ (sodium tripolyphosphate), is an anhydrous or crystallizing with 6 H ₂ O, non-hygroscopic, white, water-soluble salt of the general formula NaO-[P(O)(ONa)-O] _n -Well with n=3. In 100 g water, about 17 g dissolve at room temperature, about 20 g at 60°, and about 32 g at 100° of the anhydrous salt; after After heating the solution for two hours at 100°, about 8% orthophosphate and 15% diphosphate are formed by hydrolysis. In the production of pentasodium triphosphate, phosphoric acid is reacted with soda solution or caustic soda in a stoichiometric ratio and the solution. dehydrated by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (also soap scum, etc.). Pentapotassium triphosphate, K ₅ P ₃ O ₁₀ (potassium tripolyphosphate), is commercially available, for example, in the form of a 50% by weight solution (>23% P ₂ O ₅ , 25% K ₂ O). There are also sodium potassium tripolyphosphates which can also be used within the scope of the present invention. These arise, for example, when sodium trimetaphosphate is hydrolyzed with KOH:

(NaPO ₃ ) ₃ + 2 KOH → Na ₃ K ₂ P ₃ O ₁₀ + H ₂ O

These can be used just like sodium tripolyphosphate, potassium tripolyphosphate or mixtures of these 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.

With regard to component e), a preferred embodiment of the agent contains 1.5% by weight to 5% by weight of polymeric polycarboxylate, selected in particular from the polymerization or copolymerization products of acrylic acid, methacrylic acid and/or maleic acid. Among these, the homopolymers of acrylic acid and among these, in turn, those with an average molar mass in the range from 5,000 D to 15,000 D (PA standard) are particularly preferred.

Enzymes that can be used in the agents are those from the class of lipases, cutinases, amylases, pullulanases, mannanases, cellulases, hemicellulases, xylanases and peroxidases and 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 ^® . Enzymatic active substances 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. Any enzymes used can be adsorbed on carriers and/or embedded in encapsulating substances in order to protect them against premature inactivation. Detergents preferably contain them in amounts of up to 10% by weight, in particular from 0.2% by weight to 2% by weight.

In a preferred embodiment, the agent contains 5% by weight to 65% by weight, in particular 8 to 55% by weight, of anionic and/or nonionic surfactant, up to 60% by weight, in particular 0.5 to 40% by weight. -% builder and 0.2% to 5% by weight enzyme from the lipases, cutinases, amylases, pullulases, mananases, cellulases, oxidases and peroxidases and mixtures thereof.

The organic solvents that can be used in the detergents, especially if they are in liquid or pasty form, include alcohols with 1 to 4 carbon atoms, in particular methanol, ethanol, isopropanol and tert-butanol, diols with 2 to 4 carbon atoms, in particular ethylene glycol and propylene glycol, and mixtures thereof and the ethers which can be derived from the classes of compounds mentioned. Such water-miscible solvents are preferably present in the compositions in amounts of not more than 30% by weight, in particular from 6% by weight to 20% by weight.

Polymers originating from nature that can be used as thickeners in aqueous liquid agents are, for example, agar-agar, carrageenan, tragacanth, gum arabic, alginates, pectins, polyoses, guar flour, locust bean gum, starch, dextrins, gelatine and casein, cellulose derivatives such as carboxymethyl cellulose, hydroxyethyl and propyl cellulose, and polymeric polysaccharide thickeners such as xanthan gum; fully synthetic polymers such as polyacrylic and polymethacrylic compounds, vinyl polymers, polycarboxylic acids, polyethers, polyimines, polyamides and polyurethanes can also be used as thickeners.

To set a desired pH value that does not result automatically from mixing the other components, the agents can contain acids that are compatible with the system and the environment, in particular citric acid, acetic acid, tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid and/or adipic acid, but also contain mineral acids, in particular sulfuric acid, or bases, in particular ammonium or alkali metal hydroxides. Such pH regulators are preferably contained in the agents in not more than 20% by weight, in particular from 1.2% by weight to 17% by weight.

Polymers capable of releasing dirt, which are often referred to as "soil release" active substances or as "soil repellents" because of their ability to make the treated surface, for example the fiber, dirt-repellent, are, for example, nonionic or cationic cellulose derivatives. The particularly polyester-active soil release 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 dirt-removing polyesters include those compounds that are formally accessible by esterification of two monomer parts, the first monomer being a dicarboxylic acid HOOC-Ph-COOH and the second monomer being a diol HO-(CHR ¹¹ -) _a OH, which can also be used as a polymeric diol H-(O-(CHR ¹¹ -) _a ) _b OH may be present. Ph is an o-, m- or p-phenylene radical which can carry 1 to 4 substituents selected from alkyl radicals having 1 to 22 carbon atoms, sulfonic acid groups, carboxyl groups and mixtures thereof, R ¹¹ is hydrogen, an alkyl radical having 1 to 22 carbon atoms and mixtures thereof, a is a number from 2 to 6 and b a number from 1 to 300. The polyesters obtainable from these preferably contain both monomer diol units -O-(CHR ¹¹ -) _a O- and polymer diol units -(O-(CHR ¹¹ -) _a ) _b O-. 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 in the polymer diol units 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-removing polyesters is in the range from 250 to 100,000, in particular from 500 to 50,000 The acid on which the radical Ph is based is preferably selected from terephthalic acid, isophthalic acid, phthalic acid, trimellitic acid, mellitic acid, the isomers of sulfophthalic acid, sulfoisophthalic acid and sulfoterephthalic acid and mixtures thereof. If their acid groups are not part of the ester bonds in the polymer, they are preferably present in salt form, in particular as an alkali metal or ammonium salt. Among these, the sodium and potassium salts are particularly preferred. If desired, instead of the HOOC-Ph-COOH monomer, small proportions, in particular not more than 10 mol % based on the proportion of Ph with the meaning given above, of other acids which have at least two carboxyl groups can be present in the soil-removing polyester. These include, for example, alkylene and alkenylenedicarboxylic acids such as malonic acid, succinic acid, fumaric acid, maleic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid. Preferred diols HO-(CHR ¹¹ -) _a OH include those in which R ¹¹ is hydrogen and a is from 2 to 6 and those in which a is 2 and R ¹¹ is selected from hydrogen and the alkyl radicals 1 to 10, in particular 1 to 3 carbon atoms is selected. Among the last-mentioned diols, those of the formula HO-CH ₂ -CHR ¹¹ -OH, in which R ¹¹ has the meaning given above, are particularly preferred. Examples of diol components are ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,2-decanediol, 1, 2-dodecanediol and neopentyl glycol. Particularly preferred among the polymeric diols is polyethylene glycol with an average molar mass in the range from 1000 to 6000. If desired, these polyesters can also be end-capped, suitable end groups being alkyl groups having 1 to 22 carbon atoms and esters of monocarboxylic acids. The end groups bonded via ester bonds can be based on alkyl, alkenyl and aryl monocarboxylic acids having 5 to 32 carbon atoms, in particular 5 to 18 carbon atoms. 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, melissic acid, benzoic acid, which can carry 1 to 5 substituents with a total of up to 25 carbon atoms, in particular 1 to 12 carbon atoms, for example tert-butylbenzoic acid . The end groups can also be based on hydroxymonocarboxylic acids with 5 to 22 carbon atoms, which include, for example, hydroxyvaleric acid, hydroxycaproic acid, ricinoleic acid, their hydrogenation product hydroxystearic acid and o-, m- and p-hydroxybenzoic acid. The hydroxy monocarboxylic acids can in turn via their hydroxyl group and their carboxyl group can be connected to one another and are therefore present several times in an end group. The number of hydroxymonocarboxylic acid units per end group, i.e. their degree of oligomerization, is preferably in the range from 1 to 50, in particular from 1 to 10. In a preferred embodiment of the invention, polymers of ethylene terephthalate and polyethylene oxide terephthalate in which the polyethylene glycol units have molecular weights of 750 to 5000 and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate is 50:50 to 90:10, used alone or in combination with cellulose derivatives.

The color transfer inhibitors suitable for use in detergents for washing textiles 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 agents can contain anti-crease agents, since textile fabrics, especially those made from rayon, wool, cotton and mixtures thereof, can tend to wrinkle because the individual fibers are sensitive to bending, buckling, pressing and squeezing transversely to the fiber direction. These include, for example, synthetic products based on fatty acids, fatty acid esters, fatty acid amides, fatty acid alkylol esters, fatty acid alkylolamides or fatty alcohols, which are usually reacted with ethylene oxide, or products based on lecithin or modified phosphoric acid esters.

Graying inhibitors have the task of keeping the dirt detached from the hard surface and in particular from the textile fibers suspended in the liquor. Water-soluble colloids, usually of an organic nature, are suitable for this purpose, for example starch, glue, gelatin, salts of ether carboxylic acids or ether sulfonic 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. Furthermore, starch derivatives other than those mentioned above can be used, for example aldehyde starches. Cellulose ethers such as carboxymethyl cellulose (Na salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof are preferably used, for example in amounts of 0.1 to 5% by weight, based on the detergent.

The agents can contain optical brighteners, including, in particular, derivatives of diaminostilbene disulfonic acid or their alkali metal salts. Suitable are, for example, salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or similarly constructed compounds that instead of morpholino - carry a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group. Brighteners of the substituted diphenylstyryl type can also be present, for example the alkali metal salts of 4,4'-bis(2-sulfostyryl)diphenyl, 4,4'-bis(4-chloro-3-sulfostyryl)diphenyl, or 4-(4-chlorostyryl)-4'-(2-sulfostyryl)diphenyls. Mixtures of the aforementioned optical brighteners can also be used.

In particular when used in machine washing processes, it can be advantageous to add customary foam inhibitors to the detergents. Examples of suitable foam inhibitors are soaps of natural or synthetic origin which have a high proportion of C ₁₈ -C ₂₄ fatty acids. Examples of suitable non-surfactant foam inhibitors are organopolysiloxanes and mixtures thereof with microfine, optionally silanated silica, and paraffins, waxes, microcrystalline waxes and mixtures thereof with silanated silica or bis-fatty acid alkylenediamides. Mixtures of different foam inhibitors are also used with advantage, for example those made of 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 bistearylethylenediamide are particularly preferred.

Peroxygen compounds which may be present in the detergents, in particular the detergents in solid form, include, in particular, organic peracids or peracid salts of organic acids, such as phthalimidopercaproic acid, perbenzoic acid or salts of diperdodecanedioic acid, hydrogen peroxide and inorganic salts which release hydrogen peroxide under the washing conditions, such as perborate, percarbonate and/or or persilicate. Hydrogen peroxide can also be generated with the help of an enzymatic system, ie an oxidase and its substrate. If solid peroxygen compounds are to be used, they can be used in the form of powders or granules, which can also be coated in a manner known in principle. Alkali metal percarbonate, alkali metal perborate monohydrate, alkali metal perborate tetrahydrate or, in particular in liquid compositions, hydrogen peroxide in the form of aqueous solutions containing 3% by weight to 10% by weight of hydrogen peroxide is particularly preferably used. Peroxygen compounds are preferably present in detergents in amounts of up to 50% by weight, in particular from 5% by weight to 30% by weight.

In addition, customary bleach activators, which form peroxocarboxylic acids or peroxoimidic acids under perhydrolysis conditions, and/or customary bleach-activating transition metal complexes can be used. The component of the bleach activators which is optionally present, in particular in amounts of from 0.5% by weight to 6% by weight, comprises the N- or O-acyl compounds which are customarily used, for example polyacylated alkylenediamines, in particular tetraacetylethylenediamine, acylated glycolurils, in particular tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, urazoles, diketopiperazines, sulfurylamides and cyanurates, also carboxylic acid anhydrides, especially phthalic anhydride, carboxylic acid esters, especially sodium isononanoyl phenolsulfonate, and acylated sugar derivatives, especially pentaacetyl glucose, and cationic nitrile derivatives such as trimethylammonium acetonitrile salts. To avoid interaction with the peroxygen compounds during storage, the bleach activators can be coated with encapsulating substances in a known manner have been coated or granulated, with the aid of carboxymethylcellulose granulated tetraacetylethylenediamine with an average grain size of 0.01 mm to 0.8 mm, granulated 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine, and/ or trialkylammonium acetonitrile formulated in particulate form is particularly preferred. Such bleach activators are preferably present in detergents in amounts of up to 8% by weight, in particular from 2% by weight to 6% by weight, based in each case on the detergent as a whole.

The production of solid compositions presents no difficulties and can be carried out in a manner known in principle, for example by spray drying or granulation. To produce the agents with an increased bulk density, in particular in the range from 650 g/l to 950 g/l, a process having an extrusion step is preferred. Detergents in the form of aqueous solutions or solutions containing other customary solvents are particularly advantageously produced by simply mixing the ingredients, which can be added to an automatic mixer as such or as a solution.

In an embodiment that is also preferred, the agents, in particular in concentrated liquid form, are present as a portion in a completely or partially water-soluble envelope. The portioning makes it easier for the consumer to dose.

The funds can be packed in foil bags, for example. Pouch packaging made from water-soluble film eliminates the need for the consumer to tear open the packaging. In this way, a single portion measured for a wash cycle can be conveniently dosed 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 wash basin. The film bag surrounding the wash portion dissolves without leaving any residue when a certain temperature is reached.

There are numerous processes in the prior art for producing water-soluble detergent portions which are in principle also suitable for producing detergents which can be used within the scope of the present invention. The best-known methods are the tubular film method with horizontal and vertical sealing seams. The thermoforming process (deep-drawing process) is also suitable for the production of film bags or dimensionally stable detergent portions. However, the water-soluble envelopes do not necessarily have to consist of a film material, but can also be dimensionally stable containers that can be obtained, for example, by means of an injection molding process.

Furthermore, methods for producing water-soluble capsules from polyvinyl alcohol or gelatin are known, 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 shaping cavity. The capsules are filled and sealed either synchronously or in sequential steps, in which case the capsules are filled through a small opening. The capsules are filled, for example by a filling wedge, which is arranged above two counter-rotating drums, which have spherical hemispheres on their surface. The drums carry polymer tapes that cover the cavities of the hemispheres. Sealing takes place at the positions where the polymer tape of one drum meets the polymer tape of the opposite drum. At the same time, the filling material is injected into the capsule that is being formed, with the injection pressure of the filling liquid pressing the polymer strips into the cavities of the hemisphere. A process for the production of water-soluble capsules, in which first the filling and then the sealing takes place, is based on the so-called Bottle-Pack ^® process. Here, a tube-like preform is fed into a two-part cavity. The cavity is closed, with the lower tube section being sealed, the tube is then inflated to form the capsule shape in the cavity, filled and finally sealed.

The casing 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). In the context of the present invention, particularly suitable polyvinyl alcohols 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 also contain 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. It is preferred if 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 12,000 g /mol to 80,000 g/mol and in particular from 13,000 g/mol to 70,000 g/mol. It is also preferred if the thermoplastics are used 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 the water-soluble polymeric thermoplastic.

examples Example 1: Production of polymers

Unless otherwise stated, the following characterization methods were used. GPC (Gel Permeation Chromatography):
To determine the average molecular weight of the polymers obtained, gel permeation chromatography was carried out in THF as the solvent. The GPC system was calibrated with linear polystyrene standards in the molar mass range of 682 - 2,520,000 g/mol.

OH number:

The hydroxyl number was determined titrimetrically based on ASTM E 1899-97.

amine number:

The amine number was determined by titration with trifluoromethanesulfonic acid.

P1: 74.6 g (0.50 mol) triethanolamine and 5.53 g 50% (weight %) KOH solution were mixed and then dehydrated in an autoclave at 100° C. and <10 mbar for two hours. The autoclave was rendered inert by flushing it three times with nitrogen and an inlet pressure of 2 bar was set. The reactor was then heated to 120-130°C and 1307 g (22.5 mol) of propylene oxide was added to produce three 15 PO/OH arms (total 45 PO/triethanolamine). After the end of the metering, the reaction was allowed to react until the pressure was constant. Volatile components were removed within two hours at 90 °C and 20 mbar. The product was characterized by 1H-NMR, OH number, amine number and GPC.

P2: 99.68 g (0.60 mol) triethanolamine and 6.00 g 50% strength (% by weight) KOH solution were mixed and then dehydrated in an autoclave at 100° C. and <10 mbar for two hours. The autoclave was rendered inert by flushing it three times with nitrogen and an inlet pressure of 2 bar was set. The reactor was then heated to 120-130°C and 1261 g (21.7 mol) of propylene oxide was added to produce three 12 PO/OH arms (total 36 PO/triethanolamine). After the end of the metering, the reaction was allowed to react until the pressure was constant. Volatile components were removed within two hours at 90 °C and 20 mbar. The product was characterized by 1H-NMR, OH number, amine number and GPC.

P3: 366 g (4.9 mol) of tert -butylamine and 18.3 g of water were used. The autoclave was rendered inert by flushing it three times with nitrogen and then an admission pressure of 2 bar was set. Then the reactor was heated to 100°C and 581 g (10.0 mol) of propylene oxide was added to produce tert -butylamine + 2PO. After the end of the dosing, the reaction was allowed to proceed react until the pressure was constant. Volatile components were removed within two hours at 80 °C and 20 mbar. The intermediate was characterized by 1H NMR, OH number, amine number and GPC.

170 g (0.89 mol) of the intermediate and 5.30 g of 50% strength (% by weight) KOH solution were mixed and then dewatered in an autoclave at 130° C. and <10 mbar for two hours. The autoclave was rendered inert by flushing it three times with nitrogen and then an admission pressure of 2 bar was set. Then the reactor was heated to 120-130°C and 1150 g (19.8 mol) of propylene oxide was added to produce two 12 PO/OH arms (total 24 PO/ tert -butylamine). After the end of the metering, the reaction was allowed to react until the pressure was constant. Volatile components were removed within two hours at 80 °C and 20 mbar. The product was characterized by 1H-NMR, OH number, amine number and GPC.

P4: 104 g (0.54 mol) triisopropanolamine and 4.2 g 50% strength (% by weight) KOH solution were mixed and then dewatered in an autoclave at 100° C. and <10 mbar for two hours. The autoclave was rendered inert by flushing it three times with nitrogen and an inlet pressure of 2 bar was set. The reactor was then heated to 120-130°C and 1415 g (24.4 mol) of propylene oxide was added to produce three 15 PO/OH arms (total 45 PO/triisopropanolamine). After the end of the metering, the reaction was allowed to react until the pressure was constant. Volatile components were removed within two hours at 90 °C and 20 mbar. The product was characterized by 1H-NMR, OH number, amine number and GPC.

Example 2: Washing trials

Textile fabrics made from the materials listed in Table 2, which had been provided with the standardized stains also listed in Table 2, were washed at 30° C. with washing liquors each containing 0.88 g/l of a detergent C1, W1, W2, or W3 the composition given in Table 1, washed and then dried. The resulting lightness values (Y values) were determined. It can be seen that when a polymer that is essential to the invention was added, the washing results were significantly better than without it. Table 1: Detergent composition (% by weight) Ingredient / Agent V1 w1 W2 W3 W4 Linear C _10-13 alkyl benzene sulfonate 22 22 22 22 22 C _13/15 oxo alcohol with 8 EO 24 24 24 24 24 C _12-18 fatty acid 7.5 7.5 7.5 7.5 7.5 polymer P1 - 5 - - polymer P2 - - 5 - - polymer P3 - - - 5 - Polymer P4 - - - - 5 propylene glycol 8th 8th 8th 8th 8th glycerin 10.5 10.5 10.5 10.5 10.5 Optical brightener 0.6 0.6 0.6 0.6 0.6 monoethanolamine 6 6 6 6 6 DTPMPA 7Na 0.7 0.7 0.7 0.7 0.7 ethanol 3 3 3 3 3 Soil release polymer Texcare ^® SRN 170 1.4 1.4 1.4 1.4 1.4 Perfume 1.7 1.7 1.7 1.7 1.7 water on 100

Claims (15)

1. The use of polymers, consisting of (mono)amino-based alkoxylates having an average molecular weight M_w of 600 - 10 000 g/mol, for enhancing the primary detergency of laundry detergent compositions when washing textiles in in particular aqueous and surfactant-containing washing liquid with respect to soiling, wherein the polymer comprises two or three chains of alkylene oxide units per nitrogen atom, wherein the soiling is surfactant- or enzyme-sensitive soiling, and wherein the polymer comprises more than 90 mol% propylene oxide units, based on the sum total of all alkylene oxide units, and 10 to 18 alkylene oxide units per alkylene oxide chain.
2. The use according to claim 1, wherein said use is effected by adding the polymer to a composition which is free of the corresponding polymer or to a washing liquor which comprises a composition which is free of the corresponding polymer.
3. The use according to claim 2, wherein the amount of polymer added, based on the amount of composition which is free of the corresponding polymer, is in the range from 0.01% by weight to 20% by weight, in particular from 1% by weight to 15% by weight.
4. A method for removing surfactant- or enzyme-sensitive soiling from textiles, wherein a polymer, consisting of (mono)amino-based alkoxylates, preferably propoxylates, having an average molecular weight M_w of 600 - 10 000 g/mol, in an in particular aqueous and surfactant-containing washing liquor is brought into contact with soiled textiles, wherein the polymer comprises two or three chains of alkylene oxide units per nitrogen atom, and wherein the polymer comprises more than 90 mol% propylene oxide units, based on the sum total of all alkylene oxide units, and 10 to 18 alkylene oxide units per alkylene oxide chain.
5. The method according to claim 4 or the use according to any of claims 1 to 3, wherein the washing liquor is produced by adding from 10 ml to 100 ml, in particular from 15 ml to 75 ml, preferably from 25 ml to 50 ml, of a liquid water-containing laundry detergent composition to 12 liters to 60 liters, in particular 15 liters to 20 liters, of water.
6. The use according to claim 2 or 3 or the method according to claim 5, wherein the composition has a surfactant concentration of at least 30% by weight, in particular in the range from 30% by weight to 65% by weight and in particular from 50% by weight to 38% by weight.
7. The use or method according to any of the preceding claims, wherein the polymer, consisting of (mono)amino-based alkoxylates having an average molecular weight M_w of 600 - 10 000 g/mol, comprises exclusively propylene oxide units, based on the sum total of all alkylene oxide units.
8. The use or method according to any of the preceding claims, wherein the polymer, consisting of (mono)amino-based alkoxylates having an average molecular weight M_w of 600 - 10 000 g/mol, is based on a starter selected from the list consisting of triethanolamine, triisopropanolamine and tert-butylamine.
9. The use or method according to claim 8, wherein the polymer, consisting of (mono)amino-based alkoxylates having an average molecular weight M_w of 600 - 10 000 g/mol, is based on triethanolamine.
10. The use or method according to claim 8, wherein the polymer, consisting of (mono)amino-based alkoxylates having an average molecular weight M_w of 600 - 10 000 g/mol, is based on triisopropanolamine.
11. The use or method according to claim 8, wherein the polymer, consisting of (mono)amino-based alkoxylates having an average molecular weight M_w of 600 - 10 000 g/mol, is based on tert-butylamine.
12. The use or method according to any of the preceding claims, wherein the polymer, consisting of (mono)amino-based alkoxylates having an average molecular weight M_w of 600 - 10 000 g/mol, comprises, per alkylene oxide chain, 12 to 16 alkylene oxide units and preferably 12 to 15 alkylene oxide units.
13. The use or method according to claim 12, wherein the polymer, consisting of (mono)amino-based alkoxylates having an average molecular weight M_w of 600 - 10 000 g/mol, comprises 12 alkylene oxide units per alkylene oxide chain.
14. The use or method according to claim 12, wherein the polymer, consisting of (mono)amino-based alkoxylates having an average molecular weight M_w of 600 - 10 000 g/mol, comprises 15 alkylene oxide units per alkylene oxide chain.
15. The use or method according to any of the preceding claims, wherein the weight-average molar mass of the polymer, consisting of (mono)amino-based alkoxylates having an average molecular weight M_w of 600 - 10 000 g/mol, is in the range from 1300 - 6000 g/mol, and preferably 1400 - 4500 g/mol.