EP3617297B1 - Polymer agents which improve primary washing power - Google Patents

Description

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

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

From the international patent application WO 2014/154508 A1 It is known that the application of block copolymers of polyether alcohol (meth)acrylic acid esters and amino alcohol or ammonium alcohol (meth)acrylic acid esters to textiles facilitates the removal of soiling that subsequently settles on the textiles. From the international patent application WO 2017/005793 A1 It is known that poly-alkoxylated poly-alkanolamines and poly-alkoxylated poly-alkyleneimines show advantages in the reduction of fat residues. From the patent application US 2016/340619 A1 Liquid detergents are known which contain, for example, glycerin (PO _1-10 ) and ethoxylated polyethyleneimine. The patent application WO 2009/095823 A1 discloses liquid detergents containing, for example, ethoxylated tetraethylenepentamine and polyethyleneimine-600-EO20.

Surprisingly, it has now been found that certain combinations of a few high molecular weight polymers have particularly good primary detergency enhancing properties.

The invention relates to the use of combinations of components a), b), and c) for increasing the primary detergency of detergents when washing textiles in, in particular, aqueous and surfactant-containing washing liquid against, in particular, surfactant- or enzyme-sensitive stains, where component a) is a polyalkoxylated amine with a weight-average molecular weight M _w in the range from 600 g/mol to 10,000 g/mol, which is obtainable by reacting ammonia or primary alkyl or hydroxyalkylamines which have 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 from 600 g/mol to 10,000 g/mol, which is obtainable by reacting diols or triols with primary and/or secondary OH groups which have a molecular weight M _w in the range from 60 g/mol to 200 g/mol, with alkylene oxides, and component c) is a polyalkoxylated polyalkyleneimine which is obtainable by reacting polyalkyleneimines with alkylene oxides.

Preferred polyalkoxylated amines (component a) have a weight-average molecular weight M _w in the range from 1300 g/mol to 6000 g/mol, in particular from 1400 g/mol to 4500 g/mol. (The average molecular weights given here and later for other polymers are weight-average molecular weights M _w which can basically be determined by gel permeation chromatography using 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 monoalkyl-dialkanolamine 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, 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 amines obtainable in this way can be block or random structures. Particular preference is given, inter alia, to a polyalkoxylated amine obtainable by propoxylation of triethanolamine, preferably with a length of the three side 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 side 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.

• in der R für eine lineare, gegebenenfalls verzweigte oder gegebenenfalls cyclische Alkylgruppe mit 1 bis 12 C-Atomen oder einer Gruppe -(CH₂CHR'O)_n"-(CH₂CHR"O)_m"-H steht,
• R' und R" unabhängig voneinander für H, CH₃ oder CH₂CH₃ stehen,
• n, n' und n" unabhängig voneinander für Zahlen von 0 bis 30, vorzugsweise von 0 bis 10 und insbesondere 0 bis 5 stehen, und
• m, m` und m" unabhängig voneinander für Zahlen von 0 bis 30, vorzugsweise von 5 bis 20 und insbesondere von 12 bis 16 stehen,
• mit der Maßgabe, dass die Summe n + n'+ n" + m + m'+ m" mindestens 14 ist, vorzugsweise im Bereich von 18 bis 100 und insbesondere im Bereich von 20 bis 70 liegt. Bevorzugt ist in den Verbindungen der Formel I mindestens einer der Reste R` und R" eine CH₃-Gruppe.

Preferred polyalkoxylated amines also satisfy the general formula I,

• in which 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 represent H, CH ₃ or CH ₂ CH ₃ ,
• n, n' and n" independently represent numbers from 0 to 30, preferably from 0 to 10 and in particular 0 to 5, and
• m, m` and m" independently 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 the compounds of the 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 in the range from 1300 g/mol to 6000 g/mol, in particular from 1400 g/mol to 4500 g/mol. To prepare them, one can start in a known manner from a diol or triol with a molecular weight preferably in the range from 70 g/mol to 150 g/mol, 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 diols or triols obtainable in this way 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 glycerin, ethylene glycol, 1,2-propanediol, trimethylolpropane, butanediol, 1,1,1-tris(hydroxymethyl)ethane, or a mixture of at least two of these.

• in der R für eine lineare, gegebenenfalls verzweigte oder gegebenenfalls cyclische Alkylgruppe mit 1 bis 12 C-Atomen oder einer Gruppe -(CH₂CHR'O)_n"-(CH₂CHR"O)_m"-H steht,
• R' und R" unabhängig voneinander für H, CH₃ oder CH₂CH₃ stehen,
• n, n' und n" unabhängig voneinander für Zahlen von 0 bis 30, vorzugsweise von 0 bis 10 und insbesondere 0 bis 5 stehen, und
• m, m` und m" unabhängig voneinander für Zahlen von 0 bis 30, vorzugsweise von 5 bis 20 und insbesondere von 12 bis 16 stehen,
• mit der Maßgabe, dass die Summe n + n'+ n" + m + m'+ m" mindestens 14 ist, vorzugsweise im Bereich von 18 bis 100 und insbesondere im Bereich von 20 bis 70 liegt.

Preferred alcohol polyalkoxylates also satisfy the general formula II

• in which 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 represent H, CH ₃ or CH ₂ CH ₃ ,
• n, n' and n" independently represent numbers from 0 to 30, preferably from 0 to 10 and in particular 0 to 5, and
• m, m` and m" independently 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 that carries polyalkoxy groups on the N atoms. It preferably has a weight-average molecular weight Mw in the range from 5000 g/mol to 60000 g/mol, in particular from 10000 g/mol to 22500 g/mol. The polyalkyleneimine has primary amino functions at the ends and preferably both secondary and tertiary amino functions in the interior; if appropriate, it can also have only secondary amino functions in the interior, so that a linear rather than a branched-chain polyalkyleneimine is obtained. 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 from 1:0.2 to 1:1, in particular in the range from 1:0.5 to 1:0.8. The polyalkyleneimine preferably has a weight-average molecular weight in the range from 500 g/mol to 50,000 g/mol, in particular from 550 g/mol to 2000 g/mol. The N atoms in the polyalkyleneimine are preferably separated from one another by alkylene groups having 2 to 12 C atoms, in particular 2 to 6 C atoms, although not all alkylene groups need to have the same number of C atoms. Ethylene groups, 1,2-propylene groups, 1,3-propylene groups and mixtures thereof are particularly preferred. The primary amino functions in the polyalkyleneimine can carry 1 or 2 polyalkoxy groups and the secondary amino functions 1 polyalkoxy group, although not every amino function has to be substituted by an alkoxy group. 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 of these. 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 can be replaced by an alkyl ether function having 1 to 10, in particular 1 to 3, carbon 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 from 1:10 to 10:1, in particular from 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 from 1:10 to 10:1, in particular from 3:7 to 7:3.

The invention further relates to a method for removing soiling from textiles, particularly soiling sensitive to surfactants or enzymes, in which a detergent and the active ingredient combination mentioned are brought into contact with soiled textiles in a washing liquor that is particularly aqueous and contains surfactants. This method can be carried out manually or mechanically, for example using a household washing machine. It is possible to use the particularly liquid agent and the active ingredient combination simultaneously or one after the other. The simultaneous application can be carried out particularly advantageously by using a detergent that contains the active ingredient combination. Surfactant- or enzyme-sensitive soiling is understood to mean soiling that can usually be at least partially removed by surfactants or with the help of enzymes, such as soiling from oil, grease, make-up or grass, mousse au chocolat or egg. The active ingredient combination used according to the invention also contributes to the removability of such soiling in the absence of enzymes or in particular in the absence of bleaching agents.

The use according to the invention and the method according to the invention are preferably implemented by adding the active ingredient combination to an agent free of the active ingredient combination and its components or to a washing liquor which contains an agent free of the active ingredient combination or its components, the amount of active ingredient combination added, based on the amount of the agent free of the active ingredient combination or its components, preferably being in the range from 0.01% by weight to 20% by weight, in particular from 1% by weight to 10% by weight. The combination essential to the invention is particularly preferably 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 from 30% by weight to 45% by weight and in particular 32% by weight to 38% by weight. It is preferred that 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 water-containing 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 method according to the invention, it is preferred if the concentration of the active ingredient combination defined above in the aqueous washing 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. The method according to the invention and the use according to the invention are preferably carried out at temperatures in the range from 10 °C to 95 °C, in particular in the range from 20 °C to 40 °C. The method according to the invention and the use according to the invention are preferably carried out at pH values in the range from pH 5 to pH 12, in particular from pH 7 to pH 11.

Detergents that can be used in conjunction with the use according to the invention or in the method according to the invention in addition to the active ingredient combination, which can be present in particular as powdered solids, in post-compacted particle form, as solutions or suspensions and in particular as water-containing liquid agents, can contain all known ingredients that are customary in such agents. The agents can in particular contain builder substances, surface-active surfactants, water-miscible organic solvents, enzymes, sequestering agents, electrolytes, pH regulators, polymers with special effects, such as soil release polymers, color transfer inhibitors, graying inhibitors, crease-reducing and shape-retaining polymeric active ingredients, and other additives such as optical brighteners, foam regulators, dyes and fragrances.

The invention further relates to a water-containing liquid detergent which, based on the total weight of the detergent, contains at least 30% by weight, preferably in the range from 30% by weight to 65% by weight and in particular from 45% by weight to 58% by weight of surfactant, 4% by weight to 25% by weight, in particular 6% by weight to 15% by weight of water and 0.01% by weight to 20% by weight, in particular 1% by weight to 15% by weight of the combination essential to the invention.

The agents may contain one or more surfactants, particularly anionic surfactants, non-ionic surfactants and mixtures thereof, but may also contain cationic and/or amphoteric surfactants.

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 linear and methyl-branched radicals in the mixture, as is usually the case in oxo alcohol radicals. In particular, 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. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 EO or 4 EO, C _9-11 alcohol with 7 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C _12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C _12-14 alcohol with 3 EO and C _12-18 alcohol with 5 EO. The stated degrees of ethoxylation represent statistical averages which can correspond to a whole or a fractional number for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).

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 methyl-branched in the 2-position, aliphatic radical with 8 to 22, preferably 12 to 18 C atoms and G is the symbol that stands for a glycose unit with 5 or 6 C atoms, preferably glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.

Another class of preferably used nonionic surfactants, which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain.

Non-ionic surfactants of the amine oxide type, for example N-coconut alkyl-N,N-dimethyl amine oxide and N-tallow alkyl-N,N-dihydroxyethyl amine oxide, and fatty acid alkanolamides can also be used. The amount of these non-ionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of that.

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

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

in which R is an aliphatic acyl radical having 6 to 22 carbon atoms, R ¹ is hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl radical having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups. The polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride. The group of polyhydroxy fatty acid amides also includes compounds of the formula

in which R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ¹ is a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R ² is a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, with C _1-4 alkyl or phenyl radicals being preferred and [Z] is a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this radical. [Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy- or N-aryloxy-substituted compounds can be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as a catalyst.

Anionic surfactants used include those of the sulfonate and sulfate type. Sulfonate-type surfactants used are preferably C _9-13 alkylbenzenesulfonates, olefinsulfonates, i.e. mixtures of alkene and hydroxyalkanesulfonates, and disulfonates, such as They are obtained, for example, from C _12-18 monoolefins with a terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products. Also suitable are alkanesulfonates obtained from C _12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. The esters of α-sulfofatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.

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

• in der R für einen linearen, verzweigtkettigen oder cyclischen gesättigten Kohlenwasserstoffrest mit 12 bis 18, insbesondere 12 bis 14 C-Atomen und M für ein zur Ladungsneutralisation des Schwefelsäurehalbesters führendes Gegenkation steht, insbesondere ein Natrium- oder Kaliumion oder ein Ammoniumion der allgemeinen Formel R¹R²R³R⁴N⁺,
• in der R¹, R², R³, und R⁴ unabhängig voneinander für Wasserstoff, eine Alkylgruppe mit 1 bis 4 C-Atomen oder eine Hydroxyalkylgruppe mit 2 bis 3 C-Atomen steht. Bevorzugte Reste R leiten sich von nativen C₁₂-C₁₈-Fettalkoholen, wie beispielsweise von Kokosfettalkohol, Talgfettalkohol, Lauryl-, Myristyl-, Cetyl- oder Stearylalkohol, oder den C₁₀-C₂₀-Oxoalkoholen oder sekundären Alkoholen dieser Kettenlängen ab. Weiterhin bevorzugt sind Alkylsulfate der genannten Kettenlänge, welche einen synthetischen, auf petrochemischer Basis hergestellten geradkettigen Alkylrest enthalten, die ein analoges Abbauverhalten besitzen wie die adäquaten Verbindungen auf der Basis von fettchemischen Rohstoffen. C₁₂-C₁₆-Alkylsulfate und C₁₂-C₁₄-Alkylsulfate sind besonders bevorzugt.

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 semiester, in particular a sodium or potassium ion or an ammonium ion of the general formula R ¹ R ² R ³ R ⁴ N ⁺ ,
• in which R ¹ , R ² , R ³ , and R ⁴ independently of one another represent hydrogen, an alkyl group with 1 to 4 C atoms or a hydroxyalkyl group with 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 chain length mentioned which contain a synthetic, petrochemically based straight-chain alkyl radical, which have a 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.

Also suitable are the 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 _9-11 alcohols with an average of 3.5 moles of ethylene oxide (EO) or C _12-18 fatty alcohols with 1 to 4 EO.

Other suitable anionic surfactants are the salts of alkyl sulfosuccinic acid, which are also referred to as sulfosuccinates or sulfosuccinic acid esters and are the monoesters and/or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contain 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 in themselves are non-ionic surfactants. Sulfosuccinates, whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are particularly preferred. It is also possible to use alk(en)ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk(en)yl chain or its salts.

Other anionic surfactants that may be considered include soaps. Saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and particularly soap mixtures derived from natural fatty acids, e.g. coconut, palm kernel or tallow fatty acids, are suitable.

The anionic surfactants, including the soaps, can be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases such as mono-, di- or triethanolamine. The anionic surfactants are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts.

Cationic and/or amphoteric surfactants can also be used instead of the surfactants mentioned or in combination with them.

worin jede Gruppe R¹ unabhängig voneinander ausgewählt ist aus C_1-6-Alkyl-, -Alkenyl- oder -Hydroxyalkylgruppen; jede Gruppe R² unabhängig voneinander ausgewählt ist aus C_8-28-Alkyl- oder -Alkenylgruppen; R³ = R¹ oder (CH₂)_n-T-R²; R⁴ = R¹ oder R² oder (CH₂)_n-T-R²; T = -CH₂-, - O-CO- oder -CO-O- und n eine ganze Zahl von 0 bis 5 ist.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.

Such surfactants are contained in detergents in amounts of preferably 5% by weight to 65% by weight. As stated above, particularly preferred detergents are liquid and have surfactant contents of at least 30% by weight, preferably in the range from 30% by weight to 65% by weight and in particular from 45% by weight to 58% by weight. Such concentrated liquid detergents are advantageous because they involve lower use of resources, which is particularly due to a lower transport weight and a reduced consumption size. For example, compared to less concentrated agents, a smaller bottle size and thus less packaging material is needed to achieve the same application performance. In addition, such highly concentrated agents are preferred by consumers because they require little storage space in households.

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

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. The 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 and polyaspartic acid, polyphosphonic acids, in particular aminotris(methylenephosphonic acid), ethylenediaminetetrakis(methylenephosphonic acid) and 1-hydroxyethane-1,1-diphosphonic acid, polymeric hydroxy compounds such as dextrin and polymeric (poly)carboxylic acids, in particular polycarboxylates accessible by oxidation of polysaccharides or dextrins, and/or polymeric acrylic acids, methacrylic acids, maleic acids and copolymers thereof, which may also contain small proportions of polymerizable substances without carboxylic acid functionality polymerized in. The relative molecular mass of homopolymers of unsaturated carboxylic acids is generally between 5 000 g/mol and 200,000 g/mol, that of the copolymers between 2,000 g/mol and 200,000 g/mol, preferably 50,000 g/mol to 120,000 g/mol, 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, although less preferred, compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinyl methyl ethers, vinyl esters, ethylene, propylene and styrene, in which the proportion of acid is at least 50% by weight. Terpolymers which contain two unsaturated acids and/or their salts as monomers and vinyl alcohol and/or an esterified vinyl alcohol or a carbohydrate as the third monomer can also be used as water-soluble organic builder substances. The first acidic monomer or its salt is derived from a monoethylenically unsaturated Cs-Cs carboxylic acid and preferably from a 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 which is substituted in the 2-position with an alkyl or aryl radical. Such polymers generally have a relative molecular mass between 1,000 g/mol and 200,000 g/mol. Other preferred copolymers are those which have acrolein and acrylic acid/acrylic acid salts or vinyl acetate as monomers. The organic builder substances can be used in the form of aqueous solutions, preferably in the form of 30 to 50 percent by weight aqueous solutions, in particular for producing liquid agents. All of the acids mentioned are generally used in the form of their water-soluble salts, especially their alkali salts.

Such organic builder substances can, if desired, be present in amounts of up to 40% by weight, in particular up to 25% by weight and preferably from 1% by weight to 8% by weight. Amounts in the upper half of the ranges mentioned are preferably used in paste-like or liquid, in particular water-containing, agents.

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 of these are tetrasodium diphosphate, disodium dihydrogen diphosphate, pentasodium triphosphate, so-called sodium hexametaphosphate and the corresponding potassium salts or mixtures of sodium and potassium salts. Particularly suitable water-insoluble, water-dispersible inorganic builder materials are crystalline or amorphous alkali aluminosilicates, in amounts of up to 50% by weight, preferably not more than 40% by weight and in liquid agents in particular from 1% to 5% by weight. Among these, preference is given to crystalline sodium aluminosilicates in detergent quality, in particular zeolite A, P and optionally X. Amounts close to the upper limit mentioned are preferably used in solid, particulate agents. Suitable aluminosilicates in particular do not contain any particles with a grain size of more than 30 µm and preferably consist of at least 80% by weight of particles with a size of less than 10 µm. Their calcium binding capacity is usually in the range of 100 mg to 200 mg CaO per gram.

Suitable substitutes or partial substitutes for the aluminosilicate mentioned are crystalline alkali silicates, which can be present alone or in a mixture with amorphous silicates. The alkali silicates which can be used as builders preferably have a molar ratio of alkali oxide to 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 the sodium silicates, in particular the amorphous sodium silicates, with a molar ratio Na ₂ O:SiO ₂ of 1:2 to 1:2.8. Crystalline silicates which can be present alone or in a mixture with amorphous silicates are preferably crystalline layered silicates of the general formula Na ₂ Si _x O _2x+1 y H ₂ O, in which x, the so-called modulus, is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4. Preferred crystalline layered silicates are those in which x in the general formula mentioned assumes the values 2 or 3. 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 of the above general formula, in which x is a number from 1.9 to 2.1, produced from amorphous alkali silicates can also be used. In a further preferred embodiment, a crystalline sodium layer 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 of 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, in particular zeolite, is also present as an additional builder substance, the weight ratio of aluminosilicate to silicate, in each case based on anhydrous active substances, is preferably 1:10 to 10:1. In agents which contain 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.

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

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

wobei die Mengenangaben sich auf das gesamte Waschmittel beziehen. Dies gilt auch für alle folgenden Mengenangaben, sofern nicht ausdrücklich anders angegeben.In a preferred embodiment, the agent has a water-soluble builder block. The use of the term "builder block" is intended to express that the agent does not contain any builder substances other than those that are water-soluble, i.e. all builder substances contained in the agent are combined in the "block" characterized in this way, with the exception of the amounts of substances that may be commercially present in small quantities as impurities or stabilizing additives in the other ingredients of the agent. The term "water-soluble" is to be understood to mean that the builder block dissolves in the water at the concentration determined by the amount used. of the agent containing it under the usual conditions, dissolves without residue. Preferably, at least 15% by weight and up to 55% by weight, in particular 25% by weight to 50% by weight of water-soluble builder block are contained in the agents. This preferably consists of the builder components

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

The quantities refer to the entire detergent. This also applies to all following quantities, unless expressly stated otherwise.

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.%.

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

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.

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

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, among which metaphosphoric acids (HPO ₃ ) _n and orthophosphoric acid H ₃ PO ₄ can be distinguished alongside higher molecular weight representatives. The phosphates combine several advantages: They act as alkali carriers, prevent limescale deposits on machine parts or limescale incrustations in fabrics and also contribute to the cleaning performance. Sodium dihydrogen phosphate, 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 easily soluble in water. When heated, they lose their water of crystallization and turn into the weakly acidic diphosphate (disodium hydrogen diphosphate, Na ₂ H ₂ P ₂ O ₇ ) at 200°C, and into sodium trimetaphosphate (Na ₃ P ₃ O ₉ ) and Madrell's salt at higher temperatures. NaH ₂ PO ₄ reacts acidically; it is formed when phosphoric acid is adjusted to a pH of 4.5 with sodium hydroxide solution and the mash is sprayed. Potassium dihydrogen phosphate (primary or monobasic potassium phosphate, potassium biphosphate, KDP), 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 easily soluble in water. Disodium hydrogen phosphate (secondary sodium phosphate), Na ₂ HPO ₄ , is a colorless, highly water-soluble crystalline salt. It exists anhydrous and with 2 moles (density 2.066 gcm ^-3 , water loss at 95°), 7 moles (density 1.68 gcm ^-3 , melting point 48° with loss of 5 H ₂ O) and 12 moles of water (density 1.52 gcm ^-3 , melting point 35° with loss of 5 H ₂ O), becomes anhydrous at 100° and changes to the diphosphate Na ₄ P ₂ O ₇ when heated to a higher temperature. Disodium hydrogen phosphate is produced by neutralizing phosphoric acid with soda solution using phenolphthalein as an indicator. Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K ₂ HPO ₄ , is an amorphous, white salt that is easily soluble in water. Trisodium phosphate, tertiary sodium phosphate, Na ₃ PO ₄ , are colorless crystals that 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 easily soluble in water under alkaline reaction and is prepared 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 , a melting point of 1340° and is easily soluble in water with an alkaline reaction. It is formed, for example, by heating Thomas slag with coal and potassium sulfate. Despite the higher price, the more easily 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). Substances are 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 mixing phosphoric acid with soda in a stoichiometric ratio and the solution is dehydrated 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 gcm ^-3 that is soluble in water, with the pH value of the 1% solution at 25° being 10.4. Condensation of NaH ₂ PO ₄ or KH ₂ PO ₄ produces higher molecular weight sodium and potassium phosphates, of which one can distinguish between cyclic representatives, the sodium or potassium metaphosphates, and chain-like types, the sodium or potassium polyphosphates. A variety of names are used for the latter in particular: fused or calcined phosphates, Graham's salt, Kurrol's and Madrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates. The technically important pentasodium triphosphate, Na ₅ P ₃ O ₁₀ (sodium tripolyphosphate), is a non-hygroscopic, white, water-soluble salt of the general formula NaO-[P(O)(ONa)-O] _n -Na with n=3, which crystallizes anhydrous or with 6 H ₂ O. About 17 g of the anhydrous salt dissolve in 100 g of water at room temperature, about 20 g at 60°, and about 32 g at 100°; after heating the solution at 100° for two hours, hydrolysis produces about 8% orthophosphate and 15% diphosphate. 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 available in the form of a 50% by weight solution (> 23% P ₂ O ₅ , 25% K ₂ O). There are also sodium potassium tripolyphosphates, which can also be used in the context of 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

These can be used in the same way as sodium tripolyphosphate, potassium tripolyphosphate or mixtures of the two; mixtures of sodium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of potassium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of sodium tripolyphosphate and potassium tripolyphosphate and sodium potassium tripolyphosphate can also be used.

With regard to the builder component e), a preferred embodiment of the agent contains 1.5% by weight 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, the homopolymers of acrylic acid and, among these, those with an average molecular weight in the range from 5,000 D to 15,000 D (PA standard) are particularly preferred.

Enzymes that can be used in the products include those from the class of lipases, cutinases, amylases, pullulanases, mannanases, cellulases, hemicellulases, xylanases and peroxidases as well as mixtures thereof, for example amylases such as Termamyl ^® , Amylase-LT ^® , Maxamyl ^® , Duramyl ^® and/or Purafect ^® OxAm, lipases such as Lipolase ^® , Lipomax ^® , Lumafast ^® , Lipozym ^® and/or Lipex ^® , cellulases such as Celluzyme ^® and/or Carezyme ^® . Enzymatic active ingredients obtained from fungi or bacteria such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus, Humicola lanuginosa, Humicola insolens, Pseudomonas pseudoalcaligenes or Pseudomonas cepacia are particularly suitable. The enzymes used, if any, can be adsorbed on carriers and/or embedded in coating substances in order to protect them against premature inactivation. They are preferably contained in detergents in amounts of up to 10% by weight, in particular from 0.2% by weight to 2% by weight.

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

The organic solvents that can be used in the detergents, especially when they are 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 that can be derived from the above-mentioned classes of compounds. Such water-miscible solvents are preferably present in the detergents in amounts not exceeding 30% by weight, especially from 6% by weight to 20% by weight.

Naturally derived polymers that can be used as thickeners in aqueous liquid agents include agar-agar, carrageenan, tragacanth, gum arabic, alginates, pectins, polyoses, guar flour, locust bean gum, starch, dextrins, gelatin and casein, cellulose derivatives such as carboxymethylcellulose, hydroxyethyl and hydroxypropyl cellulose, and polymeric polysaccharide thickeners such as xanthan; fully synthetic polymers such as polyacrylic and polymethacrylic compounds, vinyl polymers, polycarboxylic acids, polyethers, polyimines, polyamides and polyurethanes can also be used as thickeners.

To set a desired pH value that does not arise automatically from the mixture of the other components, the agents can contain system- and environmentally compatible acids, in particular citric acid, acetic acid, tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid and/or adipic acid, but also mineral acids, in particular sulfuric acid, or bases, in particular ammonium or alkali hydroxides. Such pH regulators are The compositions preferably contain no more than 20% by weight, in particular from 1.2% to 17% by weight.

Examples of soil-removing polymers, which are often referred to as "soil release" agents or as "soil repellents" because of their ability to make the treated surface, for example the fiber, dirt-repellent, are non-ionic or cationic cellulose derivatives. The soil-removing polymers, which are particularly polyester-active, include copolyesters of dicarboxylic acids, for example adipic acid, phthalic acid or terephthalic acid, diols, for example ethylene glycol or propylene glycol, and polydiols, for example polyethylene glycol or polypropylene glycol. The soil-removing polyesters that are preferably used include those compounds that are formally accessible by esterification of two monomer parts, where the first monomer is a dicarboxylic acid HOOC-Ph-COOH and the second monomer is a diol HO-(CHR ¹¹ -) _a OH, which can also be present as a polymeric diol H-(O-(CHR ¹¹ -) _a ) _b OH. In this formula, Ph is an o-, m- or p-phenylene radical which can carry 1 to 4 substituents selected from alkyl radicals having 1 to 22 C atoms, sulfonic acid groups, carboxyl groups and mixtures thereof, R ¹¹ is hydrogen, an alkyl radical having 1 to 22 C atoms and mixtures thereof, a is a number from 2 to 6 and b is a number from 1 to 300. Preferably, the polyesters obtainable from these contain both monomer diol units -O-(CHR ¹¹ -) _a O- and polymer diol units -(O-(CHR ¹¹ -) _a ) _b O-. The molar ratio of monomer diol units to polymer diol units is preferably 100:1 to 1:100, in particular 10:1 to 1:10. In the polymer diol units, the degree of polymerization b is preferably in the range from 4 to 200, in particular from 12 to 140. The molecular weight or the average molecular weight or the maximum of the molecular weight distribution of preferred soil-releasing polyesters is in the range from 250 to 100,000, in particular from 500 to 50,000. The acid underlying the residue Ph is preferably selected from terephthalic acid, isophthalic acid, phthalic acid, trimellitic acid, mellitic acid, the isomers of sulfophthalic acid, sulfoisophthalic acid and sulfoterephthalic acid and mixtures thereof. If their acid groups are not part of the ester bonds in the polymer, they are preferably in salt form, in particular as an alkali or ammonium salt. Among these, the sodium and potassium salts are particularly preferred. If desired, instead of the monomer HOOC-Ph-COOH, small amounts, in particular not more than 10 mol% based on the amount of Ph with the meaning given above, of other acids which have at least two carboxyl groups can be contained in the soil-releasing polyester. These include, for example, alkylene and alkenylene dicarboxylic acids such as malonic acid, succinic acid, fumaric acid, maleic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid. The preferred diols HO-(CHR ¹¹ -) _a OH include those in which R ¹¹ is hydrogen and a is a number from 2 to 6, and those in which a has the value 2 and R ¹¹ is selected from hydrogen and the alkyl radicals with 1 to 10, in particular 1 to 3, carbon atoms. Among the latter diols, those of the formula HO-CH ₂ -CHR ¹¹ -OH, in which R ¹¹ has the meaning given above, are particularly preferred. Examples of diol components are Ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,2-decanediol, 1,2-dodecanediol and neopentyl glycol. Particularly preferred among the polymeric diols is polyethylene glycol with an average molecular weight in the range from 1000 to 6000. If desired, these polyesters can also be end-capped, with alkyl groups with 1 to 22 carbon atoms and esters of monocarboxylic acids being possible as end groups. The end groups bound via ester bonds can be based on alkyl, alkenyl and arylmonocarboxylic acids with 5 to 32 carbon atoms, in particular 5 to 18 carbon atoms. These include valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, undecenoic acid, lauric acid, lauroleic acid, tridecanoic acid, myristic acid, myristoleic acid, pentadecanoic acid, palmitic acid, stearic acid, petroselinic acid, petroselaidic acid, oleic acid, linoleic acid, linolaidic acid, linolenic acid, eleostearic acid, arachidic acid, gadoleic acid, arachidonic acid, behenic acid, erucic acid, brassidic acid, clupanodonic acid, lignoceric acid, cerotic acid, melissic acid, benzoic acid, which can carry 1 to 5 substituents with a total of up to 25 C atoms, in particular 1 to 12 C atoms, for example tert-butylbenzoic acid. The end groups can also be based on hydroxymonocarboxylic acids with 5 to 22 carbon atoms, which include, for example, hydroxyvaleric acid, hydroxycaproic acid, ricinoleic acid, its hydrogenation product hydroxystearic acid, and o-, m- and p-hydroxybenzoic acid. The hydroxymonocarboxylic acids can in turn be linked to one another via their hydroxyl group and their carboxyl group and can therefore be present multiple times in an end group. Preferably, the number of hydroxymonocarboxylic acid units per end group, i.e. their degree of oligomerization, is in the range from 1 to 50, in particular from 1 to 10. 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.

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 optionally other monomers.

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

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. Water-soluble colloids, usually of an organic nature, are suitable for this purpose, for example starch, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose, or salts of acidic sulfuric acid esters of cellulose or starch. Water-soluble polyamides containing acidic groups are also suitable for this purpose. Starch derivatives other than those mentioned above can also 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 preferred, for example in amounts of 0.1 to 5% by weight, based on the agent.

The agents can contain optical brighteners, among these in particular derivatives of 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 which carry a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group instead of the morpholino group. Brighteners of the substituted diphenylstyryl type can also be present, for example the alkali salts of 4,4'-bis(2-sulfostyryl)-diphenyl, 4,4'-bis(4-chloro-3-sulfostyryl)-diphenyl, or 4-(4-chlorostyryl)-4'-(2-sulfostyryl)-diphenyl. Mixtures of the above-mentioned optical brighteners can also be used.

Particularly when used in machine washing processes, it can be advantageous to add conventional foam inhibitors to the agents. Suitable foam inhibitors include, for example, soaps of natural or synthetic origin that have a high proportion of C ₁₈ -C ₂₄ fatty acids. Suitable non-surfactant-type foam inhibitors include, for example, organopolysiloxanes and mixtures thereof with microfine, optionally silanized silica, as well as paraffins, waxes, microcrystalline waxes and mixtures thereof with silanized silica or bis-fatty acid alkylenediamides. Mixtures of different foam inhibitors are also advantageously used, for example those made from silicones, paraffins or waxes. The foam inhibitors, in particular silicone and/or paraffin-containing foam inhibitors, are preferably bound to a granular, water-soluble or water-dispersible carrier substance. Mixtures of paraffins and bis-stearylethylenediamide are particularly preferred.

Peroxygen compounds that may be contained in the agents, particularly 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 that release hydrogen peroxide under the washing conditions, such as perborate, percarbonate and/or persilicate. Hydrogen peroxide can 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. Particular preference is given to using alkali percarbonate, alkali perborate monohydrate, alkali perborate tetrahydrate or, in particular in liquid agents, hydrogen peroxide in the form of aqueous solutions containing 3% to 10% by weight of hydrogen peroxide. Peroxygen compounds are preferably present in detergents in amounts of up to 50% by weight, in particular from 5% to 30% by weight.

In addition, conventional bleach activators which form peroxocarboxylic acids or peroxoimidic acids under perhydrolysis conditions and/or conventional transition metal complexes which activate the bleach can be used. The optional component of the bleach activators, which is present in particular in amounts of 0.5% by weight to 6% by weight, comprises the N- or O-acyl compounds which are usually used, for example multiply acylated alkylenediamines, in particular tetraacetylethylenediamine, acylated glycolurils, in particular tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, urazoles, diketopiperazines, sulfurylamides and cyanurates, as well as carboxylic acid anhydrides, in particular phthalic anhydride, carboxylic acid esters, in particular sodium isononanoylphenolsulfonate, and acylated sugar derivatives, in particular pentaacetylglucose, and cationic nitrile derivatives such as trimethylammonium acetonitrile salts. To avoid interaction with the peroxygen compounds during storage, the bleach activators can be coated with coating substances or granulated in a known manner, with tetraacetylethylenediamine granulated with the aid of carboxymethylcellulose with average grain sizes of 0.01 mm to 0.8 mm, granulated 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine, and/or trialkylammonium acetonitrile prepared in particle form being particularly preferred. In detergents, such bleach activators are preferably contained in amounts of up to 8% by weight, in particular from 2% by weight to 6% by weight, in each case based on the entire detergent.

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. To produce agents with increased bulk density, in particular in the range from 650 g/l to 950 g/l, a process comprising an extrusion step is preferred. Detergents in the form of aqueous solutions or solutions containing other conventional solvents are particularly advantageously produced by simply mixing the ingredients, which can be added in bulk or as a solution to an automatic mixer.

In a preferred embodiment, the agents, in particular in concentrated liquid form, are present as a portion in a completely or partially water-soluble coating. The portioning makes it easier for the consumer to dose. Such an agent portion preferably comprises 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.

The products can be packed in foil bags, for example. Bags made of water-soluble foil make it unnecessary for the consumer to tear open the packaging. This makes it easy to dispense a single portion for one wash cycle by placing the bag directly in the washing machine or by throwing the bag into a certain amount of water, for example in a bucket, bowl or hand basin. The foil bag surrounding the wash portion dissolves without leaving any residue when a certain temperature is reached.

In the prior art, there are numerous processes for producing water-soluble detergent portions, which are basically also suitable for producing agents that can be used in the context of the present invention. The best-known processes are the tubular film process with horizontal and vertical sealing seams. The thermoforming process (deep-drawing process) is also suitable for producing film bags or dimensionally stable detergent portions. The water-soluble casings do not necessarily have to be made of a film material, however, but can also be dimensionally stable containers that can be obtained, for example, by means of an injection molding process.

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 degree of filling. The processes are based on the water-soluble polymer being introduced into a shaping cavity. The capsules are filled and sealed either synchronously or in successive steps, with the latter case being filled through a small opening. The capsules are filled, for example, by a filling wedge arranged above two counter-rotating drums that have spherical half-shells on their surface. The drums guide polymer bands that cover the spherical half-shell cavities. Sealing takes place at the positions where the polymer band of one drum meets the polymer band of the opposite drum. At the same time, the filling material is injected into the capsule being formed, with the injection pressure of the filling liquid pressing the polymer bands into the spherical half-shell cavities. A process for producing water-soluble capsules, in which the capsules are filled first and then sealed, is based on the so-called Bottle-Pack ^® process. In this process, a tube-like preform is fed into a two-part cavity. The cavity is closed, the lower section of the tube being sealed, then the tube is inflated to form the capsule shape in the cavity, filled and finally sealed.

The shell material used to produce the water-soluble portion is preferably a water-soluble polymeric thermoplastic, particularly preferably selected from the group (optionally partially acetalized) polyvinyl alcohol, polyvinyl alcohol copolymers, polyvinylpyrrolidone, polyethylene oxide, gelatin, cellulose and derivatives thereof, starch and derivatives thereof, blends and composites, inorganic salts and mixtures of the materials mentioned, preferably hydroxypropylmethylcellulose and/or polyvinyl alcohol blends. Polyvinyl alcohols are commercially available, for example under the trademark Mowiol ^® (Clariant). Polyvinyl alcohols that are particularly suitable in the context of the present invention are, for example, Mowiol ^® 3-83, Mowiol ^® 4-88, Mowiol ^® 5-88, Mowiol ^® 8-88 and Clariant L648. The water-soluble thermoplastic used to produce the portion can optionally additionally comprise polymers selected from the group comprising acrylic acid-containing polymers, polyacrylamides, oxazoline polymers, polystyrene sulfonates, polyurethanes, polyesters, polyethers and/or mixtures of the above polymers. 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.

Claims (10)

1. Use of combinations of components a), b) and c) for increasing the primary washing power of detergents in the washing of textiles in washing liquids which are in particular aqueous and contain surfactants with respect to soiling which is in particular sensitive to surfactants or enzymes, wherein

   component a) is a polyalkoxylated amine with a weight average molecular weight M_w in the range from 600 g/mol to 10000 g/mol, which is obtainable by reacting ammonia or primary alkyl or hydroxyalkylamines, which have a molecular weight below 200 g/mol, with alkylene oxides,

   component b) is an alcohol polyalkoxylate with a weight-average molecular weight M_w in the range from 600 g/mol to 10000 g/mol, which is obtainable by reacting di- or triols with primary and/or secondary OH groups, which have a molecular weight M_w in the range from 60 g/mol to 200 g/mol, with alkylene oxides,

   and component c) is a polyalkoxylated polyalkyleneimine which is obtainable 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 M_w in the range from 1300 g/mol to 6000 g/mol, in particular from 1400 g/mol to 4500 g/mol, in that the alcohol polyalkoxylate (component b) has a weight-average molecular weight M_w in the range from 1300 g/mol to 6000 g/mol, in particular from 1400 g/mol to 4500 g/mol, and/or in that the polyalkoxylated polyalkyleneimine has a weight-average molecular weight Mw in the range from 5000 g/mol to 60000 g/mol, in particular from 10,000 g/mol to 22500 g/mol.
3. Use according to claim 1 or 2, characterized in that it is carried out by adding the polymer to an agent free of the active ingredient combination and its components or to a washing liquor which contains an agent free of the active ingredient combination or its components.
4. Use according to claim 3, characterized in that the amount of the active ingredient combination added, based on the amount of the agent free from the active ingredient combination or its components, is in the range from 0.01 % to 20 % by weight, in particular from 1 % to 15 % by weight.
5. Process for removing soiling from textiles, in particular soiling which is sensitive to surfactants or enzymes, characterized in that a combination of components a), b) and c) in a washing liquor which is in particular aqueous and contains surfactants is brought into contact with soiled textiles, wherein

   component a) is a polyalkoxylated amine with a weight average molecular weight M_w in the range from 600 g/mol to 10000 g/mol, which is obtainable by reacting ammonia or primary alkyl or hydroxyalkylamines, which have a molecular weight below 200 g/mol, with alkylene oxides,

   component b) is an alcohol polyalkoxylate with a weight-average molecular weight M_w in the range from 600 g/mol to 10000 g/mol, which is obtainable by reacting di- or triols with primary and/or secondary OH groups, which have a molecular weight M_w in the range from 60 g/mol to 200 g/mol, with alkylene oxides,

   and component c) is a polyalkoxylated polyalkyleneimine which is obtainable by reacting polyalkyleneimines with alkylene oxides.
6. Process 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 water-containing 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 detergent, contains at least 30 % by weight, preferably in the range from 30 % by weight to 6 5% by weight and in particular from 45 % by weight to 58 % by weight of surfactant, 4 % by weight to 25 % by weight, in particular 6% by weight to 15 % by weight of water and 0.01% by weight to 20 % by weight, in particular 1 % by weight to 15 % by weight of a combination of components a), b), and c), where

   component a) is a polyalkoxylated amine with a weight-average molecular weight M_w in the range from 600 g/mol to 10000 g/mol, which is obtainable by reacting ammonia or primary alkyl or hydroxyalkylamines which have a molecular weight below 200 g/mol with alkylene oxides,

   component b) is an alcohol polyalkoxylate with a weight-average molecular weight M_w in the range from 600 g/mol to 10000 g/mol, which is obtainable by reacting diols or triols with primary and/or secondary OH groups, which have a molecular weight Mw in the range from 60 g/mol to 200 g/mol, with alkylene oxides, and component

   c) is a polyalkoxylated polyalkyleneimine, which is obtainable by reacting polyalkyleneimines with alkylene oxides.
8. The agent according to claim 7, characterized in that it is present as a portion in a wholly or partially water-soluble coating.
9. Composition portion according to claim 8, characterized in that it comprises 5 g to 35 g, in particular from 7 g to 25 g, of the liquid composition.
10. Use, process 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 in the range from 1:10 to 10:1, in particular from 3:7 to 7:3, and/or the weight ratio of component b) to component c) is in the range from 1:10 to 10:1, in particular from 3:7 to 7:3.