Novel polyalkylene imine derivatives and detergents and cleaning agents containing such

Description

[0001] The present invention relates to the use of certain esterified polyalkyleneimine polyalkoxylates for enhancing the primary washing and cleaning power of washing and cleaning agents when washing textiles or cleaning hard surfaces, in particular against oily and / or greasy soils.

[0002] In addition to the ingredients essential for the washing process, such as surfactants and builder materials, detergents typically contain other components that can be summarized under the term "washing aids" and include such diverse groups of active ingredients as foam regulators, graying inhibitors, bleaching agents, bleach activators, and dye transfer inhibitors. Such adjuvants also include substances whose presence enhances the washing power of surfactants without them usually having to exhibit pronounced surfactant properties themselves. The same applies, analogously, to cleaning agents for hard surfaces. Such substances are often referred to as washing power enhancers or, due to their particularly pronounced effect on oil- or grease-based soils, as "fat boosters."International patent application WO 99 / 49009 A1 discloses the contribution of optionally N-substituted polyalkyleneimines to the physical stability of HEDP-containing liquid detergents. It is also known that polyalkoxylated polyalkyleneimines can suspend soil detached from textile fibers in the wash liquor. For example, international patent application WO 2013 / 17120 A1 discloses detergents containing polyalkyleneimines to prevent redeposition of soil on the laundry fibers. These polyalkyleneimines have a polyalkoxylation substitution on a maximum of 3 nitrogen atoms and have an end group with a molecular weight below 100, in particular a methyl group, on the polyalkoxy unit.

[0003] The international patent application WO 2009 / 087523 A2 discloses the combination of glycosyl hydrolases with fat-removing polyalkoxylated polyalkyleneimines, which can carry a C 1-4 alkyl group at the end of the polyalkoxy unit not bound to the polyalkyleneimine.

[0004] US 2005 / 085404 A1 discloses polyalkyleneimine-alkylene oxide copolymers comprising an alkyleneimine monomer unit with polyalkylene oxide and useful as cleaning agents.

[0005] WO9967353 A1 discloses detergent compositions containing hydrophobic alkoxylated polyalkyleneimine soil dispersants compatible with a bleaching agent.

[0006] The present invention is based on the object of further increasing the effectiveness of polyalkyleneimine-based compounds for removing oil and grease-containing soils.

[0007] This was achieved by a polymer obtainable by reacting polyalkoxylated polyalkyleneimines with hydroxy- or aminoalkylcarboxylic acids and / or reactive hydroxy- or aminoalkylcarboxylic acid derivatives.

[0008] The polyalkoxylated polyalkyleneimine is a polymer with a polyalkyleneimine backbone bearing polyalkoxy groups on the nitrogen atoms. It preferably has a weight-average molecular weight Mw in the range from 500 g / mol to 200,000 g / mol, in particular from 5,000 g / mol to 100,000 g / mol. The polyalkyleneimine has primary amino functions at the ends and preferably both secondary and tertiary amino functions in the interior; optionally, it can also have only secondary amino functions in the interior, resulting in a linear rather than a branched-chain polyalkyleneimine. The ratio of primary to secondary amino groups in the polyalkyleneimine is preferably in the range from 1:0.5 to 1:1.5, in particular in the range from 1:0.7 to 1:1. The ratio of primary to tertiary amino groups in the polyalkyleneimine is preferably in the range of 1:0.2 to 1:1, in particular in the range of 1:0.5 to 1:0.8.The polyalkyleneimine preferably has a weight-average molecular weight in the range from 400 g / mol to 10,000 g / mol, in particular from 600 g / mol to 1,800 g / mol. The nitrogen atoms in 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 not all alkylene groups need to have the same number of carbon atoms. Particular preference is given to ethylene groups, 1,2-propylene groups, 1,3-propylene groups, 1,4-butylene groups, and mixtures thereof, in particular ethylene groups. The primary amino functions in the polyalkyleneimine can carry one or two polyalkoxy groups, and the secondary amino functions can carry one polyalkoxy group, although not every amino function needs to be substituted by an alkoxy group. The average number of alkoxy groups per primary and secondary amino function in the polyalkoxylated polyalkylenimine is preferably 1 to 100 and in particular 5 to 15.The alkoxy groups in the polyalkoxylated polyalkyleneimine are preferably ethoxy, propoxy, or butoxy groups, or mixtures thereof, especially ethoxy groups. Polyalkoxylated polyalkyleneimines are obtainable, for example, by reacting polyalkyleneimines with alkylene oxides corresponding to the alkoxy groups, for example, ethylene oxide, propylene oxide, butylene oxide, or mixtures thereof. If several different alkylene oxides are to be reacted, they can be used simultaneously or one after the other; in the latter variant, alkoxy blocks are formed in the polyalkoxy substituents. If desired, a portion, preferably no more than 30% of the N atoms in the polyalkoxylated polyalkyleneimine can be oxidized to N-oxides by known methods or quaternized by introducing alkyl groups.

[0009] By reacting the polyalkoxylated polyalkyleneimine with the hydroxy- or aminoalkylcarboxylic acid or its reactive derivative, for example, its ester with a short-chain alcohol such as methanol or ethanol, its anhydride, or its lactam or lactone, ester bonds are formed between the carbonyl carbon of the hydroxy- or aminoalkylcarboxylic acid and the oxygen atom of the terminal hydroxy group of the polyalkoxy substituent on the N atoms of the polyalkoxylated polyalkyleneimine. Optionally, further hydroxy- or aminoalkylcarboxylic acid or its reactive derivative can react with the hydroxy or amino group of the thus formed hydroxy- or aminocarboxylic acid ester, resulting in ester-bound polyhydroxycarboxylic acid ester end groups or polyaminocarboxamide end groups.In these, the average number of repeating units originating from the hydroxy- or aminoalkylcarboxylic acid is preferably in the range from 1 to 100, in particular from 5 to 15. Preferred hydroxycarboxylic acids are selected from the group comprising δ-hydroxyvaleric acid, ε-hydroxycaproic acid, and mixtures thereof. Preferred aminocarboxylic acids are selected from the group comprising β-aminopropanoic acid, γ-aminobutanoic acid, δ-aminovaleric acid, ε-aminocaproic acid, and mixtures thereof. If desired, at least some of the terminal hydroxyl groups originating from the hydroxycarboxylic acid or the amino group originating from the aminocarboxylic acid can be esterified or amidated by reaction with a non-hydroxy- or amino-substituted carboxylic acid or a reactive carboxylic acid derivative, for example its ester with a short-chain alcohol such as methanol or ethanol, its anhydride, or its halide.The carboxylic acids are preferably selected from the group comprising acetic acid, hexanoic acid, heptanoic acid, benzoic acid, octanoic acid, methyloctanoic acid, isononanoic acid, decanoic acid, undecanoic acid, undecenoic acid, dodecanoic acid, myristic acid, stearic acid, oleic acid, linolenic acid, palmitoleic acid, arachidonic acid, tall oil acid, and mixtures thereof. Such terminally esterified or amidated derivatives obtainable in this way are used according to the present invention to enhance the primary washing and cleaning power of washing and cleaning agents when washing textiles or cleaning hard surfaces, particularly against oily and / or greasy soils.

[0010] Preferably, the polymer is a compound or a mixture of several compounds of the general formula (I), in the R is a linear or branched alkylene radical having 2 to 4 C atoms or mixtures thereof, B is a branching point, x is a number from 1 to 200, y is a number from 1 to 200 and z is a number from 0 to 100, with the proviso that the sum x+y+z is chosen such that the average molecular weight of the polyalkyleneimine nucleus (i.e., the compound with E = H) is in the range from 400 g / mol to 10,000 g / mol, and E is H or a group of the general formula II or mixtures thereof, in which R 1< represents a linear or branched alkylene radical having 2 to 4 C atoms or mixtures thereof, m represents a number from 3 to 60, in particular from 20 to 30, X represents O or NH, R 2< represents methylene, ethylene or a linear or branched alkylene or mono- or polyunsaturated alkenylene radical having 3 to 11 C atoms or mixtures thereof, n represents a number from 0 to 100, in particular from 5 to 15, and R 3< represents H when n is 0, and represents H, the methyl, ethyl or ethenyl group, a linear, branched or cyclic alkyl or mono- or polyunsaturated alkenyl radical having 3 to 21 C atoms, in particular 2 to 10 C atoms when n is greater than 0, with the Proviso that - in each case based on the number of groups E in the compound of formula I - at least 1%, preferably 40% to 100% of the groups E are not H and in at least 1%, preferably 80% to 100% of the groups E the index n stands for a number greater than 0.

[0011] The branching point in formula I can preferably be realized in that B stands for a group R 4< which otherwise corresponds to R, wherein one end of the group R 4< is bonded to an N atom marked B from a molecule of formula I and the other end of the group R 4< is bonded to an N atom marked B from the same or a second molecule of formula I.

[0012] If desired, a part, preferably not more than 30% based on their number, of the N atoms shown in formula I can carry a further substituent R 5<, so that quaternized units R 5< represents O -< or a linear alkyl group with 1 to 4 carbon atoms; counteranions, which include, for example, chloride, bromide, iodide, sulfate, and mixtures thereof, are present in sufficient numbers to balance the positive charges of the polymer's nitrogen atoms. The additional R 5< radicals can be introduced by known oxidation or quaternization reactions.

[0013] The above-mentioned polyalkyleneimine polyalkoxylate derivatives are prepared by reacting polyalkoxylated polyalkyleneimine with hydroxy- or aminoalkylcarboxylic acid or its reactive derivative in a "grafting from" approach and optionally subsequent reaction with non-hydroxy- or amino-substituted carboxylic acid or corresponding reactive carboxylic acid derivative under esterification or transesterification conditions.

[0014] The use of such polymers in washing textiles or cleaning hard surfaces enhances the primary washing and cleaning power of detergents and cleaning agents, particularly against oily and / or greasy soils. The invention therefore relates to the use of the polymers essential to the invention to enhance the primary washing and cleaning power of detergents and cleaning agents when washing textiles or cleaning hard surfaces against soils, particularly against oily and / or greasy soils.

[0015] The use according to the invention is preferably carried out by adding the active ingredient to an agent free of the active ingredient or to a washing or cleaning liquor which contains an agent free of the active ingredient, the amount of active ingredient added being preferably in the range from 0.1% by weight to 10% by weight, in particular from 1% by weight to 5% by weight, based on the amount of agent free of the active ingredient. The active ingredient essential to the invention is particularly preferably used together with, in particular, liquid washing agents which, based on the total weight of the agent, have a surfactant concentration of at least 30% by weight, preferably in the range from 35% by weight to 70% by weight and in particular 40% by weight to 50% by weight. It is preferred that the washing liquor is produced by diluting a liquid, water-containing washing agent with water in volume ratios in the range from 1:100 to 1:10,000, in particular 1:500 to 1:2,500.The last two advantages also apply to detergents containing the active ingredient essential to the invention.

[0016] In the context of the use according to the invention, it is preferred if the concentration of the active ingredient 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 0.29 g / l, in particular 0.0029 g / l to 0.14 g / l. In the use according to the invention, temperatures in the range from 10 °C to 95 °C, in particular in the range from 20 °C to 40 °C are preferably used. The use according to the invention is preferably carried out at pH values ​​in the range from pH 1 to pH 12, in particular from pH 7 to pH 11.

[0017] Detergents that can be used in conjunction with the inventive use in addition to the active ingredient mentioned, which can be present in particular as powdered solids, in densified particle form, as solutions or suspensions, and especially as water-containing liquid agents, can contain all known ingredients commonly found in such agents. The agents can contain, in particular, builders, surface-active surfactants, water-miscible organic solvents, enzymes, sequestering agents, electrolytes, pH regulators, polymers with special effects, such as soil-release polymers, dye transfer inhibitors, graying inhibitors, crease-reducing and shape-retaining polymeric active ingredients, and other auxiliaries, such as optical brighteners, foam regulators, dyes, and fragrances.

[0018] Further disclosed herein is a water-based liquid detergent which, based on the total weight of the detergent, contains at least 30% by weight, preferably in the range of 35% by weight to 70% by weight and in particular 40% by weight to 50% by weight of surfactant, 30% by weight to 70% by weight, in particular 30% by weight to 65% by weight of water, and 0.1% by weight to 10% by weight, in particular 1% by weight to 5% by weight of the essential active ingredient. The detergents may contain one or more surfactants, with particular consideration being given to anionic surfactants, nonionic surfactants, and mixtures thereof, but may also contain cationic and / or amphoteric surfactants.

[0019] All nonionic surfactants known to the person skilled in the art can be used as nonionic surfactants. Preferably, alkoxylated, advantageously ethoxylated, especially 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 are used as nonionic surfactants, in which the alcohol radical can be linear or, preferably, methyl-branched in the 2-position, or can contain a mixture of linear and methyl-branched radicals, as is usually the case in oxo alcohol radicals. However, alcohol ethoxylates with linear radicals from alcohols of native origin with 12 to 18 carbon atoms, e.g., 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 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 thereof, 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 averages, which for a specific product can correspond to a whole or fractional number. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).

[0020] Alternatively or in addition to these non-ionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples of these are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO. In addition, alkyl glycosides of the general formula R 5< O(G) x can also be used as further non-ionic surfactants, in which R 5< corresponds to a primary straight-chain or methyl-branched, in particular 2-methyl-branched, aliphatic radical having 8 to 22, preferably 12 to 18 C atoms, and G is the symbol representing a glycose unit having 5 or 6 C atoms, preferably glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is between 1.2 and 1.4.

[0021] 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 with 1 to 4 carbon atoms in the alkyl chain.

[0022] Nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N,N-dimethylamine oxide and N-tallowalkyl-N,N-dihydroxyethylamine oxide, and fatty acid alkanolamides can also be used. The amount of these nonionic surfactants is preferably no more than that of the ethoxylated fatty alcohols, in particular no more than half that amount.

[0023] Other suitable surfactants are polyhydroxy fatty acid amides of the formula in which R represents an aliphatic acyl radical having 6 to 22 carbon atoms, R 1< represents hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms, and [Z] represents 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 that can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine, or an alkanolamine, followed by 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 represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R 1< represents a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R 2< represents a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, with C 1-4 alkyl or phenyl radicals being preferred and [Z] represents a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this radical. [Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.The N-alkoxy- or N-aryloxy-substituted compounds can be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as a catalyst.

[0024] Examples of anionic surfactants used include sulfonates and sulfates. Sulfonate-type surfactants that are preferred are C9-13 alkylbenzenesulfonates, olefinsulfonates, i.e., mixtures of alkene and hydroxyalkanesulfonates, and disulfonates, such as those obtained, for example, from C12-18 monoolefins with a terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products. Also suitable are alkanesulfonates obtained from C12-18 alkanes, for example, by sulfochlorination or sulfoxidation followed by hydrolysis or neutralization. Esters of α-sulfofatty acids (estersulfonates), for example, the α-sulfonated methyl esters of hydrogenated coconut, palm kernel, or tallow fatty acids, are also suitable.

[0025] Other suitable anionic surfactants are sulfated fatty acid glycerol esters. Fatty acid glycerol esters are understood to be the mono-, di-, and triesters, as well as mixtures thereof, as obtained by esterifying glycerol with 1 to 3 mol of fatty acid or by transesterifying triglycerides with 0.3 to 2 mol of glycerol. Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids with 6 to 22 carbon atoms, for example, caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid, or behenic acid.

[0026] Also suitable are alkyl sulfates of the general formula RO-SO 3 M, in which R is a linear, branched-chain or cyclic saturated hydrocarbon radical having 12 to 18, in particular 12 to 14, C atoms and M is a counter cation leading to the charge neutralization of the sulfuric acid 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 +< , in which R 1< , R 2< , R 3< , and R 4< independently of one another are hydrogen, an alkyl group having 1 to 4 C atoms or a hydroxyalkyl group having 2 to 3 C atoms. Preferred R radicals are derived from native 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 stated chain length that contain a synthetic, petrochemically produced straight-chain alkyl radical, which exhibit degradation behavior similar to that of the corresponding compounds based on oleochemical raw materials. C 12 -C 16 alkyl sulfates and C 12 -C 14 alkyl sulfates are particularly preferred.

[0027] Also suitable are the sulfuric acid monoesters of straight-chain or branched C 7-21 alcohols ethoxylated with 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C 9-11 alcohols with an average of 3.5 mol of ethylene oxide (EO) or C 12-18 fatty alcohols with 1 to 4 EO.

[0028] Other suitable anionic surfactants include the salts of alkyl sulfosuccinic acid, also known as sulfosuccinates or sulfosuccinic acid esters, which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols. Preferred sulfosuccinates contain C 8-18 fatty alcohol residues or mixtures thereof. Particularly preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty alcohols, which, considered individually, are nonionic surfactants. Sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution are particularly preferred. It is also possible to use alk(en)ylsuccinic acid, preferably with 8 to 18 carbon atoms in the alk(en)yl chain, or salts thereof.

[0029] Other anionic surfactants that may be considered include soaps. Suitable examples include saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid, and behenic acid, as well as soap mixtures derived from natural fatty acids, such as coconut, palm kernel, or tallow fatty acids.

[0030] The anionic surfactants, including soaps, can be present 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 present in the form of their sodium or potassium salts, especially in the form of the sodium salts.

[0031] Instead of the surfactants mentioned or in combination with them, cationic and / or amphoteric surfactants can also be used.

[0032] Cationic compounds of the following formulas can be used as cationic active substances: wherein each group R 1< is independently selected from C 1-6 alkyl, alkenyl or hydroxyalkyl groups; each group R 2< 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.

[0033] Such surfactants are present in detergents in amounts of preferably 1 wt.% to 80 wt.%. As stated above, particularly preferred detergents are liquid and have surfactant contents of at least 30 wt.%, preferably in the range of 32 wt.% to 45 wt.%. Such concentrated liquid detergents are advantageous because they involve lower resource consumption, which is particularly due to their lower transport weight and reduced consumption size. For example, compared to lower-concentration detergents, a smaller bottle size and thus less packaging material are required to achieve the same performance. Furthermore, such highly concentrated detergents are preferred by consumers because they require little storage space in households.

[0034] Fabric softening compounds can be used to care for textiles and improve their properties, such as a softer feel (softening) and reduced electrostatic charge (increased comfort). The active ingredients in these formulations are quaternary ammonium compounds with two hydrophobic residues, such as disteraryldimethylammonium chloride. However, due to its insufficient biodegradability, this compound is increasingly being replaced by quaternary ammonium compounds containing ester groups in their hydrophobic residues as predetermined breaking points for biodegradation.

[0035] 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 conventional manner. Dimethylolethyleneurea is a suitable finishing agent.

[0036] A detergent preferably contains at least one water-soluble and / or water-insoluble, organic and / or inorganic builder. Water-soluble organic builder substances include polycarboxylic acids, in particular citric acid and sugar acids; monomeric and polymeric aminopolycarboxylic acids, in particular methylglycinediacetic acid, nitrilotriacetic acid, and ethylenediaminetetraacetic acid, as well as polyaspartic acid; polyphosphonic acids, in particular aminotris(methylenephosphonic acid), ethylenediaminetetrakis(methylenephosphonic acid), and 1-hydroxyethane-1,1-diphosphonic acid; polymeric hydroxy compounds such as dextrin; and polymeric (poly)carboxylic acids, in particular polycarboxylates obtainable by oxidation of polysaccharides or dextrins; and / or polymeric acrylic acids, methacrylic acids, maleic acids, and copolymers thereof, which may also contain small amounts of polymerizable substances without carboxylic acid functionality.The relative molecular mass of homopolymers of unsaturated carboxylic acids is generally between 5,000 g / mol and 200,000 g / mol, and that of copolymers between 2,000 g / mol and 200,000 g / mol, preferably 50,000 g / mol to 120,000 g / mol, in each case based on the free acid. A particularly preferred acrylic acid-maleic acid copolymer has a relative molecular mass of 50,000 g / mol to 100,000 g / mol. Suitable, albeit less preferred, compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinyl methyl ethers, vinyl esters, ethylene, propylene, and styrene, in which the proportion of acid is at least 50 wt. %. Terpolymers containing 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, 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, with maleic acid being particularly preferred, and / or a derivative of an allylsulfonic acid substituted in the 2-position with an alkyl or aryl radical. Such polymers generally have a relative molecular weight between 1,000 g / mol and 200,000 g / mol. Further preferred copolymers are those containing acrolein and acrylic acid / acrylic acid salts or vinyl acetate as monomers. The organic builder substances can be used, in particular for the production of liquid compositions, in the form of aqueous solutions, preferably in the form of 30 to 50 percent by weight aqueous solutions.All of the acids mentioned are generally used in the form of their water-soluble salts, especially their alkali salts.

[0037] Such organic builder substances can, if desired, be present in amounts of up to 40 wt.%, in particular up to 25 wt.%, and preferably from 1 wt.% to 8 wt.%. Amounts in the upper half of the above-mentioned ranges are preferably used in paste-like or liquid, especially water-based, compositions.

[0038] Particularly suitable water-soluble inorganic builder materials are polymeric alkali phosphates, which can be present in the form of their alkaline, neutral, or acidic sodium or potassium salts. Examples include tetrasodium diphosphate, disodium dihydrogen diphosphate, pentasodium triphosphate, sodium hexametaphosphate, and the corresponding potassium salts or mixtures of sodium and potassium salts. Particularly suitable water-insoluble, water-dispersible inorganic builder materials are crystalline or amorphous alkali aluminosilicates, in amounts of up to 50 wt.%, preferably not more than 40 wt.%, and in liquid compositions, in particular from 1 wt.% to 5 wt.%. Among these, crystalline sodium aluminosilicates of detergent quality, in particular zeolite A, P, and optionally X, are preferred. Amounts close to the stated upper limit are preferably used in solid, particulate compositions.Suitable aluminosilicates, in particular, contain no particles with a grain size larger than 30 µm and preferably consist of at least 80 wt.% particles with a size smaller than 10 µm. Their calcium binding capacity is generally in the range of 100 mg to 200 mg CaO per gram.

[0039] Suitable substitutes or partial substitutes for the aluminosilicate mentioned are crystalline alkali silicates, which can be present alone or in a mixture with amorphous silicates. The alkali silicates usable as builders preferably have a molar ratio of alkali oxide to SiO 2 of less than 0.95, in particular from 1:1.1 to 1:12, and can be amorphous or crystalline. Preferred alkali silicates are sodium silicates, in particular amorphous sodium silicates, with a molar Na 2 O:SiO 2 ratio of 1:2 to 1:2.8. As crystalline silicates, which can be present alone or in a mixture with amorphous silicates, crystalline layered silicates of the general formula Na 2 Si x O 2x+1 · y H 2 O are preferably used, in which x, the so-called modulus, is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values ​​for x are 2, 3 or 4.Preferred crystalline layered silicates are those in which x in the general formula mentioned takes on the values ​​2 or 3. In particular, both β- and δ-sodium disilicates (Na 2 Si 2 O 5 y H 2 O) are preferred. Virtually anhydrous crystalline alkali silicates produced from amorphous alkali silicates and having the above general formula, in which x is a number from 1.9 to 2.1, can also be used. In a further preferred embodiment, a crystalline sodium layered silicate with a modulus of 2 to 3 is used, such as can be produced from sand and soda. Crystalline sodium silicates with a modulus in the range from 1.9 to 3.5 are used in a further preferred embodiment. In a preferred embodiment, a granular compound of alkali silicate and alkali carbonate is used, such as is commercially available under the name Nabion ®< 15.If alkali aluminosilicate, especially zeolite, is also present as an additional builder substance, the weight ratio of aluminosilicate to silicate, based on anhydrous active substances, is preferably 1:10 to 10:1. In agents containing both amorphous and crystalline alkali silicates, the weight ratio of amorphous alkali silicate to crystalline alkali silicate is preferably 1:2 to 2:1 and in particular 1:1 to 2:1.

[0040] Builder substances are preferably contained in detergents in amounts of up to 60% by weight, in particular from 5% by weight to 40% by weight.

[0041] In a preferred embodiment, the product comprises a water-soluble builder block. The use of the term "builder block" is intended to express that the product contains no builder substances other than those that are water-soluble. This means that all builder substances contained in the product are combined in the "block" thus characterized, with the possible exception of those substances that may be present in small quantities as impurities or stabilizing additives in the other ingredients of the product as is customary in the trade. The term "water-soluble" is understood to mean that the builder block dissolves without residue at the concentration resulting from the amount of the product containing it used under normal conditions. Preferably, at least 15% by weight and up to 55% by weight, in particular 25% to 50% by weight, are used.-% of water-soluble builder block is included in the products. This preferably consists of the builder components. a) 5 wt.% to 35 wt.% citric acid, alkali citrate and / or alkali carbonate, which may also be at least partially replaced by alkali bicarbonate, b) up to 10 wt.% alkali silicate with a modulus in the range of 1.8 to 2.5, c) up to 2 wt.% phosphonic acid and / or alkali phosphonate, d) up to 50 wt.% alkali phosphate, and e) up to 10 wt.% polymeric polycarboxylate, The quantities refer to the entire detergent. This also applies to all subsequent quantities, unless expressly stated otherwise.

[0042] In a preferred embodiment, the water-soluble builder block contains at least 2 of the builder components b), c), d) and e) in amounts greater than 0 wt.%.

[0043] With regard to the builder component a), in a preferred embodiment, 15% by weight to 25% by weight of alkali metal carbonate, which may be at least partially replaced by alkali metal bicarbonate, and up to 5% by weight, in particular 0.5% by weight to 2.5% by weight of citric acid and / or alkali metal citrate are present. In an alternative embodiment, the builder 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% by weight of alkali metal carbonate, which may be at least partially replaced by alkali metal bicarbonate. If both alkali metal carbonate and alkali metal bicarbonate are present, the builder component a) preferably comprises alkali metal carbonate and alkali metal bicarbonate in a weight ratio of 10:1 to 1:1.

[0044] With regard to the builder component b), a preferred embodiment contains 1 wt.% to 5 wt.% alkali silicate with a modulus in the range of 1.8 to 2.5.

[0045] With regard to the builder component c), a preferred embodiment contains 0.05% to 1% by weight of phosphonic acid and / or alkali metal phosphonate. Phosphonic acids also include optionally substituted alkylphosphonic acids, which may also contain multiple phosphonic acid moieties (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, aminotris(methylenephosphonic acid), N,N,N',N'-ethylenediaminetetrakis(methylenephosphonic acid), and acylated derivatives of phosphorous acid, which can also be used in any desired mixtures.

[0046] With regard to the builder component d), a preferred embodiment contains 15% to 35% by weight of alkali phosphate, in particular trisodium polyphosphate. Alkali phosphate is the collective name for the alkali metal (in particular sodium and potassium) salts of the various phosphoric acids, which include metaphosphoric acids (HPO 3 ) n and orthophosphoric acid H 3 PO 4 alongside higher molecular weight representatives. The phosphates combine several advantages: They act as alkali carriers, prevent limescale deposits on machine parts and limescale 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 that are very soluble in water. When heated, they lose their water of crystallization and, at 200°C, convert into the weakly acidic diphosphate (disodium hydrogen diphosphate, Na2H2P2O7). At higher temperatures, they convert into sodium trimetaphosphate (Na3P3O9) and Madrell's salt. NaH2PO4 is acidic; it is formed when phosphoric acid is adjusted to a pH of 4.5 with sodium hydroxide solution and the mash is sprayed. Potassium dihydrogen phosphate (primary or monobasic potassium phosphate, potassium biphosphate, KDP), KH2PO4, is a white salt with a density of 2.33 gcm-3, a melting point of 253°C (decomposes to form (KPO3)x, potassium polyphosphate), and is easily soluble in water. Disodium hydrogen phosphate (secondary sodium phosphate), Na 2 HPO 4 , is a colorless, very easily water-soluble crystalline salt.It exists in anhydrous form and with 2 mol (density 2.066 gcm -3 , water loss at 95°), 7 mol (density 1.68 gcm -3 , melting point 48° with loss of 5 H 2 O) and 12 mol water (density 1.52 gcm -3 , melting point 35° with loss of 5 H 2 O). It becomes anhydrous at 100° and, upon higher heating, converts into the diphosphate Na 4 P 2 O 7. Disodium hydrogen phosphate is prepared 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 slightly soluble in water. Trisodium phosphate, tertiary sodium phosphate, Na 3 PO 4 , are colorless crystals which have a density of 1.62 gcm -3< and a melting point of 73-76°C (decomposition) as dodecahydrate, a melting point of 100°C as decahydrate (corresponding to 19-20% P 2 O 5 ) and a density of 2.536 gcm -3< in anhydrous form (corresponding to 39-40% P 2 O 5 ).Trisodium phosphate is readily soluble in water under alkaline conditions 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°C, and is readily soluble in water under alkaline conditions. It is formed, for example, by heating Thomas slag with coal and potassium sulfate. Despite their higher price, the more readily soluble, and therefore highly effective, potassium phosphates are often preferred over 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 a decahydrate (density 1.815-1.836 gcm -3 , melting point 94° with loss of water). The substance is colorless crystals that are soluble 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 a stoichiometric ratio and dewatering the solution by spraying. The decahydrate complexes heavy metal salts and hardness-forming agents and therefore reduces the hardness of the water. Potassium diphosphate (potassium pyrophosphate), K 4 P 2 O 7 , exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33 g cm -3<, which is soluble in water; the pH of a 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, which can be divided into cyclic representatives, sodium and potassium metaphosphates, and chain-like types, sodium and potassium polyphosphates. A variety of names are in use, especially for the latter: fused or calcined phosphates, Graham's salt, Kurrol's salt and Madrell's salt.All higher sodium and potassium phosphates are collectively referred to as condensed phosphates. The technically important pentasodium triphosphate, Na5P3O10 (sodium tripolyphosphate), is a non-hygroscopic, white, water-soluble salt with the general formula NaO-[P(O)(ONa)-O]n-Na with n=3, which crystallizes anhydrously or with 6 H2O. About 17 g of the anhydrous salt dissolve in 100 g of water at room temperature, about 20 g at 60°C, and about 32 g at 100°C; after heating the solution at 100°C for two hours, hydrolysis produces about 8% orthophosphate and 15% diphosphate. In the production of pentasodium triphosphate, phosphoric acid is reacted with soda solution or sodium hydroxide solution in a stoichiometric ratio, and the solution is dehydrated by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.).Pentapotassium triphosphate, K 5 P 3 O 10 (potassium tripolyphosphate), is commercially available, for example, in the form of a 50 wt.% solution (> 23% P 2 O 5 , 25% K 2 O). Sodium potassium tripolyphosphates also exist, which can also be used in the present invention. These are formed, 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 .

[0047] These can 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 can also be used.

[0048] With regard to the builder component e), a preferred embodiment of the composition contains 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 are particularly preferred, and among these, those with an average molecular weight in the range of 5,000 D to 15,000 D (PA standard).

[0049] Suitable enzymes for use in the products 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-LTO, 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 ingredients derived from fungi or bacteria, such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus, Humicola lanuginosa, Humicola insolens, Pseudomonas pseudoalcaligenes, or Pseudomonas cepacia, are particularly suitable. The enzymes used, if present, can be adsorbed onto carriers and / or embedded in coating substances to protect them against premature inactivation. They are preferably present in detergents in amounts of up to 10% by weight, in particular from 0.2% to 2% by weight.

[0050] In a preferred embodiment, the agent contains 5 wt.% to 50 wt.%, in particular 8 to 30 wt.% anionic and / or non-ionic surfactant, up to 60 wt.%, in particular 5 to 40 wt.% builder substance and 0.2 wt.% to 2 wt.% enzyme selected from lipases, cutinases, amylases, pullulanases, mannanases, cellulases, oxidases and peroxidases and mixtures thereof.

[0051] The organic solvents usable in the detergents, especially when in liquid or pasty form, include alcohols with 1 to 4 carbon atoms, especially methanol, ethanol, isopropanol, and tert-butanol; diols with 2 to 4 carbon atoms, especially ethylene glycol and propylene glycol; and mixtures thereof and the ethers derived from the aforementioned classes of compounds. Such water-miscible solvents are preferably present in the detergents in amounts not exceeding 30% by weight, especially from 6% to 20% by weight.

[0052] Naturally derived polymers that can be used as thickeners in aqueous liquid agents include 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; in addition, fully synthetic polymers such as polyacrylic and polymethacrylic compounds, vinyl polymers, polycarboxylic acids, polyethers, polyimines, polyamides and polyurethanes can also be used as thickeners.

[0053] To adjust a desired pH value that does not arise automatically from the mixing of the other components, the products 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. Such pH regulators are preferably present in the products in amounts of no more than 20% by weight, in particular between 1.2% and 17% by weight.

[0054] The 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, if appropriate, other monomers.

[0055] The products may contain anti-crease agents, as textile fabrics, especially those made of rayon, wool, cotton, and their blends, can be prone to crease because the individual fibers are sensitive to bending, kinking, pressing, and crushing across the fiber direction. These include, for example, synthetic products based on fatty acids, fatty acid esters, fatty acid amides, fatty alkylol esters, fatty alkylolamides, or fatty alcohols, which are usually reacted with ethylene oxide, or products based on lecithin or modified phosphoric acid esters.

[0056] The purpose of graying inhibitors is to keep the dirt detached from the hard surface, and in particular from the textile fiber, suspended in the liquor. Suitable for this purpose are water-soluble colloids, usually of an organic nature, such as 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. Starch derivatives other than those mentioned above can also be used, for example aldehyde starches. Preference is given to cellulose ethers, such as carboxymethylcellulose (sodium salt), methylcellulose, hydroxyalkylcellulose, and mixed ethers, such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose, and mixtures thereof, for example in amounts of 0.1 to 5% by weight, based on the agent.

[0057] The agents may contain optical brighteners, among these in particular derivatives of diaminostilbenedisulfonic acid or its alkali metal salts. Suitable examples are salts of 4,4'-bis(2-anilino-4-morpholino-1,3,5-triazinyl-6-amino)stilbene-2,2'-disulfonic acid or similarly structured compounds that 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 above-mentioned optical brighteners can also be used.

[0058] Particularly when used in automatic washing processes, it can be advantageous to add conventional foam inhibitors to the detergents. Suitable foam inhibitors include, for example, soaps of natural or synthetic origin that contain a high proportion of C 18 -C 24 fatty acids. Suitable non-surfactant foam inhibitors include, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica, as well as paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica or bisfatty acid alkylenediamides. Mixtures of different foam inhibitors, for example, those made of silicones, paraffins, or waxes, are also advantageously used. 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.In particular, mixtures of paraffins and bistearylethylenediamide are preferred.

[0059] Suitable peroxygen compounds which may be present in the agents, particularly those in solid form, are in particular organic peracids or peracidic 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 persilicate. Hydrogen peroxide can also be generated 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. Particular preference is given to alkali percarbonate, alkali perborate monohydrate, alkali perborate tetrahydrate or, particularly in liquid agents, hydrogen peroxide in the form of aqueous solutions containing 3% to 10% by weight.-% hydrogen peroxide. Peroxygen compounds are preferably present in detergents in amounts of up to 50 wt.%, in particular from 5 wt.% to 30 wt.%.

[0060] In addition, conventional bleach activators that form peroxocarboxylic acids or peroxoimidic acids under perhydrolysis conditions and / or conventional bleach-activating transition metal complexes can be used. The optional component of the bleach activators, particularly present in amounts of 0.5 wt.% to 6 wt.%, includes the commonly used N- or O-acyl compounds, for example, polyacylated alkylenediamines, especially tetraacetylethylenediamine, acylated glycolurils, especially tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, urazoles, diketopiperazines, sulfurylamides, and cyanurates, as well as carboxylic acid anhydrides, especially phthalic anhydride, carboxylic acid esters, especially sodium isononanoylphenolsulfonate, and acylated sugar derivatives, especially pentaacetylglucose, as well as cationic nitrile derivatives such as trimethylammonium acetonitrile salts.To prevent interaction with the peroxygen compounds during storage, the bleach activators can be coated with coating substances or granulated in a known manner. Tetraacetylethylenediamine granulated with carboxymethylcellulose 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 trialkylammonium acetonitrile formulated in particle form are particularly preferred. In detergents, such bleach activators are preferably present in amounts of up to 8 wt.%, in particular from 2 wt.% to 6 wt.%, based in each case on the total detergent.

[0061] The production of solid detergents is straightforward and can be carried out in a known manner, for example, by spray drying or granulation. For the production of detergents with increased bulk density, particularly in the range of 650 g / l to 950 g / l, a process including an extrusion step is preferred. Detergents in the form of aqueous solutions or solutions containing other conventional solvents are particularly advantageously produced by simply mixing the ingredients, which can be added in bulk or as a solution to an automatic mixer.

[0062] In a preferred embodiment, the agents, especially in concentrated liquid form, are presented as a portion in a fully or partially water-soluble coating. This portioning facilitates dosing for the consumer.

[0063] The detergents can be packaged in foil pouches, for example. Pouches made of water-soluble foil eliminate the need for consumers to tear open the packaging. This allows for convenient dosing of a single portion, sufficient for one wash cycle, by placing the pouch directly into the washing machine or by dropping it into a specific amount of water, for example, in a bucket, bowl, or hand basin. The foil pouch surrounding the wash portion dissolves without leaving any residue when a certain temperature is reached.

[0064] Numerous processes exist in the prior art for producing water-soluble detergent portions, which are also fundamentally suitable for producing agents usable within the scope of the present invention. The most well-known processes are the tubular film process with horizontal and vertical seals. The thermoforming process (deep-drawing process) is also suitable for producing film pouches or dimensionally stable detergent portions. However, the water-soluble casings do not necessarily have to be made of a film material; they can also be dimensionally stable containers, which can be obtained, for example, by means of an injection molding process.

[0065] Furthermore, processes for producing water-soluble capsules from polyvinyl alcohol or gelatin are known, which in principle offer the possibility of providing capsules with a high fill level. The processes are based on the introduction of the water-soluble polymer into a forming cavity. The filling and sealing of the capsules takes place either synchronously or in sequential steps, with the latter being done through a small opening. The capsules are filled, for example, by a filling wedge arranged above two counter-rotating drums that have spherical half-shells on their surface. The drums guide polymer bands that cover the spherical half-shell cavities. Sealing takes place at the positions where the polymer band of one drum meets the polymer band of the opposite drum.At the same time, the filling material is injected into the developing capsule, with the injection pressure of the filling liquid pressing the polymer bands into the spherical half-shell cavities. A process for producing water-soluble capsules, in which filling occurs first and then sealing, is based on the so-called Bottle-Pack® process. In this process, a tube-like preform is inserted into a two-part cavity. The cavity is closed, sealing the lower tube section. The tube is then inflated to form the capsule shape within the cavity, filled, and finally sealed.

[0066] The shell material used to produce the water-soluble portion is preferably a water-soluble polymeric thermoplastic, particularly preferably selected from the group consisting of (optionally partially acetalized) polyvinyl alcohol, polyvinyl alcohol copolymers, polyvinylpyrrolidone, polyethylene oxide, gelatin, cellulose and derivatives thereof, starch and derivatives thereof, blends and composites, inorganic salts, and mixtures of the materials mentioned, preferably hydroxypropylmethylcellulose and / or polyvinyl alcohol blends. Polyvinyl alcohols are commercially available, for example under the trademark Mowiol® (Clariant). Polyvinyl alcohols particularly suitable for the present invention include, 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 may optionally additionally comprise polymers selected from the group comprising acrylic acid-containing polymers, polyacrylamides, oxazoline polymers, polystyrenesulfonates, 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 from 12,000 g / mol to 80,000 g / mol and in particular from 13,000 g / mol to 70,000 g / mol.It is further preferred if the thermoplastics are present in amounts of at least 50% by weight, preferably at least 70% by weight, particularly preferably at least 80% by weight and in particular at least 90% by weight, in each case based on the weight of the water-soluble polymeric thermoplastic. Examples Example 1: Preparation of a polyethoxylated polyethyleneimine with poly-ε-hydroxycaproic acid ester end group

[0067] 81 g (0.008 mol) of the polyethoxylated polyethyleneimide (PEI 600 EO 20 ), obtainable for example according to Example 3 of the international patent application WO 2006 / 108857 from polyethyleneimine (Mw = 600 g / mol) and ethylene oxide, 63.9 g (0.54 mol) of ε-caprolactone and dibutyltin dilaurate (0.5 wt.% based on the weight of the sum of the reactants) were stirred under a nitrogen atmosphere at 125 °C for 6 h, cooled to room temperature and thus 91.5 g of the polymer PEI 600 EO 20 εCL 5 were obtained. The polymer had an average of 20 units of ethylene oxide per N atom of the core and 5 units of ε-caprolactone, which were additionally grafted onto each hydroxyl group of the ethylene oxide block. Example 2: Quaternization

[0068] 0.24 g (2 mmol) of dimethyl sulfate was added to 20 g (1 mmol) of PEI 600 EO 20 εCL 5 C 12 and the reaction mixture was stirred at 60°C under a nitrogen atmosphere. Stirring was continued for another 3 h, and after cooling to room temperature, the polymer with 22% quaternization was obtained.

Claims

1. Use of polymers obtainable by reaction of alkoxylated polyalkyleneimines with hydroxy- or aminoalkylcarboxylic acids and / or reactive hydroxy- or aminoalkylcarboxylic acid derivatives, and optionally subsequent esterification or amidation of at least some of the terminal hydroxyl groups or amino groups originating from the hydroxycarboxylic acid, hydroxyl groups originating from the hydroxycarboxylic acid or amino groups originating from the aminocarboxylic acid by reaction with non-hydroxy- or amino-substituted carboxylic acid or its reactive carboxylic acid derivative, in order to increase the primary washing and cleaning power of detergents and cleaning agents when washing textiles or cleaning hard surfaces, in particular with respect to oil- and / or grease-containing soiling.

2. Use according to claim 1, characterized in that the polymer is added to an agent free of the polymer or to a washing or cleaning liquor which contains an agent free of the polymer, the amount of polymer added, based on the amount of agent free of the polymer, being in the range from 0.1% by weight to 10% by weight, in particular from 1% by weight to 5% by weight3. Use according to one of the preceding claims, characterized in that the average degree of alkoxylation of the N atoms in the alkoxylated polyalkyleneimine is in the range from 1 to 100, in particular from 5 to 15.

4. Use according to one of the preceding claims, characterized in that the hydroxyalkylcarboxylic acid is selected from the group comprising δ-hydroxyvaleric acid, ε-hydroxycaproic acid and mixtures thereof, in that the reactive hydroxyalkylcarboxylic acid derivative is selected from the lactones of said hydroxyalkylcarboxylic acids and mixtures thereof, that the aminoalkylcarboxylic acid is selected from the group comprising β-aminopropanoic acid, γ-aminobutanoic acid, δ-aminovaleric acid, ε-aminocaproic acid and mixtures thereof, and / or that the reactive aminoalkylcarboxylic acid derivative is selected from the lactams of said aminoalkylcarboxylic acids and mixtures thereof.

5. Use according to one of the preceding claims, characterized in that the polymer is a compound or a mixture of several compounds of the general formula (I), in the R is a linear or branched alkylene radical with 2 to 4 carbon atoms or mixtures of these, B for a branching point, x is a number from 1 to 200, y is a number from 1 to 200 and z is a number from 0 to 100, with the proviso that the sum x+y+z is chosen such that the average molecular weight of the polyalkyleneimine nucleus is in the range from 400 g / mol to 10 000 g / mol, and E stands for H or for a group of the general formula II or mixtures thereof, in the R1 is a linear or branched alkylene radical with 2 to 4 carbon atoms or mixtures of these, m for a number from 3 to 60, in particular from 20 to 30, X for O or NH, R2 represents methylene, ethylene or a linear or branched alkylene or mono- or polyunsaturated alkenylene radical with 3 to 11 carbon atoms or mixtures of these, n is a number from 0 to 100, in particular from 5 to 15, and R3 represents H when n is 0, and represents H, the methyl, ethyl or ethenyl group, a linear, branched or cyclic alkyl or mono- or polyunsaturated alkenyl radical having 3 to 21 carbon atoms, in particular 2 to 10 carbon atoms, when n is greater than 0, with the provisos that - in each case based on the number of groups E in the compound of the formula I - at least 1 %, in particular 40 % to 100 %, of the groups E are not H and in at least 1 %, in particular 80 % to 100 %, of the groups E n is a number greater than 0.

6. Use according to claim 5, characterized in that some, in particular not more than 30%, based on their number, of the N atoms shown in formula I carry a further substituent R5 so that quaternized units are formed. in which R5 stands for O- or a linear alkyl group with 1 to 4 carbon atoms and counter anions are present in a number which leads to the balancing of the positive charges of the nitrogen atoms of the polymer.