ES2987953T3 - Combination of polymeric active ingredients that improve primary washing power - Google Patents

Abstract

The cleaning performance of detergents is to be improved. This was mainly achieved by using combinations of polyalkoxylated amine, polyalkoxylated alcohol and/or polyalkoxylated polyalkyleneimine. (Automatic translation with Google Translate, no legal value)

Description

DESCRIPTION

Combination of polymeric active ingredients that improve primary washing power

The present invention relates to the use of combinations of certain polymers to improve the primary washing power of detergents when washing textiles against soils that are especially sensitive to surfactants or enzymes.

In addition to the ingredients essential to the washing process, such as surfactants and building materials, detergents generally contain other ingredients which can be summarised under the term washing auxiliaries and which comprise different groups of active ingredients such as foam regulators, greying inhibitors, bleaching agents, bleach activators and colour transfer inhibitors. These auxiliaries also include substances whose presence improves the washing performance of surfactants without usually having to exhibit pronounced surfactant behaviour. These substances are often referred to as washing power enhancers.

From international patent application WO 2014/154508 A1 it is known that the application of block copolymers of polyether esters of (meth)acrylic alcohol and aminoalcoholic or ammonium esters of (meth)acrylic alcohol to textiles facilitates the removal of subsequently deposited dirt on the textiles. From international patent application WO 2017/005793 A1 it is known that polyalkoxylated polyalkanolamines and polyalkoxylated polyalkyleneimines have advantages in reducing grease residues. US patent application 2016/340619 A1 discloses liquid detergents containing, for example, glycerol-(PO1-10) and ethoxylated polyethyleneimine. Patent application WO 2009/095823 A1 discloses liquid detergents containing, for example, ethoxylated tetraethylenepentamine and polyethyleneimine-600-OE20.

Surprisingly, it has now been discovered that certain combinations of lower molecular weight polymers have particularly good primary washing power-enhancing properties.

The object of the invention is the use of combinations of components a), b) and c) for improving the primary washing power of detergents when washing textiles in washing liquids, in particular aqueous and surfactant-containing washing liquids, against soils which are particularly sensitive to surfactants or enzymes, wherein component a) is a polyalkoxylated amine with a weight average molecular weight M<w>in the range of 600 g/mol to 10,000 g/mol, which is obtained by reacting ammonia or primary alkyl or hydroxyalkyl amines having a molecular weight of less than 200 g/mol, with alkylene oxides, component b) is an alcohol polyalkoxylate with a weight average molecular weight M<w>in the range of 600 g/mol to 10,000 g/mol, which is obtained by reacting di- or triols with primary and/or secondary OH groups, which have a molecular weight of less than 200 g/mol, and component c) is a polyalkoxylated amine with a weight average molecular weight M<w>in the range of 600 g/mol to 10,000 g/mol, which is obtained by reacting di- or triols with primary and/or secondary OH groups, which have a molecular weight of less than 200 g/mol, and component d) is a polyalkoxylated amine with a weight average molecular weight M<w>in the range of 600 g/mol to 10,000 g/mol, which is obtained by reacting di- or triols with primary and/or secondary OH groups, which have a molecular weight of less than 200 g/mol, and component e) is a polyalkoxylated amine with a weight average molecular weight M<w>in the range of 600 g/mol to 10,000 g/mol, which is obtained by reacting di- or triols with primary and/or secondary OH groups, which have a molecular weight of less than 200 g/mol, and component f) is a polyalkoxylated amine with a weight average molecular weight M<w molecular weight M<w>between 60 g/mol and 200 g/mol, with alkylene oxides, and component c) is a polyalkoxylated polyalkyleneimine obtained by reacting polyalkyleneimines with alkylene oxides.

Preferred polyalkoxylated amines (component a) have a weight average molecular weight M<w>of between 1300 g/mol and 6000 g/mol, in particular between 1400 g/mol and 4500 g/mol. (The average molecular weights stated here and below for other polymers are weight average molecular weights M<w>which can in principle be determined by gel permeation chromatography with the aid of an RI detector, the measurement being conveniently carried out against an external standard.) They can be prepared in a known manner from ammonia, a monoalkylamine, a monoalkyl-monoalkanolamine or a monoalkyldialkanolamine or a mono-, di- or trialkanolamine, for example triethanolamine, methyl-, ethyl-, propyl- and isopropyl-diethanolamine, methyl-, ethyl-, propyl- and isopropyl-diisopropanolamine, tripropanolamine, triisopropanolamine, N,N-di-(2-hydroxyethyl)cyclohexylamine, N,N-di-(2-hydroxypropyl)cyclohexylamine, n-butylamine, n-hexylamine, n-octylamine, isopropylamine, sec-butylamine, tert-butylamine, cyclohexylamine, 2-ethylhexylamine, 2-phenylethylamine and mixtures thereof, which is reacted with an alkylene oxide, in particular selected from the group consisting of ethylene oxide, phenyl oxide, phenyldimethylamine ... of propylene oxide, butylene oxide and mixtures thereof, in particular with a mixture comprising propylene oxide and preferably ethylene oxide, particularly preferably with propylene oxide. The polyalkoxylated amines thus obtained may be block or random structures. Particularly preferred, among others, is a polyalkoxylated amine obtainable by propoxylation of triethanolamine, preferably with a length of the three lateral arms of 15 propylene oxide units each. Also preferred is a polyalkoxylated amine, obtainable by propoxylation of triisopropanolamine, preferably with a length of the three lateral arms of 15 propylene oxide units each. Also suitable are polyalkoxylated monoalkylamines with a linear, branched or cyclic alkyl group, wherein the alkoxylation is 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. Also preferred is a polyalkoxylated amine obtainable by propoxylation of tert-butylamine, preferably with a length of the two side arms of 12 propylene oxide units each.

Preferred polyalkoxylated amines also satisfy the general formula I,

wherein R represents a linear, optionally branched or optionally cyclic alkyl group with 1 to 12 C atoms or a group -(CH<2>CHR'O)<n>"-(CH<2>CHR"O)<m>”-H, R' and R" independently of each other represent H, CH<3>or CH<2>CH<3>, n, n' and n" independently of each other represent numbers from 0 to 30, preferably from 0 to 10 and in particular from 0 to 5, and m, m' and m" independently of each other represent numbers from 0 to 30, preferably from 5 to 20 and in particular from 12 to 16, with the proviso that the sum n n'+ n" m m'+ m" is at least 14, preferably in the range from 18 to 100 and in particular in the range from 20 to 70. Preferably, in In compounds of formula I at least one of the radicals R' and R" is a CH<3> group.

Preferred alcohol polyalkoxylates (component b) have a weight average molecular weight M<w>of between 1300 g/mol and 6000 g/mol, in particular between 1400 g/mol and 4500 g/mol. For their preparation, a diol or triol with a molecular weight preferably in the range of 70 g/mol to 150 g/mol can be used in a known manner, which is reacted in particular under alkaline conditions with an alkylene oxide, in particular selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide and mixtures thereof, in particular with a mixture containing propylene oxide and preferably ethylene oxide, particularly preferably with propylene oxide. The polyalkoxylated di- or triols thus obtained can be block or random structures. In preferred embodiments of the present invention, the diol or triol is a cyclic diol or cyclic triol or glycerol, ethylene glycol, 1,2-propanediol, trimethylolpropane, butanediol, 1,1,1-tris(hydroxymethyl)ethane, or a mixture of at least two of them.

The preferred alcohol polyalkoxylates also satisfy the general formula II

wherein R represents a linear, optionally branched or optionally cyclic alkyl group having 1 to 12 C atoms or a group -(CH<2>CHR'O)<n>"-(CH<2>CHR"O)<m>”-H, R' and R" independently of one another represent H, CH<3>or CH<2>CH<3>, n, n' and n" independently of one another represent numbers from 0 to 30, preferably from 0 to 10 and in particular from 0 to 5, and m, m' and m" independently of one another represent numbers from 0 to 30, preferably from 5 to 20 and in particular from 12 to 16, with the proviso that the sum n n'+ n" m m'+ m" is at least 14, preferably in the range from 18 to 100 and in particular in the range from 20 to 70.

The polyalkoxylated polyalkyleneimine (component c) is a polymer with a polyalkyleneimine backbone carrying polyalkoxy groups on the N atoms. It preferably has a weight average molecular weight M<w>of between 5000 g/mol and 60,000 g/mol, in particular between 10,000 g/mol and 22,500 g/mol. The polyalkyleneimine has primary amino functions at the ends and preferably secondary and tertiary amino functions in the interior; if necessary, it can also have only secondary amino functions in the interior, so that a straight-chain rather than a branched polyalkyleneimine is obtained. The ratio of primary to secondary amino groups in the polyalkyleneimine is preferably in the range of 1:0.5 to 1:1.5, in particular in the range of 1:0.7 to 1:1. The ratio of primary to tertiary amino groups in the polyalkyleneimine is preferably between 1:0.2 and 1:1, and in particular between 1:0.5 and 1:0.8. The polyalkyleneimine preferably has a weight average molecular weight of between 500 g/mol and 50,000 g/mol, in particular between 550 g/mol and 2,000 g/mol. The N atoms of the polyalkyleneimine are preferably separated from one another by alkylene groups having 2 to 12 carbon atoms, in particular 2 to 6 carbon atoms, although it is not necessary that all alkylene groups have the same number of carbon atoms. Particularly preferred are ethylene, 1,2-propylene, 1,3-propylene groups and mixtures thereof. The primary amino functions in the polyalkyleneimine may carry 1 or 2 polyalkoxy groups and the secondary amino functions 1 polyalkoxy group, although not all amino functions have to be substituted by alkoxy groups. The average number of alkoxy groups per primary and secondary amino function in the polyalkoxylated polyalkyleneimine is preferably 5 to 100, in particular 10 to 50. The alkoxy groups in the polyalkoxylated polyalkyleneimine are preferably ethoxy, propoxy or butoxy groups or mixtures thereof. The polyalkoxylated polyalkyleneimines are accessible by reacting the polyalkyleneimines with epoxides corresponding to the alkoxy groups. If desired, the terminal OH function of at least some of the polyalkoxy substituents may be replaced by an alkyl ether function having 1 to 10, in particular 1 to 3 C atoms.

In the active ingredient combination used according to the invention, the weight ratio of component a) to component c) is preferably in the range of 1:10 to 10:1, in particular 3:7 to 7:3. In the active ingredient combination used according to the invention, the weight ratio of component b) to component c) is preferably in the range of 1:10 to 10:1, in particular 3:7 to 7:3.

Another object of the invention is a process for removing soil from textiles, in particular soil that is sensitive to surfactants or enzymes, in which a detergent and said combination of active ingredients are brought into contact with the soiled textiles in a washing liquor that is in particular aqueous and contains surfactants. This process can be carried out manually or mechanically, for example using a household washing machine. It is possible to apply the agent, in particular the liquid agent, and the combination of active ingredients simultaneously or successively. Simultaneous application is especially advantageous if a detergent containing the combination of active ingredients is used. By surfactant- or enzyme-sensitive soil is meant soil that can normally be removed, at least in part, with surfactants or with the aid of enzymes, such as oil, grease, make-up or grass soil, chocolate or egg foam. The combination of active ingredients used according to the invention also contributes to the removal of such soil in the absence of enzymes or in particular in the absence of bleaching agents.

The use according to the invention and the process according to the invention are preferably carried out by adding the active ingredient combination to a free agent of the active ingredient combination and its components or to a wash liquor containing a free agent of the active ingredient combination or its components, the amount of the added active ingredient combination being, based on the amount of the free agent of the active ingredient combination or its components, preferably in the range of 0.01% to 20% by weight, in particular 1% to 10% by weight. Particularly preferably, the combination essential for the invention is used together with, in particular, liquid detergents which, based on the total weight of the agent, have a surfactant concentration of at least 30% by weight, preferably in the range of 30% by weight to 45% by weight and, in particular, 32% by weight to 38% by weight. Preferably, the washing liquor is produced by adding 10 ml to 100 ml, in particular 15 ml to 75 ml, preferably 25 ml to 50 ml of a liquid aqueous detergent to 12 liters to 60 liters, in particular 15 liters to 20 liters of water.

In the context of the use according to the invention and the process according to the invention, it is preferable if the concentration of the active ingredient combination defined above in the aqueous wash liquor, as used for example 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. In the process according to the invention and the use according to the invention, it is preferable to work at temperatures in the range of 10 °C to 95 °C, in particular in the range of 20 °C to 40 °C. The process according to the invention and the use according to the invention are preferably carried out at pH values in the range of pH 5 to pH 12, in particular 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 combination of active ingredients and which can be present as, in particular, powdery solids, in the form of post-compacted particles, as solutions or suspensions and, in particular, as aqueous liquid agents, can contain all known ingredients which are customary in such agents. In particular, the agents can contain building 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-preserving polymeric agents, and further auxiliaries, such as optical brighteners, foam regulators, colorants and fragrances.

Another object of the invention is a water-containing liquid detergent which, based on the total weight of the detergent, contains at least 30% by weight, preferably between 30% by weight and 65% by weight and in particular between 45% by weight and 58% by weight of surfactant, between 4% and 25% by weight, in particular between 6% and 15% by weight of water and between 0.01% and 20% by weight, in particular between 1% and 15% by weight of the combination essential for the invention.

The compositions may contain one or more surfactants, in particular anionic surfactants, nonionic surfactants and mixtures thereof, but may also contain cationic and/or amphoteric surfactants.

All nonionic surfactants known to the skilled person can be used as nonionic surfactants. Preference is given to using alkoxylated, preferably ethoxylated, alcohols as nonionic surfactants, in particular primary alcohols with preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, where the alcohol residue may be linear or preferably methyl-branched in the 2-position, or may contain linear and methyl-branched residues in the mixture, as are usually present in oxoalcohol residues. Particularly preferred, however, are ethoxylated alcohols with linear residues of native alcohols with 12 to 18 carbon atoms, for example from coconut, palm, tallow fat or oleyl alcohol, and an average of 2 to 8 moles of EO per mole of alcohol. Preferred ethoxylated alcohols include, for example, C<12-14>alcohols with 3 EO or 4 EO, C<g-11>alcohols with 7 EO, C<13-15>alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C<12-18>alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C<12-14>alcohols with 3 EO and C<12-18>alcohols with 5 EO. The stated degrees of ethoxylation represent statistical average values, which may correspond to an integer or fractional number for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).

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

Another class of nonionic surfactants of preferred use, which are used as the only nonionic surfactant or in combination with other nonionic surfactants, are the alkyl esters of alkoxylated fatty acids, preferably ethoxylated or ethoxylated and propoxylated, preferably with 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-tamoalkyl-N,N-dihydroxyethylamine oxide, and alkanolamides of fatty acids, may also be used. Preferably, the amount of these nonionic surfactants is not greater than that of the ethoxylated fatty alcohols, in particular not more than half.

Other suitable surfactants are polyhydroxy fatty acid amides of the formula

wherein R is an aliphatic acyl radical having 6 to 22 carbon atoms, R1 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 are usually obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, an alkyl ester of a fatty acid or a fatty acid chloride. The group of polyhydroxy fatty acid amides also includes compounds of the formula

wherein R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R1 is a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R2 is a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, where C1-4 alkyl or phenyl radicals are preferred and [Z] represents a linear polyhydroxyalkyl radical whose alkyl chain is substituted with 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. 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 as a catalyst.

Anionic surfactants used are, for example, sulfonate and sulfate surfactants. Sulfonate surfactants are preferably C<g -13>-alkyl benzene sulfonates, olefin sulfonates, i.e. mixtures of alkene and hydroxyalkane sulfonates and disulfonates, such as those obtained from C<12 -18>-monoolefins with terminal or internal double bonds by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation products. Also suitable are alkanesulfonates obtained from alkanes with 12 to 18 carbon atoms, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. Also suitable are esters of alpha-sulfofatty acids (estersulfonates), for example alpha-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.

Other suitable anionic surfactants are sulfated glycerol esters of fatty acids. Glycerol esters of fatty acids are understood to mean mono-, di- and triesters and mixtures thereof, as obtained in the production by esterification of glycerol with 1 to 3 mol of fatty acid or in the transesterification of triglycerides with 0.3 to 2 mol of glycerol. Preferred sulfated glycerol esters of fatty acids are the sulfation 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.

Also suitable are alkyl sulphates of the general formula R-O-SO<3>M, where R represents a linear, branched or cyclic saturated hydrocarbon radical with 12 to 18, in particular 12 to 14 carbon atoms and M represents a countercation leading to charge neutralisation of the sulphuric acid half-ester, in particular a sodium or potassium ion or an ammonium ion of the general formula R<1>R<2>R<3>R<4>N<+>, where R<1>, R<2>, R<3> and R<4> independently represent hydrogen, an alkyl group with 1 to 4 carbon atoms or a hydroxyalkyl group with 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 oxoalcohols with 10 to 20 carbon atoms or secondary alcohols of these chain lengths. Also preferred are alkyl sulphates of the stated chain length which contain a synthetic straight-chain alkyl radical produced on a petrochemical basis and which exhibit a degradation behaviour analogous to that of suitable compounds based on fatty chemical feedstocks. Particularly preferred are C<12>-C<16> alkyl sulphates and C<12>-C<14> alkyl sulphates.

Also suitable are sulfuric acid monoesters of straight-chain or branched C<7-21> alcohols ethoxylated with 1 to 6 moles of ethylene oxide, such as 2-methyl-branched C<g-11> alcohols with an average of 3.5 moles of ethylene oxide (EO) or C<12-18> fatty alcohols with 1 to 4 EO.

Other suitable anionic surfactants are salts of alkylsulfosuccinic acid, which are also called sulfosuccinates or sulfosuccinic acid esters and which represent 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 themselves represent nonionic surfactants. Particularly preferred are sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution. 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 are particularly suitable as additional anionic surfactants. Suitable soaps are soaps containing saturated fatty acids, such as salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, as well as soap mixtures derived in particular from natural fatty acids, for example from coconut, palm kernel or tallow.

Anionic surfactants, including soaps, may be present in the form of their sodium, potassium or ammonium salts and also soluble salts of organic bases such as mono-, di- or triethanolamine. Anionic surfactants are preferably present in the form of their sodium or potassium salts, in particular in the form of sodium salts. Cationic and/or amphoteric surfactants may also be used instead of or in combination with the surfactants mentioned above.

Cationic active substances that can be used are, for example, cationic compounds of the following formulas:

Ri

R1-N—(CH2)n-T-R2

(CH2)n-T-R2

<R1>

R 3-Nu -(C H 2)frT-R2

R-i

»

wherein each R1 group is independently selected from C-i-e 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>-T -R<2>; T = -CH<2>-, - O-CO- or -C O -O - and n is an integer from 0 to 5.

Such surfactants are contained in the detergents in amounts of preferably 5% by weight to 65% by weight. As indicated above, particularly preferred detergents are liquid and have a surfactant content of at least 30% by weight, preferably in a range between 30% by weight and 65% by weight and in particular between 45% by weight and 58% by weight. Such concentrated liquid detergents are advantageous because they are associated with a lower use of resources, which is due in particular to a lower transport weight and a reduced consumption size, for example a smaller bottle size and therefore less packaging material is required to achieve the same application performance compared to less concentrated agents. Furthermore, these highly concentrated products are preferred by consumers because they require less storage space in households.

Textile softening compounds can be used for fabric care and to improve fabric properties such as softer feel (brightening) and reduction of electrostatic charge (improved wearing comfort). The active ingredients in these formulations are quaternary ammonium compounds with two hydrophobic residues, such as distearyldimethylammonium chloride, which is increasingly being replaced by quaternary ammonium compounds containing ester groups in their hydrophobic residues as predetermined breakpoints for biodegradation due to their 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. Dimethylolethyleneurea is suitable as a finishing agent.

A detergent preferably contains at least one water-soluble and/or water-insoluble, organic and/or inorganic builder. Water-soluble organic building blocks include polycarboxylic acids, in particular citric acid and sugar acids, monomeric and polymeric aminopolycarboxylic acids, in particular methylglycine diacetic 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, 1-diphosphonic acid, hydroxylated polymeric 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 thereof, which may also contain small amounts of Polymerizable substances without carboxylic acid functionality in polymerized form. The relative molecular weight 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 between 50,000 g/mol and 120,000 g/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, but less preferred, compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as methyl vinyl ethers, vinyl esters, ethylene, propylene and styrene, in which the proportion of acid is at least 50% by weight. Terpolymers containing two unsaturated acids and/or their salts as monomers and vinyl alcohol and/or an esterified vinyl alcohol or a carbohydrate as a third monomer can also be used as water-soluble organic building blocks. The first acid monomer or its salt is derived from a monoethylenically unsaturated Cs-Cs carboxylic acid and preferably from a C<3>-C<4> monocarboxylic acid, in particular (meth)acrylic acid. The second acid monomer or its salt may be a derivative of a C<4>-C<8> dicarboxylic acid, with maleic acid being particularly preferred, and/or a derivative of an allylsulfonic acid substituted in the 2-position by an alkyl or aryl radical. Such polymers generally have a relative molecular mass of between 1000 g/mol and 200 000 g/mol. Other preferred copolymers are those containing acrolein and acrylic acid/acrylic acid salts or vinyl acetate as monomers. The organic building blocks can be used in the form of aqueous solutions, preferably in the form of 30 to 50 percent by weight aqueous solutions, in particular for the production of liquid agents. All the acids mentioned are generally used in the form of their water-soluble salts, in particular their alkali metal salts.

If desired, said organic building substances may be present in amounts of up to 40% by weight, in particular up to 25% by weight and preferably from 1% by weight to 8% by weight. Amounts in the upper half of the ranges mentioned are preferably used in pasty or liquid agents, in particular those containing water.

Polymeric alkali metal phosphates, which may be present in the form of their neutral alkaline or acidic sodium or potassium salts, are particularly suitable as water-soluble inorganic building materials. Examples are tetrasodium diphosphate, disodium dihydrogen diphosphate, pentasodium triphosphate, the so-called sodium hexametaphosphate and the corresponding potassium salts or mixtures of sodium and potassium salts. The water-insoluble and water-dispersible inorganic building materials used are in particular crystalline or amorphous alkali metal aluminosilicates in amounts of up to 50% by weight, preferably not more than 40% by weight and in liquid agents in particular from 1% by weight to 5% by weight. Of these, crystalline sodium aluminosilicates are preferred as detergents, in particular zeolite A, P and optionally X. Amounts close to the upper limit mentioned are preferably used in solid, particulate agents. Suitable aluminosilicates do not have, in particular, particles with a size greater than 30 mm and preferably consist of at least 80% by weight of particles with a size less than 10 mm. Their calcium binding capacity is generally between 100 mg and 200 mg of CaO per gram.

Suitable substitutes or partial substitutes for the aluminosilicate mentioned are crystalline alkali silicates, which may be present alone or in admixture with amorphous silicates. The alkali silicates which can be used as scaffolding materials preferably have a molar ratio of alkali oxide to SiO2 of less than 0.95, in particular 1:1.1 to 1:12, and may be present in amorphous or crystalline form. Preferred alkali silicates are sodium silicates, in particular amorphous sodium silicates, with a Na2O:SiO2 molar ratio of 1:2 to 1:2.8. Crystalline layer silicates of the general formula Na2SixO2x+1 and H2O, where 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, are preferably used as crystalline silicates, which may be present alone or in admixture with amorphous silicates. Preferred crystalline layer silicates are those where x assumes the values 2 or 3 in the above-mentioned general formula. In particular, sodium disilicates p and 8 (Na2Si2O5 and H2O) are preferred. Virtually anhydrous crystalline alkali silicates produced from amorphous alkali silicates of the above-mentioned general formula, where x is a number between 1.9 and 2.1, may also be used. In another preferred embodiment, a layered crystalline sodium silicate with a modulus of 2 to 3 is used, such as can be produced from sand and soda. In another preferred embodiment, crystalline sodium silicates with a modulus of between 1.9 and 3.5 are used. In a preferred embodiment, a granular compound of alkali metal silicate and alkali carbonate is used, such as that commercially available under the name Nabion® 15. If alkali metal aluminosilicate, in particular zeolite, is also present as an additional building substance, the weight ratio of aluminosilicate to silicate, in each case based on anhydrous active ingredients, is preferably from 1:10 to 10:1. In compositions containing amorphous and crystalline alkali silicates, the weight ratio of amorphous alkali silicate to crystalline alkali silicate is preferably from 1:2 to 2:1, and in particular from 1:1 to 2:1.

Builder substances are preferably contained in detergents in amounts of up to 60% by weight, in particular 1% by weight to 40% by weight.

In a preferred embodiment, the agent has a water-soluble building block. The use of the term “building block” is intended to express the fact that the compositions do not contain other building substances than those that are soluble in water, i.e. all the building substances contained in the composition are combined in the “block” thus characterized, with the exception at most of the amounts of substances that may be contained as impurities or stabilizing additives in small amounts in the other ingredients of the compositions in a usual manner. The term “water-soluble” should be understood in the sense that the building block dissolves without residue in the concentration resulting from the amount of the agent containing it used under usual conditions. Preferably, the agents contain at least 15% by weight and up to 55% by weight, in particular between 25% by weight and 50% by weight of water-soluble building block. It preferably consists of the following building blocks: a) 5% to 35% by weight of citric acid, alkali citrate and/or alkali carbonate, which can also be replaced at least in part by alkali hydrogen carbonate,

b) up to 10% by weight of alkali silicate with a modulus between 1.8 and 2.5,

c) up to 2% by weight of phosphonic acid and/or alkaline phosphonate,

d) up to 50% by weight of alkali metal phosphate, and

e) up to 10% by weight of polymeric polycarboxylate,

when the quantities indicated refer to the entire detergent. This also applies to all subsequent quantities, unless expressly stated otherwise.

In a preferred embodiment, the water-soluble building block contains at least 2 of the building components b), c), d) and e) in amounts greater than 0% by weight.

With respect to the builder component a), in a preferred embodiment between 15% and 25% by weight of alkali metal carbonate is present, which can be at least partially replaced by alkali metal hydrogen carbonate, and up to 5% by weight, in particular between 0.5% and 2.5% by weight of citric acid and/or alkali metal citrate. In an alternative embodiment, the builder component a) comprises from 5% by weight to 25% by weight, in particular from 5% by weight to 15% by weight of citric acid and/or alkali citrate and up to 5% by weight, in particular from 1% by weight to 5% by weight of alkali carbonate, which can be at least partially replaced by alkali hydrogen carbonate. If both alkali metal carbonate and alkali metal hydrogen carbonate are present, the forming component a) preferably contains alkali metal carbonate and alkali metal hydrogen carbonate in a weight ratio of 10:1 to 1:1.

As regards the building component b), in a preferred embodiment, 1% by weight to 5% by weight of alkali silicate with a modulus in the range of 1.8 to 2.5 is present.

With regard to the building component c), in a preferred embodiment 0.05% by weight to 1% by weight of phosphonic acid and/or alkali metal phosphonate are present. Phosphonic acids are also understood to mean optionally substituted alkylphosphonic acids, which may also have several phosphonic acid groupings (so-called polyphosphonic acids). They are preferably selected from hydroxy- and/or aminoalkylphosphonic acids and/or their alkali metal salts, such as dimethylaminomethane diphosphonic acid, 3-aminopropane-1-hydroxy-1,1-diphosphonic acid, 1-amino-1-phenylmethane diphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid, aminotris(methylenephosphonic acid), N,N,N',N'-ethylenediamine-tetrakis(methylenephosphonic acid) and acylated derivatives of phosphorous acid, which can also be used in any mixture.

With regard to the building component d), in a preferred embodiment, between 15% and 35% by weight of alkali metal phosphate, in particular trisodium polyphosphate, are present. Alkaline phosphate is the collective term for the alkali metal (in particular sodium and potassium) salts of the various phosphoric acids, of which a distinction can be made between metaphosphoric acids (HPO<3>)<n> and orthophosphoric acid H<3>PO<4>, in addition to the higher molecular weight representatives. Phosphates combine several advantages: They act as alkali carriers, prevent limescale deposits on machine parts or limescale encrustations on fabrics and also contribute to 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 that dissolve very easily in water, lose their water of crystallization on heating and are converted into a weakly acidic diphosphate (disodium dihydroene phosphate, Na<2>H<2>P<2>O<7>) at 200 °C, and into sodium trimetaphosphate (Na<3>P<3>O<g>) and Madrell's salt at higher temperatures. NaH<2>PO<4> reacts acidically; it is formed when phosphoric acid is adjusted to a pH value of 4.5 with caustic soda and the puree is pulverized. Potassium dihydrogen phosphate (primary or monobasic potassium phosphate, potassium biphosphate, KDP), KH<2>PO<4>, is a white salt with a density of 2.33 gcm<- 3>, has a melting point of 253° (decomposition to form (KPO<3>)<x>, potassium polyphosphate) and is readily soluble in water. Disodium hydrogen phosphate (secondary sodium phosphate), Na<2>HPO<4>, is a colorless crystalline salt, very readily soluble in water. 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), it becomes anhydrous at 100° and is transformed into the diphosphate Na<4>P<2>O<7> when heated more strongly. Disodium hydrogen phosphate is obtained by neutralizing phosphoric acid with a soda solution and using phenolphthalein as an indicator. Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K<2>HPO<4>, is a white amorphous salt easily soluble in water. Trisodium phosphate, tertiary sodium phosphate, Na<3>PO<4>, are colorless crystals having a density of 1.62 gcm<-3>as a dodecahydrate and a melting point of 73–76 °C (decomposition), a melting point of 100 °C as a decahydrate (corresponding to 19–20% P<2>O<5>), and a density of 2.536 gcm<-3>in the anhydrous form (corresponding to 39–40% P<2>O<5>). Trisodium phosphate is readily soluble in water under alkaline reaction and is produced by evaporating a solution of exactly 1 mol of disodium phosphate and 1 mol of NaOH. Tripotassium phosphate (tertiary or tribasic potassium 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 produced, for example, when Thomas slag is heated with charcoal and potassium sulphate. Despite their higher price, the more readily soluble and therefore more effective potassium phosphates are often preferred to the corresponding sodium compounds. Tetrasodium diphosphate (sodium pyrophosphate), Na<4>P<2>O<7>, exists as anhydrous (density 2.534 gcm-3, melting point 988°, also stated as 880°) and as a decahydrate (density 1.815-1.836 gcm<- 3>, melting point 94° with loss of water). It is a colourless crystal that dissolves in water with an alkaline reaction. Na<4>P<2>O<7> is formed by heating disodium phosphate to >200° or by reacting phosphoric acid with soda in stoichiometric proportions and spray-drying the solution. The decahydrate forms complexes with heavy metal salts and hardness formers and thus reduces the hardness of water. Potassium diphosphate (potassium pyrophosphate), K<4>P<2>O<7>, exists as a trihydrate and is a colorless, hygroscopic powder with a density of 2.33 gcm<- 3>, which is soluble in water, therefore the pH of the 1% solution at 25° is 10.4. Condensation of NaH<2>PO<4> or KH<2>PO<4> produces higher molecular weight sodium and potassium phosphates, of which a distinction can be made between cyclic representatives, sodium or potassium metaphosphates, and chain types, sodium or potassium polyphosphates. The latter are known by various names: fused or annealed phosphates, Graham's salt, Kurrol's salt, and Madrell's salt. All higher sodium and potassium phosphates are collectively called condensed phosphates. The technically important pentasodium triphosphate, Na<s>P<a>O-<iü>(sodium tripolyphosphate), is a white, water-soluble, nonhygroscopic, crystallizing anhydrous or 6 H<2>O salt of the general formula NaO-[P(O)(ONa)-O]<n>-Na with n=3. In 100 g of water, about 17 g, at 60° about 20 g, and at 100° about 32 g of the water-free crystalline salt are dissolved; after heating the solution at 100° for two hours, about 8% orthophosphate and 15% diphosphate are formed by hydrolysis. In the production of pentasodium triphosphate, phosphoric acid is reacted with soda or caustic soda solution in a stoichiometric ratio and the solution is spray-dried. Like Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentasodium triphosphate, K<5>P<3>O<10> (potassium tripolyphosphate), for example, is commercially available as a 50% by weight solution (>23% P<2>O<5>, 25% K<2>O). Sodium and potassium tripolyphosphates also exist, which can also be used in the context of the present invention. They are formed, for example, when sodium trimetaphosphate is hydrolyzed with KOH:

(NaPO<a>)<a>+ 2 KOH ^ Na<a>^ P<a>O<-K)>+ H<2>O

These may be used in the same way as 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 may also be used.

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

Enzymes from the class of lipases, cutinases, amylases, pullulanases, mannanases, cellulases, hemicellulases, xylanases and peroxidases and mixtures thereof are suitable for use in the compositions, 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 agents 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 that can be used can be adsorbed on supports and/or incorporated into coating substances in order to protect them from premature inactivation. They are preferably contained in detergents in amounts of up to 10% by weight, in particular 0.2% to 2% by weight.

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

Organic solvents which may be used in the detergents, in particular if present in liquid or pasty form, include alcohols having 1 to 4 carbon atoms, in particular methanol, ethanol, isopropanol and tert-butanol, diols having 2 to 4 carbon atoms, in particular ethylene glycol and propylene glycol, and mixtures thereof, as well as ethers which may be derived from the aforementioned classes of compounds. Such water-miscible solvents are preferably present in the compositions in amounts not exceeding 30% by weight, in particular from 6% by weight to 20% by weight.

Natural polymers which can be used as thickeners in aqueous liquid agents include, for example, agar-agar, carrageenan, tragacanth, gum arabic, alginates, pectins, polyoses, guar gum, locust bean gum, starch, dextrins, gelatin and casein, cellulose derivatives such as carboxymethylcellulose, hydroxyethyl- and propylcellulose, 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.

In order to achieve a desired pH value which does not result automatically from mixing the other components, the compositions may 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. These pH regulators are preferably not present in the compositions in amounts of more than 20% by weight, in particular from 1.2% by weight to 17% by weight.

Soil-releasing polymers, which are often referred to as “soil-releasing” or “soil-repellent” active ingredients due to their ability to render the treated surface, e.g. fiber, soil-repellent, are, for example, nonionic or cationic derivatives of cellulose. Polymers with soil-releasing properties that are particularly active in polyester include copolyesters of dicarboxylic acids, e.g. adipic acid, phthalic acid or terephthalic acid, diols, e.g. ethylene glycol or propylene glycol, and polydiols, e.g. polyethylene glycol or polypropylene glycol. Preferred soil-release polyesters include compounds which are formally accessible by esterification of two monomeric moieties, wherein the first monomer is a dicarboxylic acid HOOC-Ph-COOH and the second monomer is a diol HO-(CHR<11>- )<a>OH, which may also be present as a polymeric diol H-(O-(CHR<11>- )<a>)<b>OH. In this case, Ph is an o-, m- or p-phenylene radical which may 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 is a number from 1 to 300. Preferably, both the monomeric di-units -O-(CHR<-n>- )<a>O- and the polymeric di-units -(O-(CHR<11>- )<a>)<b>O- are present in the polyesters obtainable therefrom. The molar ratio of the diol units of the monomer to the diol units of the polymer is preferably from 100:1 to 1:100, in particular from 10:1 to 1:10. The degree of polymerization b in the diol polymer units is preferably between 4 and 200, in particular between 12 and 140. The molecular weight or the average molecular weight or the maximum of the molecular weight distribution of the preferred soil-release polyesters is between 250 and 100,000, in particular between 500 and 50,000. The acid on which the Ph radical is based is preferably selected from terephthalic acid, isophthalic acid, phthalic acid, trimellitic acid, mellitic acid, isomers of sulfophthalic acid, sulfoisophthalic acid and sulfoterephthalic acid and mixtures thereof. If their acid groups are not part of the ester bonds of the polymer, they are preferably present in salt form, in particular as alkali metal or ammonium salts. Of these, 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 Ph ratio with the meaning given above, of other acids having at least two carboxyl groups may be present in the soil-releasing polyester. These include, for example, alkylene and alkenylenic dicarboxylic acids such as malonic acid, succinic acid, fumaric acid, maleic acid, glutaric acid, adipic acid, pimelic acid, cork acid, azelaic acid and sebacic acid. 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 alkyl radicals having 1 to 10, in particular 1 to 3, carbon atoms. Among the latter diols, those of the formula HO-CH<2>-CHR<11>-OH are especially preferred, in which R<11>has the above-mentioned meaning. 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. Among the polymeric diols, polyethylene glycol with an average molecular weight of 1000 to 6000 is particularly preferred. If desired, these polyesters can also have end groups, for which alkyl groups with 1 to 22 C atoms and esters of monocarboxylic acids can be used as end groups. The ester-linked end groups can be based on alkyl, alkenyl and aryl monocarboxylic acids having 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, laurolic acid, tridecanoic acid, myristic acid, myristoleic acid, pentadecanoic acid, palmitic acid, stearic acid, petroselinic acid, petroselaidic acid, oleic acid, linoleic acid, linolenic acid, linolenic acid, elastearic acid, arachidic acid, gadoleic acid, arachidonic acid, behenic acid, erucic acid, brassidic acid, clupanodonic acid, lignoceric acid, ceroic acid, cyclohexanediol ... melissic acid, benzoic acid, which may carry 1 to 5 substituents with a total of up to 25 C atoms, in particular 1 to 12 C atoms, for example tert-butylbenzoic. The terminal groups can also be based on hydroxymonocarboxylic acids with 5 to 22 C atoms, which include, for example, hydroxyvaleric acid, hydroxycaproic acid, ricinoleic acid, its hydrogenation product hydroxystearic acid and o-, m- and p-hydroxybenzoic acids. 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. Preferably, the number of hydroxymonocarboxylic acid units per terminal group, i.e. their degree of oligomerization, is in the range of 1 to 50, in particular 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, are used alone or in combination with cellulose derivatives.

Dye 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 possibly other monomers.

The agents may contain anti-wrinkle agents, since textile fabrics, in particular those made of rayon, wool, cotton and their blends, may have a tendency to wrinkle because the individual fibres are sensitive to bending, wrinkling, pressing and crushing transverse to the fibre direction. These include, for example, synthetic products based on fatty acids, fatty acid esters, fatty acid amides, alkyl esters of fatty acids, alkylolamides of fatty acids or fatty alcohols, which usually react with ethylene oxide, or products based on lecithin or modified phosphoric acid esters.

The purpose of anti-greying agents is to keep the soil loose from the hard surface and in particular from the textile fibres suspended in the liquor. Water-soluble colloids of mainly organic nature are suitable for this purpose, for example starch, glue, gelatin, salts of ether carboxylic acids or ether sulphonic acids of starch or cellulose or salts of sulphuric acid esters of cellulose or starch. Water-soluble polyamides containing acid 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 agents.

The agents may contain optical brighteners, in particular derivatives of diaminostilbene disulfonic acid or alkali metal salts thereof. Suitable examples are salts of 4,4'-bis(2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of a similar structure which carry a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group instead of the morpholino group. Furthermore, brighteners of the substituted diphenylstyryl type may 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)diphenyl. Mixtures of the optical brighteners mentioned above can also be used.

Particularly when used in machine washing processes, it may be advantageous to add conventional foam inhibitors to the agents. Suitable foam inhibitors include, for example, soaps of natural or synthetic origin having a high proportion of C18-C24 fatty acids. Suitable non-surface-active foam inhibitors include organopolysiloxanes and mixtures thereof with microfine, possibly silanized silicic acid, as well as paraffins, waxes, microcrystalline waxes and mixtures thereof with silanized silicic acid or bis-fatty acid alkylenediamides. Mixtures of various foam inhibitors, for example those made from silicones, paraffins or waxes, are also advantageously used. Preferably, the foam inhibitors, in particular those containing silicone and/or paraffin, are bound to a granular carrier substance which is soluble or dispersible in water. In particular, mixtures of paraffins and bis-arylethylenediamide are preferred.

Suitable peroxygen compounds which may be contained in the agents, in particular the agents in solid form, are 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 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. If solid peroxygen compounds are to be used, these can be used in the form of powders or granules, which can also be coated in a manner known in principle. Particularly preferred are alkali percarbonate, alkali perborate monohydrate, alkali perborate tetrahydrate or, in particular in liquid agents, hydrogen peroxide in the form of aqueous solutions containing between 3% and 10% by weight of hydrogen peroxide. Preferably, peroxygen compounds are present in amounts of up to 50% by weight, in particular 5% to 30% by weight, in the detergents.

In addition, conventional bleach activators which form peroxocarboxylic acids or peroxoimide acids under perhydrolysis conditions and/or conventional bleach activator transition metal complexes may be used. The optional component, present in particular in amounts of 0.5% by weight to 6% by weight, of bleach activators comprises the commonly used N- or O-acyl compounds, 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 lysate anhydride, carboxylic acid esters, in particular isononanoyl sodium phenolsulfonate, and acylated sugar derivatives, in particular pentaacetylglucose, and cationic nitrile derivatives, such as trimethylammonium acetonitrile salts. Bleach activators can be coated or granulated in a known manner with coating substances in order to prevent interaction with peroxygen compounds during storage, with particular preference being given to tetraacetylethylenediamine granulated with the aid of carboxymethyl cellulose with average particle sizes of 0.01 mm to 0.8 mm, granulated 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine and/or particulate trialkylammonium acetonitrile. Such bleach activators are preferably contained in detergents in amounts of up to 8% by weight, in particular 2% by weight to 6% by weight, in each case based on the total composition.

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

In another preferred embodiment, the agents, in particular in concentrated liquid form, are available in portions in a fully or partially water-soluble container. The portion facilitates dosing for the consumer. Said portion of agent preferably comprises from 5 g to 35 g, in particular from 7 g to 25 g, particularly preferably from 15 g to 20 g of the liquid agent.

Agents can be packaged, for example, in foil bags. Packaging in water-soluble foil bags makes it unnecessary for the consumer to open the packaging. This makes it possible to conveniently dose a single portion for a wash cycle by placing the sachet directly into the washing machine or by dropping the sachet into a certain amount of water, for example in a bucket, basin or sink. The film bag surrounding the wash portion dissolves without leaving any residue when a certain temperature is reached.

In the prior art, there are numerous processes for producing water-soluble detergent portions which are in principle also suitable for producing detergents which can be used in the context of the present invention. The best known processes are tubular film processes with horizontal and vertical sealing seams. The thermoforming process (deep-drawing process) is also suitable for producing film bags or even dimensionally stable detergent portions. However, water-soluble packaging does not necessarily have to be made of a film material, but can also be dimensionally stable packaging, which can be obtained by an injection moulding process, for example.

Processes for producing water-soluble capsules from polyvinyl alcohol or gelatin are also known, which in principle offer the possibility of providing capsules with a high degree of filling. The processes are based on the introduction of the water-soluble polymer into a moulding cavity. The capsules are filled and sealed synchronously or in successive steps, in which case the capsules are filled through a small opening. The capsules are filled, for example, by means of a filling wedge arranged above two drums which rotate against each other and have half-spherical shells on their surface. The drums carry polymer bands which cover the cavities of the hemispheres. Sealing takes place at the positions where the polymer band of one drum meets the polymer band of the opposite drum. At the same time, the filling material is injected into the forming capsule, whereby the injection pressure of the filling liquid presses the polymer bands into the half-spherical shell cavities. A process for producing water-soluble capsules, in which the capsule is filled first and then sealed, is based on the so-called Bottle-Pack® process. In this process, a tube-shaped preform is introduced into a two-part cavity. The cavity is closed and the lower section of the tube is sealed; the tube is then inflated to form the capsule 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 preferred selected from the group consisting of polyvinyl alcohol (optionally partly acetalized), polyvinyl alcohol copolymers, polyvinylpyrrolidone, polyethylene oxide, gelatin, cellulose and its derivatives, starch and its derivatives, mixtures and compounds, inorganic salts and mixtures of the mentioned materials, preferably hydroxypropylmethylcellulose and/or polyvinyl alcohol mixtures. Polyvinyl alcohols are commercially available, for example under the brand name Mowiol® (Clariant). Polyvinyl alcohols especially 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 prepare the portion may optionally further 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. It is preferred that the water-soluble thermoplastic used comprises a polyvinyl alcohol whose degree of hydrolysis is from 70 mol % to 100 mol %, preferably from 80 mol % to 90 mol %, particularly preferably from 81 mol % to 89 mol %, and especially from 82 mol % to 88 mol %. It is further preferred that the water-soluble thermoplastic used comprises a polyvinyl alcohol whose molecular weight is between 10,000 g/mol and 100,000 g/mol, preferably between 11,000 g/mol and 90,000 g/mol, more preferably between 12,000 g/mol and 80,000 g/mol and in particular between 13,000 g/mol and 70,000 g/mol. It is further preferred that the thermoplastics are present in amounts of at least 50% by weight, preferably at least 70% by weight, more 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.

Claims (10)

1. Use of combinations of components a), b) and c) to increase the primary washing power of detergents when washing textiles, in particular in aqueous and surfactant-containing washing liquid with respect to, in particular, surfactant- or enzyme-sensitive soils, where Component a) is a polyalkoxylated amine with a weight average molecular weight Mw of between 600 g/mol and 10,000 g/mol, which is obtained by reacting ammonia or primary alkyl- or hydroxyalkylamines, having a molecular weight of less than 200 g/mol, with alkylene oxides, component b) is a polyalkoxylated alcohol with a weight average molecular weight Mw between 600 g/mol and 10,000 g/mol, obtained by reacting di- or triols with primary and/or secondary OH groups, having a molecular weight Mw between 60 g/mol and 200 g/mol, with alkylene oxides, and component c) is a polyalkoxylated polyalkyleneimine obtained by reacting polyalkyleneimines with alkylene oxides. 2. Use according to claim 1, characterized in that the polyalkoxylated amine (component a) has a weight average molecular weight Mw in the range of 1300 g/mol to 6000 g/mol, in particular 1400 g/mol to 4500 g/mol, in that the polyalkoxylated alcohol (component b) has a weight average molecular weight Mw in the range of 1300 g/mol to 6000 g/mol, in particular 1400 g/mol to 4500 g/mol, and/or in that the polyalkoxylated polyalkyleneimine has a weight average molecular weight Mw between 5000 g/mol and 60000 g/mol, in particular between 10000 g/mol and 22500 g/mol. 3. Use according to claim 1 or 2, characterized in that it is carried out by adding the polymer to a free agent of the combination of active ingredients and their components or to a washing liquor containing a free agent of the combination of active ingredients or their components. 4. Use according to claim 3, characterized in that the amount of the active ingredient combination added, based on the amount of the free agent of the active ingredient combination or its components, is in the range of 0.01% to 20% by weight, in particular 1% to 15% by weight. 5. Method for removing soil from textiles, in particular soil sensitive to surfactants or enzymes, characterized in that a combination of components a), b) and c) is brought into contact with the soiled textiles in a washing solution, in particular aqueous and containing surfactants, where Component a) is a polyalkoxylated amine with a weight average molecular weight Mw of between 600 g/mol and 10,000 g/mol, which is obtained by reacting ammonia or primary alkyl- or hydroxyalkylamines, having a molecular weight of less than 200 g/mol, with alkylene oxides, component b) is a polyalkoxylated alcohol with a weight average molecular weight Mw between 600 g/mol and 10,000 g/mol, obtained by reacting di- or triols with primary and/or secondary OH groups, having a molecular weight Mw between 60 g/mol and 200 g/mol, with alkylene oxides, and component c) is a polyalkoxylated polyalkyleneimine obtained by reacting polyalkyleneimines with alkylene oxides. 6. Method according to claim 5 or use according to one of claims 1 to 4, characterized in that the washing liquor is produced by adding 10 ml to 100 ml, in particular 10 ml to 75 ml of a liquid aqueous detergent to 12 liters to 60 liters, in particular 15 liters to 20 liters, of water. 7. Aqueous liquid detergent which, based on the total weight of the composition, contains at least 30% by weight, preferably between 30% by weight and 65% by weight and in particular between 45% by weight and 58% by weight of surfactant, between 4% by weight and 25% by weight, in particular between 6% by weight and 15% by weight of water and between 0.01% by weight and 20% by weight, in particular between 1% by weight and 15% by weight of a combination of components a), b) and c), wherein Component a) is a polyalkoxylated amine with a weight average molecular weight Mw of between 600 g/mol and 10,000 g/mol, which is obtained by reacting ammonia or primary alkyl- or hydroxyalkylamines, having a molecular weight of less than 200 g/mol, with alkylene oxides, component b) is a polyalkoxylated alcohol with a weight average molecular weight Mw between 600 g/mol and 10,000 g/mol, obtained by reacting di- or triols with primary and/or secondary OH groups, having a molecular weight Mw between 60 g/mol and 200 g/mol, with alkylene oxides, and component c) is a polyalkoxylated polyalkyleneimine obtained by reacting polyalkyleneimines with alkylene oxides. 8. Agent according to claim 7, characterized in that it is present as a portion in a coating totally or partially soluble in water. 9. Agent portion according to claim 8, characterized in that it comprises 5 g to 35 g, in particular 7 g to 25 g, of the liquid agent. 10. Use, method or agent according to one of the preceding claims, characterized in that in the combination of active ingredients the weight ratio of component a) to component c) is between 1:10 and 10:1, in particular between 3:7 and 7:3, and/or the weight ratio of component b) to component c) is between 1:10 and 10:1, in particular between 3:7 and 7:3.