DE102019007302A1 - Graying inhibiting detergents - Google Patents

Abstract

What is proposed is an aqueous liquid detergent containing surfactant and, if appropriate, other customary ingredients, the agent containing a copolymer which contains heterocylene derivatives bound via ester or amide bonds to a backbone obtainable by polymerization of ethylenically unsaturated monomers.

Description

The invention relates to a liquid detergent which contains, as graying-inhibiting active ingredient, a specific copolymer with a monomer obtainable partly from renewable raw materials.

The task of graying inhibitors is to keep the dirt detached from the fibers when washing textiles suspended in the liquor and thus to prevent the dirt from being drawn back onto the textile. Water-soluble colloids of mostly organic nature are suitable for this, for example glue, gelatine, or salts of acidic sulfuric acid esters of cellulose or starch. Water-soluble polyamides containing acidic groups are also suitable for this purpose. It is also possible to use soluble starch preparations and other starch products than those mentioned above, for example degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone can also be used. Cellulose ethers such as carboxymethyl cellulose (Na salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as methyl hydroxyethyl cellulose, methylhydroxypropyl cellulose, methyl carboxymethyl cellulose and their mixtures are often used in amounts of normally 0.1 to 5% by weight, based on the detergent.

Although the cellulose ethers mentioned have a good graying-inhibiting effect, their use in water-containing liquid detergents is so narrow that in practice they can essentially not be incorporated into them. In addition to their graying inhibitor effect, which is only relevant when used in the washing process, these cellulose ethers have a comparatively low solubility in surfactant-containing systems and a strong thickening effect on aqueous systems. If they are incorporated into liquid detergents containing water and, in particular, anionic surfactants, in the concentrations desired for the graying-inhibiting effect, the result is usually either no longer flowable or pourable products, which can only be handled by the user through additional effort, for example making them water-soluble or water-insoluble packaged single-dose portions, can be achieved, or the cellulose ethers are, especially after storage, not completely dissolved in the water-containing liquid detergent or not evenly dispersed in it, which in addition to aesthetics perceived as poor, also leads to uneven dosage of the graying inhibitor active ingredient when using the agent containing it leads.

From the international patent application WO 2006/117056 A1 the use of celluloses which carry sulfoalkyl groups bonded via ether, ester or amide functions to prevent redeposition when washing textiles is known. The international patent application WO 2014/124872 A1 discloses surfactant-containing liquid detergents which contain sulfoethyl cellulose with a degree of substitution of 0.3 to 0.9 as the graying-inhibiting active ingredient.

Surprisingly, it has now been found that a good graying-inhibiting effect can also be achieved in water-containing liquid detergents without unreasonable increase in viscosity or precipitation if a copolymer defined below is used which contains heterocyclic derivatives bonded via ester or amide bonds to a backbone obtainable by polymerization of ethylenically unsaturated monomers.

enthält, in der R¹ und R³ unabhängig voneinander aus -H und -CH₃ und deren Mischungen, R² und R⁴ unabhängig voneinander aus -C(=O)O- und -C(=O)NH- und deren Mischungen, wobei deren Carbonyl-C-Atom an das die Reste R¹ und R³ tragende Rückgrat und deren einfach an die Carbonylgruppe gebundenes O- oder N-Atom an die heterocyclische Einheit gebunden ist, R⁵ aus der Gruppe umfassend H, M mit M = H, Na und/oder ½ Zn, der 2-Aminoethyl-, Benzyl-, 2-(t-Butylamino)-ethyl-, Butyl-, tert-Butyl-, 3-Chlor-2-hydroxypropyl-, Cyclohexyl-, 3,3-Diethoxypropyl-, 2-(Diethylamino)-ethyl-, 2-(2-Butoxyethyloxy)-ethyl-, 2-(2-Methoxy-polyethyloxy)-ethyl-, 2-(Diisopropylamino)-ethyl, 2-(Dimethylamino)-ethyl, 2-Ethoxyethyl-, 2-Phenoxyethyl-, 2-Ethylhexyl-, Ethyl-, Hexyl-, Hydroxybutyl-, 2-Hydroxyethyl, 2-Carboxyphenyl-, Hydroxypropyl-, Isobornyl-, Isobutyl-, Methyl-, Mono-2-oxymethylmaleat-, Mono-2-oxyethylsuccinat-, 2-N-Morpholinoethyl-, 1-Naphthyl-, Phenyl-, Propyl-, 1-Pyrenmethyl-, Poly(propylenoxy)propyl-, Stearyl-, 3-Sulfopropyl-, Tetrahydrofurfuryl-, Tri(ethylenoxy)ethyl-, 2-Carboxyethyl-, 2-Methyl-1-sulfino-propyl-, und Tris(hydroxymethyl)methyl-Gruppe sowie deren Mischungen, X aus O und NH und deren Mischungen, Z aus OH, NH₂, OR⁶ und deren Mischungen, und R⁶ aus aliphatischen Resten mit 1 bis 10 C-Atomen ausgewählt werden, die Zahlen n und m so gewählt werden, dass das zahlenmittlere Molekulargewicht des Polymers im Bereich von 1 000 g/mol bis 5 000 000 g/mol liegt, wobei der Anteil von m an der Summe aus m und n im Bereich von 20 % bis 99 %, der Anteil von n an der Summe aus m und n im Bereich von 1 % bis 80 %, das zahlenmittlere Molekulargewicht der Poly(propylenoxy)propyl-Gruppe im Bereich von 250 g/mol bis 600 g/mol und das zahlenmittlere Molekulargewicht der 2-(2-Methoxy-polyethyloxy)-ethyl-Gruppe im Bereich von 100 g/mol bis 10 000 g/mol, vorzugsweise von 200 g/mol bis 7 000 g/mol und insbesondere von 300 g/mol bis 5 000 g/mol liegt. Dabei müssen nicht alle Reste Z in der Formel (I) die gleiche Bedeutung haben. Die Bestimmung des Molekulargewichts des erfindungswesentlichen Copolymers kann beispielsweise durch Gel-Permeations-Chromatographie vorgenommen werden.The invention relates to an aqueous liquid detergent containing surfactant and, if appropriate, other conventional ingredients of detergents and cleaning agents, the agent being a copolymer of the general formula (I),

contains, in which R ¹ and R ³ independently of one another from -H and -CH ₃ and mixtures thereof, R ² and R ⁴ independently of one another from -C (= O) O- and -C (= O) NH- and mixtures thereof , the carbonyl C atom of which is ^{bonded to the backbone carrying the radicals R 1} and R ³ and whose O or N atom, which is simply bonded to the carbonyl group, is bonded to the heterocyclic unit, R ⁵ from the group comprising H, M with M. = H, Na and / or ½ Zn, the 2-aminoethyl, benzyl, 2- (t-butylamino) ethyl, butyl, tert-butyl, 3-chloro-2-hydroxypropyl, cyclohexyl, 3,3-diethoxypropyl-, 2- (diethylamino) -ethyl-, 2- (2-butoxyethyloxy) -ethyl-, 2- (2-methoxy-polyethyloxy) -ethyl-, 2- (diisopropylamino) -ethyl, 2- (Dimethylamino) ethyl, 2-ethoxyethyl, 2-phenoxyethyl, 2-ethylhexyl, ethyl, hexyl, hydroxybutyl, 2-hydroxyethyl, 2-carboxyphenyl, hydroxypropyl, isobornyl, isobutyl, methyl , Mono-2-oxymethyl maleate, mono-2-oxyethyl succinate, 2-N-morpholinoethyl, 1-naphthyl, phenyl, propyl, 1-pyrene methyl, poly (propyleneoxy) per pyl, stearyl, 3-sulfopropyl, tetrahydrofurfuryl, tri (ethyleneoxy) ethyl, 2-carboxyethyl, 2-methyl-1-sulfino-propyl, and tris (hydroxymethyl) methyl groups and mixtures thereof, X from O and NH and their mixtures, Z from OH, NH ₂ , OR ⁶ and their mixtures, and R ⁶ from aliphatic radicals with 1 to 10 carbon atoms, the numbers n and m are chosen so that the The number average molecular weight of the polymer is in the range from 1,000 g / mol to 5,000,000 g / mol, the proportion of m in the sum of m and n in the range from 20% to 99%, the proportion of n in the sum of m and n in the range from 1% to 80%, the number average molecular weight of the poly (propyleneoxy) propyl group in the range from 250 g / mol to 600 g / mol and the number average molecular weight of the 2- (2-methoxy-polyethyloxy) - ethyl group in the range from 100 g / mol to 10,000 g / mol, preferably from 200 g / mol to 7,000 g / mol and in particular from 300 g / mol to 5,000 g / mol. Not all of the Z radicals in formula (I) have to have the same meaning. The molecular weight of the copolymer essential to the invention can be determined, for example, by gel permeation chromatography.

In the copolymers of the general formula (I), R ² and / or R ⁴ is preferably -C (= O) O-, R ⁵ H, ONa, 2- (2-butoxyethyloxy) -ethyl-, 2- (2-methoxyethyloxy) ) -ethyl, 2-ethoxyethyl, 2-methoxyethyl, 2-phenoxyethyl, hydroxybutyl, 2-hydroxyethyl, 2-carboxyphenyl, hydroxypropyl, methyl, mono-2-oxymethyl maleate, mono-2- oxyethylsuccinate, 2-N-morpholinoethyl, poly (propyleneoxy) propyl, stearyl, 3-sulfopropyl, tetrahydrofurfuryl, tri (ethyleneoxy) ethyl, 2-carboxyethyl, 2-methyl-1-sulfino-propyl or tris (hydroxymethyl) methyl group, and / or Z OH or R ⁵ . The preferred number average molecular weight of the poly (propyleneoxy) propyl group is in the range from 300 g / mol to 400 g / mol.

Those copolymers of the general formula (I) whose number average molecular weight is in the range from 3,000 g / mol to 200,000 g / mol are preferred. Also preferred are those copolymers of the general formula (I) in which the proportion of m to the sum of m and n is in the range from 25% to 90% and the proportion of n to the sum of m and n is in the range of 10% up to 75%.

The copolymers suitable according to the invention can, for example, by radical polymerization of secondary 2-hydroxyalkyl-tetrahydrofuran-3,4-diol- (meth) acrylic acid esters or 2-aminoalkyl-tetrahydrofuran-3,4-diol- (meth) acrylic acid amides with (meth) acrylic acid or whose C ₁ -10 alkyl esters or amides are produced, it being possible for low molar masses to be enforced by adding chain transfer agents. The parts marked with the indices m and n can occur in blocks or randomly distributed in the copolymer essential to the invention, the random copolymers being preferred for the sake of simpler producibility. In order to generate other radicals R ² accordingly, functionalized acrylates, methacrylates, acrylamides or methacrylamides can likewise be used.

The copolymers suitable according to the invention contain, with the exception of parts originating from radical initiator or termination compounds, preferably no parts originating from monomers other than those which lead to the parts marked with the indices m and n.

An agent according to the invention preferably contains 0.01% by weight to 10% by weight, in particular 0.1% by weight to 5% by weight, of said copolymer of the general formula (I).

The invention also relates to the use of the above-mentioned copolymer of the general formula (I) in aqueous liquid detergents to improve the inhibition of graying when washing flat textile structures with the aqueous liquid detergent.

In addition to the above-mentioned copolymer and surfactants explained in more detail below, the detergent according to the invention contains water in amounts - based on the total detergent - of preferably up to 90% by weight and in particular from 30% by weight to 60% by weight, with if desired, this can also be partially exchanged for a non-aqueous, water-soluble solvent or a non-aqueous, water-soluble solvent component can also be present. Non-aqueous solvents that can be used in the liquid agents originate, for example, from the group of monohydric or polyhydric alcohols, alkanolamines or glycol ethers, provided they are miscible with water in the specified concentration range. The solvents are preferably selected from ethanol, n- or i-propanol, the butanols, ethylene glycol, butanediol, glycerine, diethylene glycol, butyl diglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-methyl glycol ether, diethylene glycol ether, diethylene glycol ether, diethylene glycol ether, diethylene glycol ether, diethylene glycol ether, diethylene glycol ether, ethylene glycol mono-n-butyl ether, , ethyl or propyl ether, dipropylene glycol monomethyl or ethyl ether, diisopropylene glycol monomethyl or ethyl ether, methoxy, ethoxy or butoxy triglycol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, propylene glycol t-butyl ether and mixtures thereof. The amount of the non-aqueous, water-soluble solvent component based on the total amount of the detergent and cleaning agent is preferably up to 15% by weight, in particular 0.5% by weight to 10% by weight. In preferred embodiments of low-water agents, the content of water that has not been exchanged for non-aqueous solvents is not more than 15% by weight, in particular 1% by weight to 8% by weight.

The liquid detergents contain surfactant, it being possible to use anionic, nonionic, cationic and / or amphoteric surfactants. The presence of anionic surfactants is preferred, mixtures of anionic and nonionic surfactants being particularly advantageous from an application point of view. The total surfactant content of the liquid agent is preferably in the range from 10% by weight to 60% by weight, in particular 15% by weight to 50% by weight, in each case based on the total liquid agent.

The nonionic surfactants used are preferably alcohol alkoxylates, i.e. alkoxylated, advantageously ethoxylated, in particular primary alcohols with preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical is linear or preferably in 2- Position can be methyl-branched or can contain linear and methyl-branched radicals in the mixture, as they are usually present in oxo alcohol radicals. In particular, however, alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are preferred. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 EO, 4 EO or 7 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 7 EO. The stated degrees of ethoxylation represent statistical mean values which, for a specific product, can be an integer or a fraction. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO. Nonionic surfactants which contain EO and PO groups together in the molecule can also be used according to the invention. Block copolymers with EO-PO block units or PO-EO block units can be used here, but also EO-PO-EO copolymers or PO-EO-PO copolymers. Mixed alkoxylated nonionic surfactants can also be used in which EO and PO units are not distributed in blocks, but rather statistically. Such products can be obtained by the simultaneous action of ethylene and propylene oxide on fatty alcohols.

In addition, alkyl glycosides, in particular of the general formula RO (G) _x , in which R is a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical with 8 to 22, preferably 12 to 18 carbon atoms, can also be used as nonionic surfactants and G is the symbol that stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is 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, in particular fatty acid methyl esters.

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

in der RCO 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 nachfolgende Acylierung mit einer Fettsäure, einem Fettsäurealkylester oder einem Fettsäurechlorid erhalten werden können. Zur Gruppe der Polyhydroxyfettsäureamide gehören auch Verbindungen der Formel (III),

in der R für einen linearen oder verzweigten Alkyl- oder Alkenylrest mit 7 bis 12 Kohlenstoffatomen, R¹ für einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest mit 2 bis 8 Kohlenstoffatomen und R² für einen linearen, verzweigten oder cyclischen 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 Zuckers erhalten, beispielsweise Glucose, Fructose, Maltose, Lactose, Galactose, Mannose oder Xylose. Die N-Alkoxy- oder N-Aryloxy-substituierten Verbindungen können dann durch Umsetzung mit Fettsäuremethylestern in Gegenwart eines Alkoxids als Katalysator in die gewünschten Polyhydroxyfettsäureamide überführt werden.Further suitable nonionic surfactants are polyhydroxy fatty acid amides of the formula (II),

in which RCO 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 (III),

in which R stands for a linear or branched alkyl or alkenyl radical with 7 to 12 carbon atoms, R ¹ for a linear, branched or cyclic alkyl radical or an aryl radical with 2 to 8 carbon atoms and R ² for a linear, branched or cyclic alkyl radical or an aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, C _1-4 -alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical whose alkyl chain has at least two hydroxyl groups is substituted, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this radical. [Z] is preferably obtained by reductive amination of a sugar such as glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy- or N-aryloxy-substituted compounds can then 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.

The content of nonionic surfactants in the liquid detergents is preferably 5% by weight to 30% by weight, in particular 7% by weight to 20% by weight and particularly preferably 9% by weight to 15% by weight, each based on the total mean. In a preferred embodiment, the nonionic surfactant is selected from alcohol alkoxylate and alkyl polyglycoside and mixtures thereof.

As anionic surfactants, for example, those of the sulfonate and sulfate type can be used. Surfactants of the sulfonate type are preferably C _9-13 alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkane sulfonates and disulfonates, such as those obtained, for example, from C _12-18 monoolefins with terminal or internal double bonds by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products is possible. _{Alkane sulfonates obtained from C 12-18} alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization, are also suitable. The esters of α-sulfo fatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.

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

The alk (en) yl sulfates are the alkali and especially the sodium salts of the sulfuric acid _{half esters of the C 12} -C ₁₈ fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁₀ -C ₂₀ oxo alcohols and those half-esters of secondary alcohols of these chain lengths are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical produced on a petrochemical basis and which have a degradation behavior similar to that of the appropriate compounds based on oleochemical raw materials. From the point of view of washing technology, preference is given to the C ₁₂ -C ₁₆ -alkyl sulphates and C12-C15-alkyl sulphates and also C14-C15-alkyl sulphates.

The sulfuric acid monoesters of the abovementioned alcohol alkoxylates, for example the straight-chain or branched C _7-21 alcohols ethoxylated with 1 to 6 moles of ethylene oxide, such as 2-methyl-branched C _9-11 alcohols with an average of 3.5 moles of ethylene oxide (EO) or C. _12-18 fatty alcohols with 1 to 4 EO are suitable. These are often referred to as ether sulfates.

Other suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and represent 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 of these. Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols which, considered in isolation, represent nonionic surfactants (see description below). 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 salts thereof.

Preferred anionic surfactants are soaps. Saturated and unsaturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, (hydrogenated) erucic acid and behenic acid and, in particular, soap mixtures derived from natural fatty acids, for example coconut, palm kernel, olive oil or tallow fatty acids, are suitable. In a preferred embodiment, the detergent contains 2% by weight to 20% by weight, in particular 3% by weight to 15% by weight and particularly preferably 5% by weight to 10% by weight fatty acid soap. Fatty acid soaps are an important component for the detergency of a liquid, especially aqueous, detergent and cleaning agent. Surprisingly, it has been shown that when the low methylated carboxymethyl cellulose ether is used, clear and stable liquid detergents are obtained even in the presence of large amounts of fatty acid soap. The use of large amounts (2 2% by weight) of fatty acid soap in such systems usually leads to cloudy and / or unstable products.

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.

The content of anionic surfactants in preferred liquid detergents is 5% by weight to 35% by weight, in particular 8% by weight to 30% by weight and particularly preferably 10% by weight to 25% by weight, based in each case on the entire remedy. It is particularly preferred that the amount of fatty acid soap is at least 2% by weight, particularly preferably at least 3% by weight and in particular from 4% by weight to 10% by weight. In a further preferred embodiment, the agents contain at least 2, in particular 3, different anionic surfactants selected from alkylbenzenesulfonate, ether sulfate and fatty acid soap.

The detergent can contain a polyacrylate which acts as a co-builder and optionally also as a thickener. The polyacrylates include polyacrylate or polymethacrylate thickeners, such as the high molecular weight homopolymers of acrylic acid crosslinked with a polyalkenyl polyether, in particular an allyl ether of sucrose, pentaerythritol or propylene (INCI name according to the "International Dictionary of Cosmetic Ingredients" of "The Cosmetic," Toiletry and Fragrance Association (CTFA) ": Carbomer), which are also known as carboxyvinyl polymers. Such polyacrylic acids are available from 3V Sigma under the trade name Polygel®, for example Polygel DA, and from Noveon under the trade name Carbopol®, for example Carbopol 940 (molecular weight approx. 4,000,000), Carbopol 941 (molecular weight approx 1,250,000) or Carbopol 934 (molecular weight approx. 3,000,000). This also includes the following acrylic acid copolymers: (i) Copolymers of two or more monomers from the group of acrylic acid, methacrylic acid and their simple esters, preferably formed with C _1-4 alkanols (INCI Acrylates Copolymers), which include, for example, the copolymers of methacrylic acid, butyl acrylate and methyl methacrylate (CAS designation according to Chemical Abstracts Service: 25035-69-2) or of butyl acrylate and methyl methacrylate (CAS 25852-37-3) and which, for example, from Rohm & Haas under the trade name Aculyn® and Acusol® as well as from Degussa (Goldschmidt) under the trade name Tego® Polymer, for example the anionic non-associative polymers Aculyn 22, Aculyn 28, Aculyn 33 (crosslinked), Acusol 810, Acusol 823 and Acusol 830 (CAS 25852-37 -3); (ii) crosslinked high molecular weight acrylic acid copolymers, including, for example, the copolymers of C _10-30 alkyl acrylates crosslinked with an allyl ether of sucrose or pentaerythritol with one or more monomers from the group of acrylic acid, methacrylic acid and their simple, preferably C _{1 -4} alkanols, esters (INCI Acrylates / C10-30 Alkyl Acrylate Crosspolymer) and which are available, for example, from Noveon under the trade name Carbopol®, e.g. the hydrophobized Carbopol ETD 2623 and Carbopol 1382 (INCI Acrylates / C10- 30 Alkyl Acrylate Crosspolymer) and Carbopol Aqua 30 (formerly Carbopol EX 473). Preferred liquid detergents contain the polyacrylate in an amount of up to 5% by weight, in particular from 0.1% by weight to 2.5% by weight. It is advantageous if the polyacrylate is a copolymer of an unsaturated mono- or dicarboxylic acid and one or more C ₁ -C ₃₀ -alkyl esters of (meth) acrylic acid.

The viscosity of the liquid detergents and cleaning agents can be measured using customary standard methods (for example Brookfield LVT-II viscometer at 20 rpm and 20 ° C., spindle 3) and is preferably in the range from 150 mPas to 5000 mPas. Preferred agents have viscosities of 500 mPas to 4000 mPas, with values of 1000 mPas to 3500 mPas being particularly preferred.

In addition, the liquid detergents can contain other ingredients that further improve their application and / or aesthetic properties. In the context of the present invention, preferred agents contain one or more substances from the group of builders, bleaches, bleach activators, enzymes, electrolytes, pH adjusters, fragrances, perfume carriers, fluorescent agents, dyes, hydrotopes, foam inhibitors, additional anti-redeposition agents or graying inhibitors, optical brighteners, Inlet inhibitors, anti-crease agents, color transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, corrosion inhibitors, antistatic agents, ironing aids, repellent and impregnating agents, swelling and slip-proofing agents and UV absorbers.

Builders that can be contained in the liquid agents include, in particular, silicates, aluminum silicates (especially zeolites), carbonates, salts of organic di- and polycarboxylic acids and mixtures of these substances.

Suitable crystalline, layered sodium silicates have the general formula NaMSi _x O _{2x + 1} -H ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2, 3 or 4 are. Preferred crystalline sheet silicates of the formula given are those in which M stands for sodium and x assumes the values 2 or 3. In particular, both β- and 5-sodium disilicates _{Na 2} Si ₂ O _{5 .yH 2} O are preferred.

It is also possible to use amorphous sodium silicates with a Na ₂ O: SiO ₂ module of 1: 2 to 1: 3.3, preferably 1: 2 to 1: 2.8 and in particular 1: 2 to 1: 2.6, which are delayed in dissolution and have secondary washing properties. The delay in dissolution compared with conventional amorphous sodium silicates can be brought about in various ways, for example by surface treatment, compounding, compaction / compression or by overdrying. In the context of this invention, the term “amorphous” is also understood to mean “X-ray amorphous”. This means that, in X-ray diffraction experiments, the silicates do not produce sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-ray radiation that have a width of several degree units of the diffraction angle. However, it can very well even lead to particularly good builder properties if the silicate particles give blurred or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted in such a way that the products have microcrystalline areas of size 10 to a few hundred nm, values up to a maximum of 50 nm and in particular up to a maximum of 20 nm being preferred. Such so-called X-ray amorphous silicates also have a delay in dissolution compared to conventional water glasses. Compressed / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates are particularly preferred.

The finely crystalline, synthetic zeolite used, containing bound water, is preferably zeolite A and / or P. Zeolite MAP® (commercial product from Crosfield) is particularly preferred as zeolite P. However, zeolite X and mixtures of A, X and / or P are also suitable and are commercially available and, for example, a co-crystallizate of zeolite X and zeolite A (approx. 80% by weight zeolite X) can also be used with preference ), which is sold by SASOL under the brand name VEGOBOND AX® and has the formula nNa ₂ O - (1-n) K ₂ O ▪ Al ₂ O ₃ ▪ (2- 2.5) SiO ₂ ▪ (3.5-5.5) H ₂ O can be described with n = 0.90 - 1.0. The zeolite can be used as a spray-dried powder or as an undried, stabilized suspension that is still moist from its manufacture. If the zeolite is used as a suspension, it can contain small additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C ₁₂ -C ₁₈ fatty alcohols with 2 to 5 ethylene oxide groups , C ₁₂ -C ₁₄ fatty alcohols with 4 to 5 ethylene oxide groups or ethoxylated isotridecanols. Suitable zeolites have an average particle size of less than 10 μm (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.

It is also possible to use the generally known phosphates as builder substances, provided that such use is not to be avoided for ecological reasons. The sodium salts of orthophosphates, pyrophosphates and especially tripolyphosphates are particularly suitable.

Sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance among the compounds which serve as bleaching agents and produce H ₂ O _{2 in water.} Other bleaching agents that can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and _{peracid salts or peracids which provide H 2} O ₂ , such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloimino peracid or diperdodecanedioic acid. If present, these are preferably used in wrapped form in order to protect them against disintegration during storage.

In order to achieve an improved bleaching effect when washing at temperatures of 60 ° C and below, bleach activators can be incorporated into the detergents and cleaning agents. Bleach activators which can be used are compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids having preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or optionally substituted perbenzoic acid. Substances which carry O- and / or N-acyl groups with the stated number of carbon atoms and / or optionally substituted benzoyl groups are suitable. Polyacylated alkylenediamines, especially tetraacetylethylenediamine (TAED), acylated triazine derivatives, especially 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, especially tetraacetylglycoluril (TAGU), N- are preferred Acylimides, in particular N-nonanoyl succinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetine, ethylene diacetate 2,5-dihydrofuran.

In addition to the conventional bleach activators or instead of them, so-called bleach catalysts can also be incorporated into the liquid detergents and cleaning agents. These substances are bleach-intensifying transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo salen complexes or carbonyl complexes. Also Mn-, Fe, Co, Ru, Mo, Ti, V and Cu complexes with nitrogen-containing tripod ligands and Co, Fe, Cu and Ru ammine complexes can be used as bleach catalysts.

Particularly suitable enzymes are those from the classes of hydrolases such as proteases, esterases, lipases or lipolytic enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. All of these hydrolases contribute to the removal of stains such as protein, fat or starchy stains and graying in the laundry. Cellulases and other glycosyl hydrolases can also help to maintain the color and increase the softness of the textile by removing pilling and microfibrils. Oxireductases can also be used to bleach or to inhibit color transfer. Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus and Humicola insolens are particularly suitable. Proteases of the subtilisin type and in particular proteases obtained from Bacillus lentus are preferably used. Enzyme mixtures, for example of protease and amylase or protease and lipase or lipolytic enzymes or protease and cellulase or of cellulase and lipase or lipolytic enzymes or of protease, amylase and lipase or lipolytic enzymes or protease, lipase or lipolytic enzymes and cellulase, but especially protease and / or lipase-containing mixtures or mixtures with lipolytic enzymes of particular interest. Examples of such lipolytically acting enzymes are the known cutinases. Peroxidases or oxidases have also proven to be suitable in some cases. Suitable amylases include in particular α-amylases, iso-amylases, pullulanases and pectinases. The cellulases used are preferably cellobiohydrolases, endoglucanases and β-glucosidases, which are also called cellobiases, or mixtures of these. Since different cellulase types differ in their CMCase and Avicelase activities, the desired activities can be set by means of targeted mixtures of the cellulases.

The bleach activators, catalysts and / or enzymes can be adsorbed and / or coated on carrier substances in order to protect them against premature decomposition. The proportion of enzymes, liquid enzyme formulations, enzyme mixtures or enzyme granules can be, for example, about 0.1% by weight to 5% by weight, preferably 0.12% by weight to about 2.5% by weight, based in each case on the total agent , amount.

A wide number of the most varied salts can be used as electrolytes from the group of inorganic salts. Preferred cations are the alkali and alkaline earth metals, preferred anions are the halides and sulfates. From a manufacturing point of view, the use of NaCl or MgCl ₂ in the agents is preferred. The proportion of electrolytes in the agents is usually not more than 8% by weight, in particular 0.5% by weight to 5% by weight.

In order to bring the pH value of the liquid agent into the desired range, the use of pH adjusting agents may be indicated. All known acids or alkalis can be used here, provided that their use is not prohibited for technical or ecological reasons or for reasons of consumer protection. The amount of these adjusting agents usually does not exceed 10% by weight of the formulation as a whole.

Another component of agents according to the invention which may be contained is a hydrotrope. Preferred hydrotropes include the sulfonated hydrotropes such as, for example, the alkylarylsulfonates or alkylarylsulfonic acids. Preferred hydrotropes are selected from xylene, toluene, cumene, naphthalene sulfonate or sulfonic acid and mixtures thereof. Counter ions are preferably selected from sodium, calcium and ammonium. The liquid agents can optionally comprise up to 20% by weight of a hydrotrope, in particular 0.05% by weight to 10% by weight.

In order to improve the aesthetic impression of the liquid agents, they can be colored with suitable dyes. Preferred dyes, the selection of which presents no difficulty to the person skilled in the art, have a high storage stability and insensitivity to the other ingredients of the agents and to light, as well as no pronounced substantivity to textile fibers in order not to stain them.

Foam inhibitors which can be used in the liquid detergents and cleaning agents are, for example, soaps, paraffins or silicone oils, which can optionally also have been applied to carrier materials.

Suitable additional anti-redeposition agents, which are also referred to as "soil repellents", are, for example, the polymers known from the prior art of phthalic acid and / or terephthalic acid or their derivatives, in particular polymers made from ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified Derivatives of these. Of these, particularly preferred are sulfonated derivatives of phthalic acid and terephthalic acid polymers.

Optical brighteners can be added to the liquid detergents and cleaning agents in order to remove yellowing of the treated textile fabrics. These substances are absorbed by the fiber and cause a lightening effect by converting ultraviolet radiation, invisible to the human eye, into visible longer-wave light, whereby the ultraviolet light absorbed from the sunlight is emitted as a faint bluish fluorescence and, with the yellow shade of yellowed laundry, results in pure white. Suitable compounds originate, for example, from the substance classes of 4,4'-diamino-2,2'-stilbene disulfonic acids (flavonic acids), 4,4'-distyrylbiphenylene, methylumbelliferones, coumarins, dihydroquinolinones, 1,3-diarylpyrazolines, naphthalic acid imides, benzoxazole, benzisoxazole - And benzimidazole systems and the pyrene derivatives substituted by heterocycles. Optical brighteners are normally used in amounts of up to 0.5% by weight, in particular from 0.03% by weight to 0.3% by weight, based on the finished composition.

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

To combat microorganisms, the liquid washing and cleaning agents can contain antimicrobial active ingredients. Here, depending on the antimicrobial spectrum and mechanism of action, a distinction is made between bacteriostats and bactericides, fungistats and fungicides, etc. Important substances from these groups are, for example, benzalkonium chlorides, alkylarylsulfonates, halophenols and phenol mercuric acetate, although these compounds can be dispensed with entirely with the agents according to the invention.

In order to prevent undesired changes to the liquid detergents and cleaning agents and / or the treated textile fabrics caused by the action of oxygen and other oxidative processes, the agents can contain antioxidants. This class of compounds includes, for example, substituted phenols, hydroquinones, catechols and aromatic amines as well as organic sulfides, polysulfides, dithiocarbamates, phosphites and phosphonates. When such antioxidants are used, the agents according to the invention are naturally free from oxidizing bleaching agents.

Increased wearing comfort can result from the additional use of antistatic agents, which are also added to the agents. Antistatic agents increase the surface conductivity and thus enable the charges that have formed to flow off better. External antistatic agents are generally substances with at least one hydrophilic molecular ligand and give the surfaces a more or less hygroscopic film. These mostly surface-active antistatic agents can be divided into nitrogen-containing (amines, amides, quaternary ammonium compounds), phosphorus-containing (phosphoric acid esters) and sulfur-containing (alkyl sulfonates, alkyl sulfates) antistatic agents. External antistatic agents are, for example, lauryl (or stearyl) dimethylbenzylammonium chlorides, which are suitable as antistatic agents for textile fabrics or as additives to detergents, with an additional softening effect being achieved.

To improve the water absorption capacity, the rewettability of the treated textile fabrics and to facilitate ironing of the treated textile fabrics, silicone derivatives, for example, can be used in the liquid detergents and cleaning agents. These also improve the rinsing behavior of the agents through their foam-inhibiting properties. Preferred silicone derivatives are, for example, polydialkyl or alkylarylsiloxanes in which the alkyl groups have one to five carbon atoms and are completely or partially fluorinated. Preferred silicones are polydimethylsiloxanes, which can optionally be derivatized and are then amino-functional or quaternized or have Si-OH, Si-H and / or Si-Cl bonds. The viscosities of the preferred silicones are at 25 ° C. in the range between 100 and 100,000 mPas, it being possible to use the silicones in amounts between 0.2 and 5% by weight, based on the total agent.

Finally, the liquid washing and cleaning agents can also contain UV absorbers which are absorbed onto the treated textile fabrics and improve the light resistance of the fibers. Compounds which have these desired properties are, for example, the compounds and derivatives of benzophenone with substituents in the 2- and / or 4-position which are effective by radiationless deactivation. Substituted benzotriazoles, acrylates substituted by phenyl in the 3-position (cinnamic acid derivatives), optionally with cyano groups in the 2-position, salicylates, organic Ni complexes and natural substances such as umbelliferone and urocanic acid are also suitable.

To reduce the decomposition of certain detergent ingredients catalyzed by heavy metals avoid, substances can be used that complex heavy metals. Suitable heavy metal complexing agents are, for example, the alkali salts of ethylenediaminetetraacetic acid (EDTA) or nitrilotriacetic acid (NTA) and alkali metal salts of anionic polyelectrolytes such as polymaleates and polysulfonates.

A preferred class of complexing agents are the phosphonates, which are used in preferred liquid agents in amounts from 0.01% by weight to 2.5% by weight, preferably from 0.02% by weight to 2% by weight and in particular from 0.03 wt% to 1.5 wt% are included. These preferred compounds include in particular organophosphonates such as, for example, 1-hydroxyethane-1,1-diphosphonic acid (HEDP), aminotri (methylenephosphonic acid) (ATMP), diethylenetriamine-penta (methylene-phosphonic acid) (DTPMP or DETPMP) and 2-phosphonobutane-1 , 2,4-tricarboxylic acid (PBS-AM), which are mostly used in the form of their ammonium or alkali metal salts.

In addition to the constituents mentioned, a liquid washing and cleaning agent can also contain particles dispersed therein, the diameter of which along their greatest spatial extent is, for example, 100 μm to 10,000 μm. Such particles can be microcapsules or speckles as well as granules, compounds and scented pearls, microcapsules or speckles being preferred.

The term “microcapsule” is understood to mean aggregates which contain at least one solid or liquid core which is enclosed by at least one continuous shell, in particular a shell made of polymer (s). These are usually finely disperse liquid or solid phases encased with film-forming polymers, during the production of which the polymers precipitate on the material to be encased after emulsification and coacervation or interfacial polymerisation. The microscopic capsules can be dried like powder. In addition to single-core microcapsules, multi-core aggregates, also called microspheres, are known which contain two or more cores distributed in the continuous shell material. Single or multi-core microcapsules can also be enclosed by an additional second, third, etc. shell. Single-core microcapsules with a continuous shell are preferred. The shell can be made of natural, semi-synthetic or synthetic materials. Of course, coating materials are, for example, gum arabic, agar-agar, agarose, maltodextrins, alginic acid or their salts, e.g. sodium or calcium alginate, fats and fatty acids, cetyl alcohol, collagen, chitosan, lecithins, gelatin, albumin, shellac, polysaccharides such as starch or Dextran, sucrose and waxes. Semi-synthetic casing materials include chemically modified celluloses, in particular cellulose esters and ethers, e.g. cellulose acetate, ethyl cellulose, hydroxypropyl cellulose, hydroxypropylmethyl cellulose and carboxymethyl cellulose, as well as starch derivatives, in particular starch ethers and esters. Synthetic shell materials are, for example, polymers such as polyacrylates, polyamides, polyvinyl alcohol or polyvinylpyrrolidone.

Sensitive, chemically or physically incompatible and volatile components (= active substances) of the liquid agent can be enclosed in the interior of the microcapsule in a way that is stable for storage and transport. The microcapsules can contain, for example, optical brighteners, surfactants, complexing agents, bleaches, bleach activators, dyes and fragrances, antioxidants, builders, enzymes, enzyme stabilizers, antimicrobial agents, anti-redeposition agents, pH adjusters, electrolytes, foam inhibitors and / or UV absorbers are located. In addition to the constituents mentioned above as ingredients of the aqueous liquid agents according to the invention, the microcapsules can contain, for example, vitamins, proteins, preservatives, detergency boosters or pearlescent agents. The fillings of the microcapsules can be solids or liquids in the form of solutions or emulsions or suspensions.

The microcapsules can have any shape within the scope of production, but they are preferably approximately spherical. Their diameter along their greatest spatial extent can, depending on the components contained in their interior and the application, be between 0.01 µm (visually not recognizable as a capsule) and 10,000 µm. Visible microcapsules with a diameter in the range from 100 μm to 7,000 μm, in particular from 400 μm to 5,000 μm, are preferred. The microcapsules can be obtained by methods known in the art, the coacervation and the interfacial polymerization being of the greatest importance. All surfactant-stable microcapsules available on the market can be used as microcapsules, for example the commercial products (the shell material is indicated in each case in brackets) Hallcrest Microcapsules (gelatine, gum arabic), Coletica Thalaspheres (maritime collagen), Lipotec Millicapsules (alginic acid, agar-agar) , Induchem Unispheres (lactose, microcrystalline cellulose, hydroxypropylmethyl cellulose); Unicerin C30 (lactose, microcrystalline cellulose, hydroxypropylmethylcellulose), Kobo Glycospheres (modified starch, fatty acid esters, phospholipids), Softspheres (modified agar agar) and Kuhs Probiol Nanospheres (phospholipids).

Alternatively, it is also possible to use particles which do not have a core-shell structure, but in which the active ingredient is in a matrix a matrix-forming material is distributed. Such particles are also known as "speckles". A preferred matrix-forming material is alginate. To produce alginate-based speckles, an aqueous alginate solution, which also contains the active ingredient or ingredients to be included, is dripped and then hardened in a precipitation bath containing ^{Ca 2+} ions or Al ^{3+ ions.} It can be advantageous that the alginate-based speckles are then washed with water and then washed in an aqueous solution with a complexing agent in order to remove free Ca ²⁺ ions or free Al ³⁺ ions, which could undesirable interactions with ingredients of the liquid detergent , for example the fatty acid soaps, can be washed out. The alginate-based speckles are then washed with water to remove excess complexing agents. Alternatively, other matrix-forming materials can be used instead of alginate. Examples of matrix-forming materials include polyethylene glycol, polyvinylpyrrolidone, polymethacrylate, polylysine, poloxamer, polyvinyl alcohol, polyacrylic acid, polyethylene oxide, polyethoxyoxazoline, albumin, gelatin, acacia, chitosan, cellulose, dextran, Ficoll®, starch, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl cellulose. Carboxymethyl cellulose, carboxymethyl cellulose, deacetylated chitosan, dextran sulfate and derivatives of these materials. The matrix formation takes place with these materials, for example, via gelation, polyanion-polycation interactions or polyelectrolyte-metal ion interactions and is well known in the prior art, as is the production of particles with these matrix-forming materials. The particles can be dispersed stably in the aqueous liquid detergents and cleaning agents. Stable means that the agents are stable at room temperature and at 40 ° C. over a period of at least 4 weeks and preferably for at least 6 weeks without the agents creaming or sedimenting.

The release of the active ingredients from the microcapsules or speckles usually takes place during the application of the agents containing them by destruction of the shell or the matrix as a result of mechanical, thermal, chemical or enzymatic action. In a preferred embodiment of the invention, the liquid detergents contain the same or different particles in amounts of 0.01 to 10% by weight, in particular 0.2 to 8% by weight and extremely preferably 0.5 to 5% by weight.

Aqueous detergents and cleaning agents can be produced inexpensively and easily in conventional mixing and filling systems. For the preparation of the liquid agents, if present, the acidic components such as, for example, the linear alkyl sulfonates, citric acid, boric acid, phosphonic acid, the fatty alcohol ether sulfates and the nonionic surfactants are preferably initially introduced. The solvent component is preferably also added at this point in time, but the addition can also take place at a later point in time. If present, the complexing agent is added to these components. A base such as NaOH, KOH, triethanolamine or monoethanolamine, followed by the fatty acid, if present, is then added. The remaining ingredients and optionally the remaining solvents of the aqueous liquid agent are then added to the mixture and the pH is adjusted to the desired value. Finally, if desired, the particles to be dispersed can be added and homogeneously distributed in the aqueous liquid agent by mixing.

Examples

Example 1: Preparation of copolymers

A: A mixture of 50 g of xylitol (0.329 mol) and 60 ml of aqueous H ₂ SO ₄ (c = 3.0 mol / l) was refluxed with stirring for 24 hours. Then 14.4 g of NaOH (0.350 mol) were added and the water was removed on a rotary evaporator until a dark brown syrup was obtained. About 150 ml of ethanol were added to this and heated to 60 ° C. with stirring; To remove the salt residues, it was filtered through a folded filter at 60.degree. C., the filtrate was admixed with 2.0 g of activated charcoal and, after stirring for 5 minutes at 60.degree. C., filtered again. The filtrate was concentrated on a rotary evaporator and the residue was distilled at 300 ° C. ^{in a high vacuum (2.0 × 10 -2 mbar).} 40.9 g of (3S, 4R) -2- (hydroxymethyl) tetrahydrofuran-3,4-diol were obtained; Yield 93%. δ ^[1 H, MeOD] = 1.83 (s, 2H); 2.28-2.66 (m, 8H); 2.69-3.03 (m, 8H) ppm δ [ ¹³ C, MeOD] = 61.64; 74.33; 78.16; 78.66; 82.33 ppm B: A solution of 20.0 g of (3S, 4R) -2- (hydroxymethyl) tetrahydrofuran-3,4-diol (149.1 mmol) in 250 ml of acetone (3.40 mol, 23 equivalents) was mixed with 95 μl H ₂ SO ₄ (w (H ₂ SO ₄ ) = 98%) were added and the reaction mixture was heated to 96 ° C. for 72 hours. Then 2 spatulas of Na ₂ CO _{2 were} added and the mixture was then filtered. The neutralized reaction mixture was concentrated on a rotary evaporator until a light brown syrup remains. After adding 1 spatula of Na ₂ CO ₂ , the syrup was distilled at 160 ° C. in a high vacuum (2.0 × 10 ^-2 mbar). 19.22 g of (4aS, 7R, 7aS) -2,2-dimethyltetrahydro-4H-furo [3,2-d] [1,3] dioxin-7-ol are illuminated as a colorless solid; Yield 74%. δ [ ¹³ C, C ₃ D ₆ O] = 19.81; 29.26; 61.40; 61.60; 72.77; 75.00; 76.46; 77.27; 97.68; 109.87 ppm C: A solution, cooled to 0 ° C, of 50.015 g (0.287 mol) (4aS, 7R, 7aS) -2,2-dimethyltetrahydro-4H-furo [3,2-d] [1,3] dioxin-7-ol 60 ml of triethylamine (0.431 mol; 1.5 equivalents) were added in 200 ml of dry tetrahydrofuran and 33.7 ml of methacrylic acid chloride (0.345 mol; 1.2 equivalents) were added at 0 ° C. The reaction mixture was slowly warmed to room temperature and stirred for 72 h at room temperature. It was then neutralized by adding 0.1 molar HCl in ethanol and the precipitate formed was filtered off. The filtrate was mixed with 2 spatulas of anhydrous Na ₂ SO ₄ and concentrated on a rotary evaporator. The yellow, viscous residue was dissolved in 100 ml of diethyl ether and _{washed several times with 50 ml of deionized H 2} O in a separating funnel. The solid formed in the extraction was filtered off. The organic ether phase was filtered successively through dried silica gel and dried aluminum oxide, each time being rinsed with 50 ml of diethyl ether. The solution was then concentrated to about ¼ of its volume on a rotary evaporator at 35 ° C. and then ^{dried in a high vacuum (2.0 × 10 -2} bar) at room temperature. 48.815 g of (4aS, 7R, 7aR) -2,2-dimethyltetrahydro-4H-furo [3,2-d] [1,3] dioxin-7-yl methacrylate were obtained as a yellow oil; Yield 73.5%. δ [ ¹³ C, CD ₂ Cl ₂ ] = 18.31; 19.45; 28.82; 60.72; 72.21; 72.77; 73.77; 79.43; 97.78; 126.29; 136.41; 166.43 ppm D: Free radical polymerization and removal of the protective group leads to polymers according to the invention.

QUOTES INCLUDED IN THE DESCRIPTION

This list of the documents listed by the applicant was generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Patent literature cited

• WO 2006/117056 A1 [0004]
• WO 2014/124872 A1 [0004]

Claims (9)

Aqueous liquid detergent containing surfactant and other common ingredients of detergents and cleaning agents, the agent being a copolymer of the general formula (I),

contains, in which R ¹ and R ³ independently of one another from -H and -CH ₃ and mixtures thereof, R ² and R ⁴ independently of one another from -C (= O) O- and -C (= O) NH- and mixtures thereof , the carbonyl C atom of which is ^{bonded to the backbone carrying the radicals R 1} and R ³ and whose O or N atom, which is simply bonded to the carbonyl group, is bonded to the heterocyclic unit, R ⁵ from the group comprising H, M with M. = H, Na and / or ½ Zn, the 2-aminoethyl, benzyl, 2- (t-butylamino) ethyl, butyl, tert-butyl, 3-chloro-2-hydroxypropyl, cyclohexyl, 3,3-diethoxypropyl-, 2- (diethylamino) -ethyl-, 2- (2-butoxyethyloxy) -ethyl-, 2- (2-methoxy-polyethyloxy) -ethyl-, 2- (diisopropylamino) -ethyl, 2- (Dimethylamino) ethyl, 2-ethoxyethyl, 2-phenoxyethyl, 2-ethylhexyl, ethyl, hexyl, hydroxybutyl, 2-hydroxyethyl, 2-carboxyphenyl-hydroxypropyl, isobornyl, isobutyl, methyl, Mono-2-oxymethyl maleate, mono-2-oxyethyl succinate, 2-N-morpholinoethyl, 1-naphthyl, phenyl, propyl, 1-pyrene methyl, poly (propyleneoxy) propy 1, stearyl, 3-sulfopropyl, tetrahydrofurfuryl, tri (ethyleneoxy) ethyl, 2-carboxyethyl, 2-methyl-1-sulfino-propyl, and tris (hydroxymethyl) methyl groups and mixtures thereof, X are selected from O and NH and their mixtures, Z from OH, NH ₂ , OR ⁶ and their mixtures, and R ⁶ from aliphatic radicals with 1 to 10 carbon atoms, that the number average molecular weight of the polymer is in the range of 1,000 g / mol is up to 5,000,000 g / mol, the proportion of m in the sum of m and n in the range from 20% to 99%, the proportion of n in the sum of m and n in the range from 1% to 80% , the number average molecular weight of the poly (propyleneoxy) propyl group in the range from 250 g / mol to 600 g / mol and the number average molecular weight of the 2- (2-methoxy-polyethyloxy) -ethyl group in the range from 100 g / mol to 10,000 g / mol. Means after Claim 1 , characterized in that it contains 0.01% by weight to 10% by weight, in particular 0.1% by weight to 5% by weight, of copolymer of the general formula (I). Use of copolymers of the general formula (I),

in which R ¹ and R ³ independently of one another from -H and -CH ₃ and mixtures thereof, R ² and R ⁴ independently of one another from -C (= O) O- and -C (= O) NH- and mixtures thereof, where whose carbonyl C atom is ^{bonded to the backbone carrying the radicals R 1} and R ³ and whose O or N atom, which is simply bonded to the carbonyl group, is bonded to the heterocyclic unit, R ⁵ from the group comprising H, M with M = H , Na and / or ½ Zn, the 2-aminoethyl, benzyl, 2- (t-butylamino) ethyl, butyl, tert-butyl, 3-chloro-2-hydroxypropyl, cyclohexyl, 3, 3-diethoxypropyl-, 2- (diethylamino) -ethyl-, 2- (2-butoxyethyloxy) -ethyl-, 2- (2-methoxy-polyethyloxy) -ethyl-, 2- (diisopropylamino) -ethyl, 2- (dimethylamino ) -ethyl, 2-ethoxyethyl, 2-phenoxyethyl, 2-ethylhexyl, ethyl, hexyl, hydroxybutyl, 2-hydroxyethyl, 2-carboxyphenyl, hydroxypropyl, isobornyl, isobutyl, methyl, mono -2-oxymethyl maleate, mono-2-oxyethyl succinate, 2-N-morpholinoethyl, 1-naphthyl, phenyl, propyl, 1-pyrene methyl, poly (propyleneoxy) propyl, Ste aryl, 3-sulfopropyl, tetrahydrofurfuryl, tri (ethyleneoxy) ethyl, 2-carboxyethyl, 2-methyl-1-sulfino-propyl, and tris (hydroxymethyl) methyl group and mixtures thereof, X from O and NH and their mixtures, Z from OH, NH ₂ , OR ⁶ and their mixtures, and R ⁶ from aliphatic radicals with 1 to 10 carbon atoms, the numbers n and m are chosen so that the number average molecular weight of the polymer im Range from 1,000 g / mol to 5,000,000 g / mol, the proportion of m in the sum of m and n in the range from 20% to 99%, the proportion of n in the sum of m and n in the range from 1% to 80%, the number average molecular weight of the poly (propyleneoxy) propyl group in the range from 250 g / mol to 600 g / mol and the number average molecular weight of the 2- (2-methoxy-polyethyloxy) -ethyl group in the range from 100 g / mol to 10,000 g / mol, in aqueous liquid detergents to improve the inhibition of graying when washing flat textile structures. Means according to one of the Claims 1 to 2 or use after Claim 3 , characterized in that in the copolymers of the general formula (I) R ² and / or R ^{4 is} -C (= O) O-. Agent or use according to one of the preceding claims, characterized in that in the copolymers of the general formula (I) R ⁵ H, Na, 2- (2-butoxyethyloxy) -ethyl-, 2- (2-methoxyethyloxy) -ethyl-, 2-ethoxyethyl, 2-methoxyethyl, 2-phenoxyethyl, hydroxybutyl, 2-hydroxyethyl, 2-carboxyphenyl, hydroxypropyl, methyl, mono-2-oxymethyl maleate, mono-2-oxyethyl succinate, 2- N-morpholinoethyl, poly (propylenoxy) propyl, stearyl, 3-sulfopropyl, tetrahydrofurfuryl, tri (ethyleneoxy) ethyl, 2-carboxyethyl, 2-methyl-1-sulfino-propyl or tris (hydroxymethyl) methyl group, the number average molecular weight of the poly (propyleneoxy) propyl group being in the range from 300 g / mol to 400 g / mol. Agent or use according to one of the preceding claims, characterized in that in the copolymers of the general formula (I) Z is OH or OR ⁶ . Agent or use according to one of the preceding claims, characterized in that the number average molecular weight of the copolymers of the general formula (I) is in the range from 3,000 g / mol to 200,000 g / mol. Agent or use according to one of the preceding claims, characterized in that in the copolymers of the general formula (I) the proportion of m in the sum of m and n in the range from 25% to 90% and the proportion of n in the sum m and n ranges from 10% to 75%. Agent or use according to one of the preceding claims, characterized in that in the copolymers of the general formula (I) the parts marked with the indices m and n occur in blocks or, preferably, randomly distributed in the copolymer essential to the invention.