Synthesis of alkoxylated polymers and their having reduced dioxane formation

Abstract

The present application relates to an alkoxylated polymer consisting of (i) triethanolamine (TEA) and / or triisopropanolamine (TIPA) units and (ii) alkylene oxide units, wherein the components are selected so as to obtain a biodegradable polymer with washing power, which can be synthesized with reduced dioxane formation. The present application further relates to a cleaning composition comprising the alkoxylated polymer, the use of the inventive polymer for enhancing the primary washing power of laundry detergents, a cleaning method and the use of (i) triethanolamine (TEA) and / or triisopropanolamine, (ii) ethylene oxide (EO) and (iii) propylene oxide (PO) for the low-dioxane production of alkoxylated polymers.

Description

[0001] This application relates to an alkoxylated polymer comprising chains of (i) triethanolamine (TEA) and / or triisopropanolamine (TIPA) units and (ii) epoxide units, wherein these components are selected to obtain a biodegradable polymer with detergency, which can be synthesized with reduced dioxane formation. This application further relates to a cleaning composition comprising the alkoxylated polymer, the use of the polymer of the invention for enhancing the primary detergency of laundry detergents, a cleaning method, and the use of (i) triethanolamine (TEA) and / or triisopropanolamine, (ii) ethylene oxide (EO), and (iii) propylene oxide (PO) for the low dioxane production of the alkoxylated polymer.

[0002] In addition to the essential components of washing methods (such as surfactants and builder materials), laundry detergents typically contain other components, collectively referred to as detergent auxiliaries, and include various groups of active substances such as foam conditioners, graying inhibitors, bleaching agents, bleach activators, and dye transfer inhibitors. These auxiliaries also include substances that enhance the detergency of surfactants without necessarily possessing significant surfactant properties themselves. These substances are often referred to as detergency enhancers.

[0003] International patent application WO 2014 / 154508 A1 discloses the absorption of block copolymers formed from polyether alcohol (meth)acrylates and amino alcohol (meth)acrylates or ammonium alcohol (meth)acrylates onto textiles to facilitate the separation of stains subsequently deposited on the textiles. International patent application WO 2017 / 005793 A1 discloses that polyalkoxylated polyalkanolamines and polyalkoxylated polyalkylene imides show benefits in reducing fatty residues. However, these alkoxylated polymers are known to be difficult to biodegrade after use, and their synthesis is known to produce significant amounts of dioxane.

[0004] Therefore, there is a need for alkoxylated polymers that have good detergency, exhibit high biodegradability, and whose synthesis is associated with reduced dioxane formation.

[0005] EP 18190901 A discloses alkoxylated polymers that exhibit satisfactory washing performance and are only propoxylated. The biodegradability of these polymers is not described, but comparative tests in this application suggest that these purely propoxylated polymers have low biodegradability.

[0006] WO 2009112379 A describes detergent-active alkoxylated polymers having alkoxy chains composed of ethylene oxide and propylene oxide and an amine core containing triethanolamine (TEA). The amine cores of these polymers have a weight-average molecular weight (Mn) of 5700 to 14300. W (g / mol). For such polymers that also possess a large amine core, low biodegradability has been shown in the tests of this invention.

[0007] It has now been unexpectedly discovered that certain low molecular weight alkoxylated triethanolamine (TEA) and / or triisopropanolamine polymers with specific ratios of ethylene oxide (EO) and propylene oxide (PO) exhibit good washing properties and show significant biodegradation during their synthesis without releasing large amounts of dioxane.

[0008] The polymer is a triethanolamine (TEA) and / or triisopropanolamine alkoxylate, wherein the triethanolamine (TEA) and / or triisopropanolamine (TIPA) core has a number-average molar mass (Mn) of less than 5000 g / mol, the alkylene oxide unit chain consists of ethylene oxide (EO) and propylene oxide (PO), and the alkoxylated polymer contains between 15% and 80% EO by weight, the alkoxylated polymer has 0.5 to 10 mol of OH groups of EO / TEA and / or TIPA, the alkoxylated polymer has 2 to 25 mol of OH groups of PO / TEA and / or TIPA, and the alkoxylated polymer has a number-average molar mass (Mn) in the range of 1000 to 30000 g / mol.

[0009] As used herein, the term "alkoxylated polymer" refers to the polymers described above. Alternatively, these polymers may also be referred to as (amino-based) alkoxylates, polymeric active substances, polymers of the present invention, or polymers of the present invention.

[0010] As used equivocally herein, "triethanolamine" or "TEA" describes compounds having the following formula:

[0011]

[0012] As used equivocally herein, "triisopropanolamine" or "TIPA" describes compounds having the following formula:

[0013]

[0014] As used herein, “number-average molar mass (Mn)” or “average molar mass” refers to the molecular weight-weighted average of the molecular weights of the polymers of the present invention. Calculations are known to those skilled in the art. The number-average molar mass (Mn) is preferably determined by gel permeation chromatography (GPC), size exclusion chromatography (SEC), or light scattering. In a preferred embodiment, the number-average molar mass (Mn) is determined by gel permeation chromatography (GPC); more preferably, tetrahydrofuran (THF) is used as the solvent, and the system is calibrated with linear polystyrene standards in the molar mass range of 682-2,520,000 g / mol.

[0015] In a preferred embodiment, the triethanolamine (TEA) and / or triisopropanolamine (TIPA) core is a pure triethanolamine (TEA) core, and the resulting polymer is a TEA alkoxylate. In a further preferred embodiment, the TEA core consists of no more than 10 TEA units, no more than 7 TEA units, no more than 5 TEA units, no more than 3 TEA units, and, in the most preferred form, one TEA unit.

[0016] As used equivalencely herein, “ethylene oxide” or “EO” describes compounds having the following formula:

[0017]

[0018] As used equivalently herein, "propylene oxide" or "PO" describes compounds having the following formula:

[0019]

[0020] The alkoxylation of triethanolamine (TEA) and / or triisopropanolamine (TIPA) units is a static reaction that does not produce a homogeneous final product, but rather yields a certain amount of very similar but slightly different polymers. Therefore, the figures used for size and ratio should be considered statically, i.e., the indicated amount or ratio is most common in a certain amount of the polymers of the present invention, but different amounts and ratios may also exist, albeit less frequently. For the bonding of the alkylene oxide chain to triethanolamine (TEA) and / or triisopropanolamine (TIPA) (each of which has three OH groups and one tertiary amine), this means that at least 70%, at least 80%, at least 90%, at least 95%, or at least 99% of the available OH groups have reacted with the alkylene oxide. In this context, "available" OH groups mean OH groups that remain after the synthesis of the triethanolamine (TEA) and / or triisopropanolamine (TIPA) core and have not been converted in this step. For example, if the TEA or TIPA core consists of only a single unit, the number of available OH groups is 3. The bond formed here is an ether bond.

[0021] The reaction at the tertiary amine should also be considered statically, as the probability of this reaction is very low. For the alkyl oxide chain bonded via a tertiary amine to triethanolamine (TEA) and / or triisopropanolamine (TIPA), this means that no more than 10%, 8%, 6%, 4%, 2%, 1%, 0.5%, or 0.1% of the amine groups have reacted with the alkyl oxide. The bond formed here is an amide bond.

[0022] Furthermore, the length / composition of individual alkyl oxide chains is also a static process. The figures here describe the starting amount and the maximum probability of that amount being present in a given quantity of the polymer of the present invention. For example, in the case of alkoxylation with 5 mol of EO / OH groups, most of the alkyl oxide chains in the polymer will have ethylene oxide units of a certain length. However, the resulting polymer will be non-uniform, and therefore may also contain alkyl oxide chains with 4 EO, 3 EO, 2 EO, 1 EO, or even unconverted OH groups in smaller numbers. Similarly, alkyl oxide chains with 7 EO, 8 EO, etc. (with decreasing probabilities) will also be present. Individual alkyl oxide units are linked to each other by ether bonds.

[0023] In preferred embodiments, the polymers of the present invention relate to variants in which the triethanolamine (TEA) and / or triisopropanolamine (TIPA) units have a number-average molar mass (Mn) of less than 3000 g / mol, preferably less than 1500 g / mol. In further preferred embodiments of the invention, the number-average molar mass (Mn) of the triethanolamine (TEA) and / or triisopropanolamine (TIPA) units is between 149 and 1300 g / mol, and even more preferably between 149 and 680 g / mol.

[0024] This application relates to one of the aforementioned polymers, wherein the alkoxylated polymer contains EO in the range of 15% to 80% by weight, preferably in the range of 19% to 60% by weight. More preferably, the polymer contains EO in the range of 20% to 45% by weight, more preferably in the range of 21% to 35% by weight.

[0025] This application further relates to one of the aforementioned polymers, wherein the alkoxylated polymer has 2 to 7 mol, preferably 3 to 6 mol, of EO / triethanolamine (TEA) and / or triisopropanolamine (TIPA) OH groups. More preferably, the polymer of the present invention contains 4 to 5 mol of EO / triethanolamine (TEA) and / or triisopropanolamine (TIPA), particularly triethanolamine (TEA) OH groups.

[0026] In a preferred embodiment, the alkoxylated polymer has 5 to 20 mol, preferably 7 to 15 mol, of PO / triethanolamine (TEA) and / or triisopropanolamine (TIPA), more preferably OH groups of triethanolamine (TEA).

[0027] In a preferred embodiment, the alkoxylation step is first performed with ethylene oxide (EO), and then with propylene oxide (PO).

[0028] Furthermore, in a preferred embodiment, the alkoxylated polymer has a number-average molar mass (Mn) in the range of 1300 to 6000 g / mol, preferably 1400 to 4500 g / mol.

[0029] In a further preferred embodiment, the polymer of the present invention has a single triethanolamine (TEA) or triisopropanolamine (TIPA) unit, more preferably a triethanolamine (TEA) unit, wherein the alkoxylated polymer contains EO in the range of 15% to 80%, 16% to 75%, 17% to 70%, 18% to 65%, or 19% to 60% by weight, wherein the alkoxylated polymer has 2 to 7 mol, 3 to 6 mol, or 4 to 5 mol of EO / triethanolamine (TEA) or triisopropanolamine (TIPA) unit OH groups, and wherein the alkoxylated polymer has 5 to 15 mol or 6 to 14 mol of PO / triethanolamine (TEA) or triisopropanolamine (TIPA) unit OH groups.

[0030] Those skilled in the art will understand that the polymer of the present invention may contain other components, such as reactants, in amounts of up to 3% by weight, up to 2% by weight, up to 1% by weight, up to 0.5% by weight, up to 0.3% by weight, or up to 0.1% by weight.

[0031] The present invention further provides a method, particularly for removing surfactant-sensitive or enzyme-sensitive stains from textiles, wherein a laundry detergent and a polymeric active substance, as specified, are brought into contact with the soiled textiles, particularly in an aqueous and surfactant-containing washing solution. This method can be carried out manually or by machine, for example, using a household washing machine. Here, a liquid composition and a polymeric active substance can be used simultaneously or sequentially. Simultaneous use can be particularly advantageously achieved by using a laundry detergent containing a polymeric active substance. Surfactant-sensitive or enzyme-sensitive stains refer to those typically at least partially removable by surfactants or by means of enzymes, such as oils, fats (e.g., animal fats, such as tallow and lard (pork fat)), cosmetics, or stains from grass, chocolate mousse, or eggs. The polymers used according to the invention contribute to the removability of such stains even in the absence of enzymes or, particularly, in the absence of bleach.

[0032] The cleaning compositions of the present invention, their use in washing according to the invention, and the methods of the invention are preferably carried out by adding a polymer composed of (mono)amino-based alkoxylates to a composition that does not contain the corresponding polymer or to a washing liquid containing a composition that does not contain the corresponding polymer, wherein the amount of the added polymer is preferably in the range of 0.01% to 20% by weight, particularly 1% to 15% by weight, based on the total weight of the composition that does not contain the corresponding polymer. Particularly preferably, the polymer essential to the invention is used with liquid laundry detergents, specifically liquid laundry detergents having a surfactant concentration in the range of at least 30% by weight, preferably 30% to 65% by weight, and particularly 50% to 58% by weight, based on the total weight of the composition. Preferably, the washing liquid is produced by adding 7 ml to 100 ml, particularly 10 ml to 75 ml, preferably 20 ml to 50 ml of liquid aqueous laundry detergent to 12 liters to 60 liters, particularly 15 liters to 20 liters of water.

[0033] The polymers essential to this invention can be obtained by methods known in principle. Here, the starting molecules TEA and / or TIPA are reacted with ethylene oxide (EO) and propylene oxide (PO) under basic catalysis.

[0034] The starting molecules are provided and dehydrated. Subsequently, epoxides are added in the desired order and amount under basic catalysis, such as using KOH.

[0035] Suitable procedures and reaction conditions for alkoxylation are generally known to those skilled in the art and are described, for example, in the standard work M. Ionescu, "Chemistry and technology of polyols for polyurethanes", Rapra Technology, Shrewsbury, UK, page 60 and following pages.

[0036] In the context of the uses and methods of the present invention, it is preferred that the concentration of the polymer as defined above in an aqueous detergent solution, such as in a washing machine and also in hand washing, is from 0.001 g / L to 5 g / L, particularly from 0.01 g / L to 2 g / L. The methods and uses of the present invention preferably relate to operation at temperatures ranging from 10°C to 95°C, particularly from 20°C to 40°C. The methods and uses of the present invention are preferably carried out at pH values ​​ranging from pH 5 to pH 12, particularly from pH 7 to pH 11.

[0037] In connection with the cleaning compositions of the present invention, their use in washing according to the invention, or the methods of the invention, laundry detergents, in addition to polymers, and which may be in particular in the form of powdered solids, recompacted granules, or solutions or suspensions, may contain all the ingredients known and customarily used in such compositions. The compositions may particularly contain builder substances, surfactants, water-miscible organic solvents, enzymes, multivalent chelating agents, electrolytes, pH adjusters, polymers with specific effects such as stain-removing polymers, dye transfer inhibitors, graying inhibitors, wrinkle-reducing and shape-retaining polymers, and additional auxiliaries such as optical brighteners, foam conditioners, dyes, and fragrances.

[0038] The composition may contain one or more surfactants, and the surfactants that can be used are in particular anionic surfactants, nonionic surfactants and mixtures thereof, but cationic and / or amphoteric surfactants may also be present.

[0039] The nonionic surfactant used can be any nonionic surfactant known to those skilled in the art. The nonionic surfactant used is preferably an alkoxylated, advantageously ethoxylated (especially primary) alcohol, which preferably has 8 to 18 carbon atoms and an average of 1 to 12 mol ethylene oxide (EO) / mol alcohol, wherein the alcohol group can be straight-chain or preferably 2-methyl-branched, or can contain a mixture of straight-chain and methyl-branched groups, as is typically found in carbonyl synthetic alcohols. However, in particular, alcohol ethoxylates are preferred, having a straight-chain group from a naturally sourced alcohol having 12 to 18 carbon atoms (e.g., from coconut alcohol, palm alcohol, tallow alcohol, or oleyl alcohol), and an average of 2 to 8 mol EO / mol alcohol. Preferred ethoxylated alcohols include, for example, C having 3 or 4 EO atoms. 12-14 Alcohols, C with 7 EO atoms 9-11 Alcohols, C with 3, 5, 7, or 8 EO atoms 13-15 Alcohols, C with 3, 5, or 7 EO atoms 12-18Alcohols and mixtures thereof, such as C with 3 EO atoms. 12-14 Alcohols and C with 5 EOs 12-18 A mixture of alcohols. The ethoxylation level is a statistical average of possible integers or fractions for a particular product. Preferred alcohol ethoxylates have a narrow homologue distribution (narrow range ethoxylate, NRE).

[0040] For these nonionic surfactants, alternatively or additionally, fatty alcohols having more than 12 EOs can also be used. Examples of these are tallow fatty alcohols having 14, 25, 30, or 40 EOs. Other nonionic surfactants that can be used are those with the general formula R 5 O(G) x Alkyl glycosides, of which R 5 This corresponds to a primary aliphatic group having 8 to 22, preferably 12 to 18, carbon atoms, either straight-chain or methyl-branched, especially 2-methyl-branched, and G is a symbol for a monosaccharide unit having 5 or 6 carbon atoms, preferably glucose. The degree of oligomerization x, indicating the distribution of monosaccharides and oligosaccharides, is any desired number between 1 and 10; preferably, x is 1.2 to 1.4.

[0041] Preferred nonionic surfactants, used as the sole nonionic surfactant or in combination with other nonionic surfactants, are alkoxylated, preferably ethoxylated, or ethoxylated and propoxylated fatty acid alkyl esters, which preferably have 1 to 4 carbon atoms in the alkyl chain.

[0042] Nonionic surfactants of the amine oxide type, such as N-cocoalkyl-N,N-dimethylamine oxide and N-tallow alkyl-N,N-dihydroxyethylamine oxide, as well as fatty acid alkanolamines, can also be used. The amount of these nonionic surfactants preferably does not exceed the amount of the ethoxylated fatty alcohol, especially not more than half of it.

[0043] Another suitable surfactant is a polyhydroxy fatty acid amide having the following formula.

[0044] ,

[0045] Where R is an aliphatic acyl group having 6 to 22 carbon atoms, R 1 [Z] is hydrogen, an alkyl or hydroxyalkyl group having 1 to 4 carbon atoms, and [Z] is a straight-chain or branched polyhydroxyalkyl group having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups. Polyhydroxy fatty acid amides are known substances that can typically be obtained by reductive amination of reducing sugars with ammonia, alkylamines, or alkanolamines, followed by acylation with fatty acids, fatty acid alkyl esters, or fatty acid acyl chlorides. The groups of polyhydroxy fatty acid amides also include compounds having the following formula.

[0046] ,

[0047] Where R is a straight-chain or branched alkyl or alkenyl group having 7 to 12 carbon atoms, R 1 It is a straight-chain, branched, or cyclic alkyl or aryl group having 2 to 8 carbon atoms, and R 2 It is a straight-chain, branched, or cyclic alkyl, aryl, or oxyalkyl group having 1 to 8 carbon atoms, wherein C 1-4 -alkyl or phenyl is preferred, and [Z] is a straight-chain polyhydroxyalkyl group whose alkyl chain is substituted with at least two hydroxyl groups, or an alkoxylated, preferably ethoxylated or propoxylated derivative of that group. [Z] is preferably obtained by reductive amination of reducing sugars (e.g., glucose, fructose, maltose, lactose, galactose, mannose or xylose). N-alkoxy- or N-aryloxy-substituted compounds can be converted into the desired polyhydroxy fatty acid amides by reacting with fatty acid methyl esters in the presence of an alkoxide as a catalyst.

[0048] The anionic surfactants used are, for example, those of the sulfonate and sulfate types. Here, a suitable sulfonate type surfactant is preferably C... 9-13 -alkylbenzene sulfonates, olefin sulfonates (i.e., mixtures of olefin sulfonates and hydroxyalkane sulfonates), and also disulfonates, such as those composed of C atoms having terminal or internal double bonds. 12-18 - Monoolefins are obtained by sulfonation with gaseous sulfur trioxide followed by basic or acidic hydrolysis of the sulfonation product. Also suitable are those obtained from C 12-18 Alkanes, for example, are alkane sulfonates obtained by chlorosulfonation or sulfonation oxidation followed by hydrolysis and / or neutralization. Also suitable are esters (ester sulfonates) of α-sulfonated fatty acids, such as α-sulfonated methyl esters of hydrogenated coconut oil fatty acids, palm kernel fatty acids, or tallow fatty acids.

[0049] Another suitable anionic surfactant is sulfated fatty acid glycerides. Fatty acid glycerides refer to monoesters, diesters, and triesters, and mixtures thereof, obtained in preparation by esterification of glycerol with 1 to 3 mol of fatty acid or by transesterification of triglycerides with 0.3 to 2 mol of glycerol. Here, preferred sulfated fatty acid glycerides are sulfated products of saturated fatty acids having 6 to 22 carbon atoms, such as hexanoic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid, or benzyl acid.

[0050] Also suitable are alkyl sulfates having the following general formula

[0051] RO-SO3M

[0052] Wherein R is a straight-chain, branched, or cyclic saturated hydrocarbon group having 12 to 18, particularly 12 to 14, carbon atoms, and M is a counter cation that causes charge neutralization of the sulfate monoester, particularly a sodium or potassium ion or an ammonium ion having the following general formula.

[0053] R 1 R 2 R 3 R 4 N +

[0054] Where R 1 R 2 R 3 and R 4 Independently, it is hydrogen, an alkyl group having 1 to 4 carbon atoms, or a hydroxyalkyl group having 2 to 3 carbon atoms. Preferred groups R are derived from natural C. 12 -C 18 Fatty alcohols, such as those derived from coconut fat alcohol, tallow fat alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, or stearyl alcohol, or those derived from C 10 -C 20 Carbonyl alcohols or secondary alcohols having these chain lengths are preferred. Furthermore, alkyl sulfates with specified chain lengths are preferred, containing synthetic straight-chain alkyl groups prepared from petrochemical products and exhibiting degradation behavior similar to suitable compounds based on oleochemical raw materials. C4 is particularly preferred. 12 -C 16 -Alkyl sulfates and C 12 -C 14 -Alkyl sulfate.

[0055] Also suitable are straight-chain or branched C atoms that have been ethoxylated with 1 to 6 mol of ethylene oxide. 7-21 - Alcohols, such as 2-methyl-branched C-chains with an average of 3.5 mol of ethylene oxide (EO). 9-11 - Alcohols or C-type compounds with 1 to 4 EO atoms 12-18 - Sulfated monoesters of fatty alcohols.

[0056] Another suitable anionic surfactant is the salt of alkyl sulfosuccinic acid, also known as sulfosuccinates or sulfosuccinic acid esters, and is a monoester and / or diester of sulfosuccinic acid with an alcohol, preferably a fatty alcohol, and especially an ethoxylated fatty alcohol. Preferred sulfosuccinates contain C 8-18Fatty alcohol groups or mixtures thereof. Particularly preferred sulfosuccinates contain fatty alcohol groups derived from ethoxylated fatty alcohols that themselves constitute nonionic surfactants. Sulfosuccinates in particular are those whose fatty alcohol groups are derived from ethoxylated fatty alcohols having a narrow homologue distribution. Alkyl succinic acids or their salts, preferably having 8 to 18 carbon atoms in the alkyl (olefin) chain, can also be used.

[0057] Other anionic surfactants available are soaps. Saturated fatty acid soaps are suitable, such as salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid, and benzyl acid, and especially soap blends derived from natural fatty acids such as coconut oil fatty acids, palm kernel fatty acids, or tallow fatty acids.

[0058] Anionic surfactants (including soaps) can be in the form of their sodium, potassium, or ammonium salts, or as soluble salts of organic bases (such as monoethanolamine, diethanolamine, or triethanolamine). Anionic surfactants are preferably in the form of their sodium or potassium salts, especially sodium salts.

[0059] Instead of the surfactants mentioned or in combination with them, cationic and / or amphoteric surfactants may also be used.

[0060] Examples of cationic active substances that can be used include cationic compounds having the following formula:

[0061]

[0062]

[0063] ,

[0064] Each R 1 The groups are independently selected from C 1-6 -alkyl, -alkenyl, or -hydroxyalkyl; each group R 2 Selected independently from C 8-28 -alkyl or -alkene; R 3 = R 1 Or (CH2) n -TR 2 ;R 4 = R 1 Or R 2 Or (CH2) n -TR 2 T = -CH2-, -O-CO, or -CO-O- and n is an integer from 0 to 5.

[0065] These surfactants are preferably present in the laundry detergent at an amount of 5% to 65% by weight. As mentioned above, particularly preferred laundry detergents are liquids and have a surfactant content in the range of at least 30% by weight, preferably 30% to 60% by weight, and especially 50% to 58% by weight. Such concentrated liquid laundry detergents are advantageous because they are associated with lower resource utilization—particularly due to reduced transport weight and dosage—meaning that smaller bottle sizes and thus less packaging material are required to achieve the same performance compared to, for example, less concentrated compositions. Furthermore, consumers prefer such highly concentrated compositions because they take up less storage space at home.

[0066] Textile softening compounds can be used to care for textiles and improve their properties, such as a softer "hand feel" (finish) and reduced static charge (increased wearing comfort). The active ingredients in these formulations are quaternary ammonium compounds with two hydrophobic groups, such as distearatedimethylammonium chloride. However, these quaternary ammonium compounds are gradually being replaced by quaternary ammonium compounds that include ester groups in their hydrophobic groups as intended breakpoints for biodegradation due to their insufficient biodegradability.

[0067] Such "ester quaternary ammonium salts" with improved biodegradability can be obtained, for example, by esterifying a mixture of methyldiethanolamine and / or triethanolamine with fatty acids and then quaternizing the reaction product with an alkylating agent in a known manner. A suitable finishing agent is dihydroxymethyl ethylidene urea.

[0068] Laundry detergents preferably contain at least one water-soluble and / or water-insoluble organic and / or inorganic builder. Water-soluble organic builder substances include polycarboxylic acids, especially citric acid and gluconic acid; monomers and polymeric aminopolycarboxylic acids, especially methylglycine diacetic acid, hypozinotriacetic acid, and ethylenediaminetetraacetic acid; as well as polyaspartic acid; polyphosphonic acids, especially aminotris(methylenephosphonic acid), ethylenediaminetetra(methylenephosphonic acid), and 1-hydroxyethane-1,1-diphosphonic acid; polymeric hydroxy compounds such as dextrin and polymeric (poly)carboxylic acids, especially polycarboxylates obtainable by oxidation of polysaccharides / dextrin; and / or polymeric acrylic acid, methacrylic acid, maleic acid, and copolymers thereof. It may also contain a small amount of polymerizable material without carboxylic acid functional groups in copolymer form. The relative molecular mass of homopolymers of unsaturated carboxylic acids is typically between 5,000 g / mol and 200,000 g / mol, and the relative molecular mass of copolymers is between 2,000 g / mol and 200,000 g / mol, preferably between 50,000 g / mol and 120,000 g / mol, in each case based on the free acid. Particularly preferred acrylic-maleic acid copolymers have a relative molecular mass of 50,000 g / mol to 100,000 g / mol. Suitable but less preferred compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers (such as vinyl methyl ether), vinyl esters, ethylene, propylene, and styrene, wherein the acid content is at least 50% by weight. Water-soluble organic building blocks that can be used also include terpolymers comprising two unsaturated acids and / or their salts as monomers and vinyl alcohol and / or esterified vinyl alcohol or carbohydrates as a third monomer. The first acidic monomer or its salt is derived from a mono-olefinically unsaturated C3-C8 carboxylic acid, and preferably a C3-C4 monocarboxylic acid, particularly (meth)acrylic acid. The second acidic monomer or its salt may be a C4-C8 dicarboxylic acid, particularly preferably a derivative of maleic acid, and / or an allyl sulfonic acid derivative with an alkyl or aryl substituted group at the 2-position. Such polymers typically have a relative molecular mass between 1,000 g / mol and 200,000 g / mol. Further preferred copolymers are those comprising acrolein and acrylic acid / acrylate or vinyl acetate as monomers. Organic detergent building materials can be particularly used to produce liquid compositions in the form of an aqueous solution, preferably in the form of a 30 to 50% by weight aqueous solution. All the acids mentioned are generally used in the form of their water-soluble salts, particularly their alkali metal salts.

[0069] If desired, such organic building blocks may be present in amounts up to 40% by weight, particularly up to 25% by weight, and preferably from 0.5% to 8% by weight. Amounts in the upper half of the mentioned range are preferably used in paste or liquid compositions, particularly aqueous compositions.

[0070] Available water-soluble inorganic building blocks particularly include polymeric alkali metal phosphates, which may be in the form of their basic, neutral, or acidic sodium or potassium salts. Examples of these are tetrasodium diphosphate, disodium dihydrogen phosphate, pentasodium triphosphate (so-called sodium hexametaphosphate), and their corresponding potassium salts, as well as mixtures of sodium and potassium salts. Water-insoluble, water-dispersible inorganic building blocks used are particularly crystalline or amorphous alkali metal aluminosilicates, in an amount up to 50% by weight, preferably not exceeding 40% by weight, and particularly 1% to 5% by weight in liquid compositions. Among these, detergent-quality crystalline sodium aluminosilicates are preferred, particularly zeolites A, P, and optionally X. Amounts close to the mentioned upper limits are preferably used in solid particulate compositions. Suitable aluminosilicates particularly do not have particles larger than 30 µm and preferably consist of particles smaller than 10 µm in at least 80% by weight. Their calcium-binding capacity is typically in the range of 100 mg to 200 mg of CaO / g.

[0071] Suitable alternatives or partial alternatives to the aluminosilicates mentioned are crystalline alkali metal silicates, which may exist alone or in mixtures with amorphous silicates. Alkali metal silicates suitable for use as detergent builders preferably have a molar ratio of alkali metal oxide to SiO2 of less than 0.95, particularly 1:1.1 to 1:12, and may be amorphous or crystalline. Preferred alkali metal silicates are sodium silicates, particularly amorphous sodium silicates, having a Na2O:SiO2 molar ratio of 1:2 to 1:2.8. The crystalline silicates used (which may exist alone or in mixtures with amorphous silicates) are preferably those with the general formula Na2Si. x O 2x+1 . crystalline folin silicates of yH2O, wherein x, referred to as the coefficient, is a number from 1.9 to 4 and y is a number from 0 to 20, and the preferred value of x is 2, 3, or 4. Preferred crystalline folin silicates are those in the general formula mentioned herein where x takes the value of 2 or 3. In particular, both β- and d-disilicates (Na2Si2O5) are preferred. .(y H2O). Alternatively, nearly anhydrous crystalline alkali metal silicates having the above general formula can be used—where x is a number from 1.9 to 2.1—produced from amorphous alkali metal silicates. In another preferred embodiment, crystalline sodium aluminosilicates having a coefficient of 2 to 3 are used, such as those produced from sand and sodium carbonate. In another preferred embodiment, crystalline sodium silicate having a coefficient in the range of 1.9 to 3.5 is used. In a preferred configuration, granular compounds formed from alkali metal silicates and alkali metal carbonates are used, such as those commercially available under the name Nabion® 15. If alkali metal aluminosilicates, particularly zeolites, are also present as additional detergent building materials, the weight ratio of aluminosilicate to silicate is preferably 1:10 to 10:1, in each case based on the anhydrous active material. In a composition comprising both amorphous and crystalline alkali metal silicates, the weight ratio of amorphous alkali metal silicate to crystalline alkali metal silicate is preferably 1:2 to 2:1, and particularly 1:1 to 2:1.

[0072] The detergent additive is preferably present in the laundry detergent in an amount of up to 60% by weight, particularly from 0.5% to 40% by weight.

[0073] In a preferred configuration, the composition comprises a water-soluble builder block. Here, the term "builder block" is used to indicate that the composition does not contain any additional builder substances other than those that are water-soluble; this means that all builder substances present in the composition are encompassed within this "block," which excludes at most amounts of substances that may be present in small quantities commercially as impurities or stabilizing additives in the remaining components of the composition. The term "water-soluble" should be understood to mean that the builder block dissolves without residue at a concentration produced under typical conditions due to the amount of the composition containing it used. Preferably, at least 15% and up to 55% by weight, particularly 25% to 50% by weight, of the water-soluble builder block are present in the composition. This water-soluble builder block preferably consists of the following components:

[0074] a) 5% to 35% by weight of citric acid, alkali metal citrate and / or alkali metal carbonate (which may also be at least partially replaced by alkali metal bicarbonate).

[0075] b) Up to 10% by weight of alkali metal silicates having a coefficient in the range of 1.8 to 2.5.

[0076] c) Up to 2% by weight of phosphonic acids and / or alkali metal phosphonates

[0077] d) Up to 50% by weight of alkali metal phosphates, and

[0078] e) Up to 10% by weight of polymeric polycarboxylate,

[0079] The amounts mentioned are based on total laundry detergent. Unless otherwise explicitly stated, this also applies to all amounts described below.

[0080] In a preferred embodiment, the water-soluble builder portion comprises at least two of components b), c), d), and e) in an amount greater than 0% by weight.

[0081] Regarding component a), in a preferred embodiment, it contains 15% to 25% by weight of an alkali metal carbonate (which may be at least partially replaced by an alkali metal bicarbonate), and up to 5% by weight, particularly 0.5% to 2.5% by weight of citric acid and / or alkali metal citrate. In an alternative embodiment, component a) comprises 5% to 25% by weight, particularly 5% to 15% by weight of citric acid and / or alkali metal citrate, and up to 5% by weight, particularly 1% to 5% by weight of an alkali metal carbonate (which may be at least partially replaced by an alkali metal bicarbonate). If both alkali metal carbonate and alkali metal bicarbonate are present, component a) preferably comprises alkali metal carbonate and alkali metal bicarbonate in a weight ratio of 10:1 to 1:1.

[0082] Regarding component b), in a preferred embodiment, there is 1% to 5% by weight of an alkali metal silicate having a coefficient in the range of 1.8 to 2.5.

[0083] Regarding component c), in a preferred embodiment, 0.05% to 1% by weight of phosphonic acid and / or alkali metal phosphonate are present. Phosphonic acid here is also considered to refer to optionally substituted alkylphosphonic acids, which may also comprise two or more phosphonic acid moieties (referred to as polyphosphonic acids). These are preferably selected from hydroxy and / or aminoalkylphosphonic acids and / or their alkali metal salts, such as dimethylaminomethane diphosphonic acid, 3-aminopropane-1-hydroxy-1,1-diphosphonic acid, 1-amino-1-phenylmethane diphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid, aminotris (methylenephosphonic acid), N,N,N',N'-ethylenediaminetetra(methylenephosphonic acid), and acylated derivatives of phosphorous acid, which may also be used in any desired mixture.

[0084] Regarding component d), in a preferred embodiment, there is 15% to 35% by weight of an alkali metal phosphate, particularly trisodium polyphosphate. Here, "alkali metal phosphate" is a collective term for alkali metal (especially sodium and potassium) salts of various phosphoric acids, which, in addition to those with higher molecular weights, can also be distinguished as metaphosphoric acid (HPO3).n Combined with orthophosphoric acid (H3PO4), phosphates offer many advantages: they act as alkali carriers, preventing scale buildup on machine parts or fabrics, and also contribute to cleaning performance. Sodium dihydrogen phosphate (NaH2PO4) acts as a dihydrate (density 1.91 g / cm³). -3 (melting point 60°) and as a monohydrate (density 2.04 g / cm³) -3 Both salts are white powders, highly soluble in water, and lose their water of crystallization upon heating, transforming into a weakly acidic diphosphate (disodium hydrogen diphosphate, Na₂H₂P₂O₇) at 200°C, and into sodium trimetaphosphate (Na₃P₃O₉) and Maddrell's salt at even higher temperatures. NaH₂PO₄ is acidic; it forms when phosphoric acid is adjusted to a pH of 4.5 with sodium hydroxide solution and then sprayed into a slurry. Potassium dihydrogen phosphate (KDP) is a primary or monobasic potassium phosphate (KDP) with a concentration of 2.33 g / cm³. -3 A white salt with a density of [insert density here], it has a melting point of 253°C (decomposes to form [insert KPO3]). x Sodium hydrogen phosphate (Na₂HPO₄) is a colorless, highly water-soluble crystalline salt, readily soluble in water. It exists anhydrously and in a solution with a density of 2 mol / L (density 2.066 g / cm³). It is potassium polyphosphate and readily soluble in water. -3 (Loss of water at 95°C), 7 mol (density 1.68 g / cm³) -3 Melting point 48°C, accompanied by the loss of 5 H₂O) and 12 mol of water (density 1.52 g / cm³). -3 It exists in the presence of 5% hydrogen phosphate (with a melting point of 35°C, accompanied by the loss of 5% H₂O), becomes anhydrous at 100°C, and transforms into diphosphate Na₄P₂O₇ upon stronger heating. Disodium hydrogen phosphate is prepared by neutralizing phosphoric acid with sodium carbonate solution using phenolphthalein as an indicator. Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate) K₂HPO₄ is an amorphous white salt readily soluble in water. Trisodium phosphate (tert-phosphate) Na₃PO₄ is a colorless crystal with a dodecahydrate concentration of 1.62 g / cm³. -3 It has a density and a melting point of 73°C-76°C (decomposition), as a decahydrate (corresponding to 19%-20% P2O5) it has a melting point of 100°C, and in its anhydrous form (corresponding to 39%-40% P2O5) it has a density of 2.536 g / cm³. -3The density of trisodium phosphate is 2.56 g / cm³. Trisodium phosphate is readily soluble in water under alkaline conditions and is prepared by evaporating and concentrating exactly 1 mol of disodium phosphate and 1 mol of NaOH solution. Tripotassium phosphate (tert- or ternary potassium phosphate) K₃PO₄ has a density of 2.56 g / cm³. -3 It is a white, hygroscopic granular powder with a density of 2.534 g / cm³, a melting point of 1340°C, and readily soluble in water under alkaline conditions. It is formed, for example, by heating Thomas slag with charcoal and potassium sulfate. Although more expensive, more soluble, and therefore highly efficient, potassium phosphate is generally preferred over corresponding sodium compounds. Tetrasodium diphosphate (sodium pyrophosphate) Na₄P₂O₇ in anhydrous form (density 2.534 g / cm³). -3 It exists as a decahydrate (with a melting point of 988°C, also stated as 880°C) and as a decahydrate (density 1.815-1.836 g / cm³). -3 It exists as a colorless crystal (melting point 94°C, accompanied by the loss of water). Both substances are soluble in water under alkaline conditions. Na4P2O7 is formed by heating disodium phosphate to >200°C or by reacting phosphoric acid with sodium carbonate in a stoichiometric ratio and then dehydrating the solution by spraying. The decahydrate complexes with heavy metal salts and hardness-forming agents, thus reducing the hardness of water. Potassium diphosphate (potassium pyrophosphate) K4P2O7 exists as a trihydrate and has a hardness of 2.33 g / cm³. -3 A colorless, hygroscopic powder of low density, soluble in water, with a pH of 10.4 for a 1% solution at 25°C. The condensation of NaH₂PO₄ or KH₂PO₄ forms higher molecular weight sodium phosphate and potassium phosphate, which can be distinguished as cyclic representatives—sodium metaphosphate and potassium metaphosphate—and chain types—sodium polyphosphate and potassium polyphosphate. Especially for the latter, numerous names are used: molten or calcined phosphates, Graham's salts, Kurrol's salts, and Madrel's salts. All higher sodium phosphates and potassium phosphates are collectively referred to as condensed phosphates. Industrially important is pentasodium triphosphate (Na₅P₃O₄). 10 Sodium tripolyphosphate (NaO-[P(O)(ONa)-O]) is a compound with the general formula NaO-[P(O)(ONa)-O]. n -Na is a non-hygroscopic white, water-soluble salt—where n = 3—that is anhydrous or crystallizes in 6H₂O. At room temperature, about 17 g of the anhydrous salt dissolves in 100 g of water, about 20 g at 60°C, and about 32 g at 100°C; after heating the solution to 100°C for two hours, hydrolysis forms about 8% orthophosphate and 15% diphosphate. In the preparation of pentaphosphate, phosphoric acid is reacted stoichiometrically with sodium carbonate or sodium hydroxide solution and the solution is dehydrated by spraying. Similar to Graem's salts and sodium diphosphate, pentaphosphate dissolves many insoluble metal compounds (including calcium soaps, etc.). Pentapotassium triphosphate (K₅P₃O₃)10 Potassium tripolyphosphate is commercially available, for example, as a 50% solution by weight (>23% P₂O₅, 25% K₂O). Sodium potassium tripolyphosphate is also available, and is similarly usable in the context of this invention. These are formed, for example, during the hydrolysis of sodium tripolyphosphate with KOH.

[0085] (NaPO3)3 + 2 KOH → Na3K2P3O 10 + H2O

[0086] These are available as sodium tripolyphosphate, potassium tripolyphosphate, or a mixture 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, potassium tripolyphosphate, and sodium potassium tripolyphosphate are also available.

[0087] Regarding component e), in a preferred embodiment of the composition, there is 1.5% to 5% by weight of a polymeric polycarboxylate, which is particularly selected from polymers or copolymers of acrylic acid, methacrylic acid, and / or maleic acid. Among these, homopolymers of acrylic acid are particularly preferred, and among these, those having an average molar mass in the range of 5000 D to 15000 D (PA standard) are preferred.

[0088] Enzymes that can be used in the composition include those from the following classes: proteases, lipases, keratins, amylases, amylopectinases, mannanases, cellulases, hemicellulases, xylanases, and peroxidases, as well as mixtures thereof, such as amylases like Termamyl®, Amylase-LT®, Maxamyl®, Duramyl®, and / or Purafect® OxAm, lipases like Lipolase®, Lipomax®, Lumafast®, Lipozym®, and / or Lipex®, and cellulases like Celluzyme® and / or Carezyme®. In the case of proteases, Bacillus subtilis protease (EC 3.4.21.62) is particularly preferred. Enzymatically active substances derived from fungi or bacteria such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus, Humicola lanuginosa, Humicola insolens, Pseudomonas asseudoalcaligenes, or Pseudomonas cepacia are particularly suitable. Any enzymes used can be adsorbed onto a carrier material and / or embedded in a coating material to protect them from premature inactivation. They are preferably present in the laundry detergent in an amount of up to 10% by weight, particularly from 0.2% to 2% by weight.

[0089] In a preferred embodiment, the composition comprises 5% to 65% by weight, particularly 8% to 55% by weight, of anionic and / or nonionic surfactants, up to 60% by weight, particularly 0.5% to 40% by weight, of a building agent, and 0.2% to 5% by weight of an enzyme selected from proteases, lipases, keratins, amylases, amylopectinases, mannanases, cellulases, oxidases, and peroxidases and mixtures thereof.

[0090] Organic solvents that can be used in laundry detergents (especially when these detergents are in liquid or paste form) include alcohols having 1 to 4 carbon atoms (especially methanol, ethanol, isopropanol, and tert-butanol), diols having 2 to 4 carbon atoms (especially ethylene glycol and propylene glycol), mixtures thereof, and ethers derived from the mentioned classes of compounds. These water-miscible solvents are preferably present in the composition in an amount not exceeding 30% by weight, particularly 6% to 20% by weight.

[0091] Examples of naturally sourced polymers that can be used as thickeners in aqueous liquid compositions include agar, carrageenan, tragacanth, gum arabic, alginate, pectin, polysaccharides, guar gum powder, carob seed powder, starch, dextrin, gelatin and casein, cellulose derivatives such as carboxymethyl cellulose, hydroxyethyl cellulose and hydroxypropyl cellulose, and polymeric polysaccharide thickeners such as xanthan gum; in addition to these, fully synthetic polymers such as polyacrylic acid and polymethacrylic acid compounds, vinyl polymers, polycarboxylic acids, polyethers, polyimides, polyamides and polyurethanes can also be used as thickeners.

[0092] To set a desired pH that is not substantially due to the mixing of the remaining components, the composition may contain system-compatible and environmentally compatible acids, particularly citric acid, acetic acid, tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid, and / or adipic acid, and inorganic acids, particularly sulfuric acid, or bases, particularly ammonium or alkali metal hydroxides. Such pH adjusters are preferably present in the composition at no more than 20% by weight, particularly from 1.2% to 17% by weight.

[0093] Polymers capable of separating dirt are generally referred to as "detergent" active substances or "antifouling agents" due to their ability to impart stain repellency to treated surfaces, such as fibers, and are, for example, nonionic or cationic cellulose derivatives. In particular, polyester active detergency polymers include copolyesters of dicarboxylic acids (e.g., adipic acid, phthalic acid, or terephthalic acid), glycols (e.g., ethylene glycol or propylene glycol), and polyethylene glycols (e.g., polyethylene glycol or polypropylene glycol). Preferably used detergency polyesters comprise those compounds that are formally obtainable through the esterification of two monomeric moieties, the first monomer being a dicarboxylic acid HOOC-Ph-COOH, and the second monomer being a glycol HO-(CHR) 11 -) a OH, which can also be a polymerized diol H-(O-(CHR) 11 -) a ) b The form of OH. Ph here refers to an ortho-, meta-, or para-phenylene group that can have 1 to 4 substituents selected from alkyl, sulfonic acid, carboxyl groups, and mixtures thereof having 1 to 22 carbon atoms. R 11 It is hydrogen, alkyl groups having 1 to 22 carbon atoms, and mixtures thereof, where a is a number from 2 to 6 and b is a number from 1 to 300. Polyesters obtained from these sources preferably contain the monomeric diol unit -O-(CHR) 11 -) a O- and polymeric diol units -(O-(CHR) 11 -) a ) bO- Both. The molar ratio of monomeric diol units to polymeric diol units is preferably 100:1 to 1:100, especially 10:1 to 1:10. The degree of polymerization b in the polymeric diol units is preferably in the range of 4 to 200, especially 12 to 140. The molecular weight or average molecular weight or maximum molecular weight distribution of the preferred detergency polyester is in the range of 250 to 100,000, especially 500 to 50,000. The acid on which the Ph group is based is preferably selected from terephthalic acid, isophthalic acid, phthalic acid, trimellitic acid, benzenehexacarboxylic acid, sulfophthalic acid, sulfoisophthalic acid and isomers of sulfoterephthalic acid, and mixtures thereof. If these acid groups are not part of the ester bond in the polymer, they are preferably in salt form, especially as alkali metal salts or ammonium salts. Among these, sodium salts and potassium salts are particularly preferred. If desired, instead of the monomer HOOC-Ph-COOH, other acids having at least two carboxyl groups can be present in the detergency polyester in low proportions, particularly based on a content of no more than 10 mol% of Ph as defined above. These include, for example, alkylene dicarboxylic acids and alkenylene dicarboxylic acids, such as malonic acid, succinic acid, fumaric acid, maleic acid, glutaric acid, adipic acid, pimelic acid, octanoic acid, azelaic acid, and sebacic acid. Preferred diols include HO-(CHR) 11 -) a OH includes R 11 It is hydrogen and a is a number from 2 to 6, and it is a number where a has a value of 2 and R 11 Selected from hydrogen and alkyl groups having 1 to 10, especially 1 to 3, carbon atoms. Among the latter diols, those having the formula HO-CH2-CHR are particularly preferred. 11 Those with -OH, of which R 11The diol components are defined above. Examples of diol components are ethylene glycol, 1,2-propanediol, 1,3-propanediol, butane-1,4-diol, pentane-1,5-diol, hexane-1,6-diol, octane-1,8-diol, decane-1,2-diol, dodecane-1,2-diol, and neopentyl glycol. Among the polymeric diols, polyethylene glycol having an average molar mass in the range of 1,000 to 6,000 is particularly preferred. If desired, these polyesters can also be end-capped, wherein the available end groups are esters of alkyl and monocarboxylic acids having 1 to 22 carbon atoms. The end groups bonded via ester bonds can be based on alkyl monocarboxylic acids, alkenyl monocarboxylic acids, and aryl monocarboxylic acids having 5 to 32 carbon atoms, especially 5 to 18 carbon atoms. These include valeric acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, undecenoic acid, lauric acid, myrcenoic acid, tridecanoic acid, myristic acid, myristoleic acid, pentadecanoic acid, palmitic acid, stearic acid, petroselaidic acid, trans-petroselaidic acid, oleic acid, linoleic acid, trans-linolenic acid, linolenic acid, tungsten acid, arachidic acid, cod oleic acid, arachidonic acid, benzyl acid, erucic acid, brassinolic acid, squalene acid, ceramide, ceramide, beeswax acid, and benzoic acid (e.g., tert-butylbenzoic acid), which may have 1 to 5 substituents with a total of no more than 25 carbon atoms, particularly 1 to 12 carbon atoms. The terminal group may also be based on hydroxy monocarboxylic acids having 5 to 22 carbon atoms, including, for example, hydroxyvaleric acid, hydroxyhexanoic acid, ricinoleic acid, its hydrogenation product hydroxystearic acid, and o-, m-, and p-hydroxybenzoic acid. Hydroxymonocarboxylic acids can be linked to each other via their hydroxyl and carboxyl groups, and thus can exist more than once in the terminal groups. The number of hydroxymonocarboxylic acid units / terminal groups (i.e., their oligomerization degree) is preferably in the range of 1 to 50, especially 1 to 10. In a preferred embodiment of the invention, the polymer formed from polyethylene terephthalate and polyethylene oxide terephthalate (wherein the polyethylene glycol units have a molar mass of 750 to 5000 and the molar ratio of polyethylene terephthalate to polyethylene oxide terephthalate is 50:50 to 90:10) is used alone or in combination with cellulose derivatives.

[0094] Dye transfer inhibitors that can be used in compositions for washing textiles include, in particular, polyvinylpyrrolidone, polyvinylimidazole, polymeric N-oxides such as poly(vinylpyridine N-oxide), and copolymers of vinylpyrrolidone with vinylimidazole and optionally other monomers.

[0095] The composition may contain anti-wrinkle agents because textile fabrics, especially those made of rayon, wool, cotton, and blends thereof, may be prone to wrinkling due to the sensitivity of individual fibers to bending, folding, pressing, and squeezing transversely to the fiber direction. These include, for example, synthetic products based on fatty acids, fatty acid esters, fatty acid amides, fatty acid alkyl alcohol esters, fatty acid alkyl alcohol amides, or fatty alcohols that have typically been reacted with ethylene oxide, or products based on lecithin or modified phosphate esters.

[0096] Ash inhibitors function to keep dirt from hard surfaces and, in particular, from textile fibers suspended in liquids. Generally, water-soluble colloids that are organic in nature are suitable for this purpose, such as salts of ether carboxylic acids or ether sulfonic acids of starch, gum, gelatin, starch, or cellulose, or salts of acidic sulfate esters of cellulose or starch. Water-soluble polyamides containing acidic groups are also suitable for this purpose. Starch derivatives other than those mentioned above, such as aldehyde starch, can also be used. 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 an amount of 0.1% to 5% by weight based on the composition.

[0097] The composition may contain optical brighteners, and in particular derivatives of diaminosinyl disulfonic acid or alkali metal salts thereof. Suitable examples are salts of 4,4'-bis(2-anilino-4-morpholino-1,3,5-triazinyl-6-amino)sinyl-2,2'-disulfonic acid or similar compounds with diethanolamine, methylamino, aniline, or 2-methoxyethylamino groups instead of morpholino groups. Substituted diphenylstyryl type brighteners may also be present, such as alkali metal salts of 4,4'-bis(2-sulfostyryl)biphenyl, 4,4'-bis(4-chloro-3-sulfostyryl)biphenyl, or 4-(4-chlorostyryl)-4'-(2-sulfostyryl)biphenyl. Mixtures of the above optical brighteners may also be used.

[0098] In particular, when used in machine washing methods, the addition of a conventional foam inhibitor to the composition can be advantageous. Examples of suitable foam inhibitors include those with a high proportion of C 18 -C 24Soaps of natural or synthetic origin of fatty acids. Suitable non-surfactant foam inhibitors are, for example, organopolysiloxanes and mixtures thereof with finely, optionally silanized silica, and paraffin, waxes, microcrystalline waxes and mixtures thereof with silanized silica or di-fatty acid alkylene diamides. It is also advantageous to use mixtures of various foam inhibitors, such as those formed from silicones, paraffins, or waxes. Foam inhibitors, especially those containing silicones and / or paraffins, are preferably combined with particulate water-soluble or water-dispersible carrier substances. In particular, mixtures of paraffins and bis-stearyl glycolamide are preferred.

[0099] Available peroxides, particularly organic peracids or peracid salts of organic acids (such as phthalimide peroxyhexanoic acid, perbenzoic acid, or diperdodecanoic acid salts), hydrogen peroxide, and inorganic salts that release hydrogen peroxide under washing conditions (such as perborates, percarbonates, and / or persilicates) may optionally be present in the composition, especially in solid form. Hydrogen peroxide can also be generated by means of an enzyme system (i.e., oxidases and their substrates). If solid peroxides are intended to be used, they can be used in powder or granule form, which can also be encapsulated in a manner known in principle. Alkali metal percarbonates, alkali metal perborate monohydrates, alkali metal perborate tetrahydrates, or particularly in liquid compositions as an aqueous solution containing 3% to 10% hydrogen peroxide by weight, are particularly preferred. The peroxides are preferably present in the laundry detergent in an amount of up to 50% by weight, particularly 5% to 30% by weight.

[0100] Alternatively, conventional bleaching activators that form peroxycarboxylic acids or peroxyimino acids under hydrolytic conditions and / or conventionally bleached activated transition metal complexes may be used. Optionally present, particularly in amounts of 0.5% to 6% by weight, the bleaching activator component encompasses typically used N- or O-acyl compounds, such as polyacylated alkylene diamines, especially tetraacetylethylenediamine, acetylated glycourea, especially tetraacetylglycourea, N-acylated hydantoin, acylhydrazine, triazole, ureaazole, diketopiperazine, sulfonamides and cyanurates, as well as carboxylic anhydrides, especially phthalic anhydrides, carboxylic esters, especially sodium isononanoylphenol sulfonate, and acylated sugar derivatives, especially pentaacetyl glucose, and cationic nitrile derivatives such as trimethylammonium acetonitrile salts. To avoid interaction with peroxides during storage, bleaching activators may be granulated or coated with a coating material in a known manner. Particularly preferred are tetraacetylethylenediamine granulated with carboxymethyl cellulose and having an average particle size of 0.01 mm to 0.8 mm, granulated 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine, and / or trialkylammonium acetonitrile manufactured in particulate form. Such bleaching activators are preferably present in the laundry detergent composition in an amount of up to 8% by weight, particularly from 2% to 6% by weight, based on the total composition in each case.

[0101] In a preferred embodiment, the cleaning composition comprises the polymer of the present invention and a biocide. "Biocide" is known to those skilled in the art and includes 2-phenoxyethanol and 4,4'-dichloro-2-hydroxydiphenyl ether.

[0102] The production of solid compositions is not difficult and can be carried out in ways known in principle, such as by spray drying or granulation. For the production of compositions with increased bulk density, particularly in the range of 650 g / l to 950 g / l, methods including an extrusion step are preferred. Laundry 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 to an automatic mixer either in pure form or as a solution.

[0103] In another preferred embodiment, the composition is in the form of a portion of a fully or partially water-soluble encapsulation, particularly in the form of a concentrated liquid. This fractionation makes it easier for consumers to measure the composition.

[0104] Here, the composition can be packaged, for example, in a film bag. The bag packaging, made of a water-soluble film, eliminates the need for consumers to tear open the packaging. In this way, it is convenient to meter the addition of a separate portion tailored for a washing cycle by placing the bag directly into a washing machine or by placing the bag in a specific amount of water (e.g., a bucket, bowl, or sink). The film bag encapsulating the washing portion dissolves without residue when a specific temperature is reached.

[0105] Existing technologies include numerous methods for producing portions of water-soluble laundry detergents, which are also, in principle, suitable for producing compositions usable in the context of this invention. The most well-known method here is the tubular film method with horizontal and vertical sealing seams. Thermoforming is also suitable for producing film bags or dimensionally stable laundry detergent portions. However, water-soluble packaging does not necessarily have to consist of film material and can also be dimensionally stable containers, for example, obtainable by injection molding.

[0106] Methods for producing water-soluble capsules made of polyvinyl alcohol or gelatin are also known, which in principle offer the option of providing capsules with high filler density. These methods are based on introducing a water-soluble polymer into a forming cavity. The filling and sealing of the capsule are performed simultaneously or sequentially, in the latter case the capsule is filled through a small hole. Here, the capsule is filled, for example, by filling wedges above two counter-rotating drums having hemispherical shells on their surfaces. The drums guide a polymer strip covering the hemispherical shell cavity. Sealing occurs at the location where the polymer strip of one drum meets the polymer strip of the opposite drum. In parallel, the material to be filled is injected into the capsule during forming, and the injection pressure of the filling liquid presses the polymer strip into the hemispherical shell cavity. One method for producing water-soluble capsules (where sealing follows filling) is based on the so-called Bottle-Pack method. It involves guiding a tubular preform into two-part cavities. The cavities are closed, with the lower tubular section sealed, and then the tube is inflated to form a capsule in the cavity, filled, and finally sealed.

[0107] The encapsulating material used to produce the water-soluble portion is preferably a water-soluble thermoplastic polymer, more preferably selected from the group consisting of (optionally partially acetalized) polyvinyl alcohol, polyvinyl alcohol copolymers, polyvinylpyrrolidone, polyethylene oxide, gelatin, cellulose and its derivatives, starch and its derivatives, blends and composites of the aforementioned materials, inorganic salts and mixtures, preferably blends of hydroxypropyl methylcellulose and / or polyvinyl alcohol. ® The product name (Clariant) is commercially available. In the context of this invention, a particularly suitable polyvinyl alcohol is, for example, Mowiol. ® 3-83, Mowiol ® 4-88, Mowiol® 5-88, Mowiol ® 8-88 and Clariant L648. The water-soluble thermoplastic used to produce this portion may optionally also comprise polymers selected from the group consisting of acrylic polymers, polyacrylamide, oxazoline polymers, polystyrene sulfonates, polyurethanes, polyesters, polyethers, and / or mixtures of said polymers. Preferably, the water-soluble thermoplastic used comprises polyvinyl alcohol having a degree of hydrolysis of 70 mol% to 100 mol%, preferably 80 mol% to 90 mol%, more preferably 81 mol% to 89 mol%, and particularly 82 mol% to 88 mol%. Further preferably, the water-soluble thermoplastic used comprises polyvinyl alcohol having a molecular weight in the range of 10,000 g / mol to 100,000 g / mol, preferably 11,000 g / mol to 90,000 g / mol, more preferably 12,000 g / mol to 80,000 g / mol, and particularly 13,000 g / mol to 70,000 g / mol. Further preferred is that the thermoplastic is present in an amount of at least 50% by weight, preferably at least 70% by weight, more preferably at least 80% by weight, and especially at least 90% by weight, in each case based on the weight of the water-soluble thermoplastic polymer.

[0108] In another aspect, this application relates to the use of the following in the production of low-dioxane polymers of the present invention: (i) triethanolamine (TEA) and / or triisopropanolamine (TIPA), (ii) ethylene oxide (EO), and (iii) propylene oxide (PO). The limitations mentioned above also apply to this aspect concerning the polymers of the present invention. As used herein, the term "low-dioxane" refers to the dioxane content in a (liquid) solution of the polymer of the present invention. This solution may also be a clean composition of the present invention. In further preferred embodiments, the dioxane content in the polymer solution is less than 15 ppm, less than 10 ppm, less than 9 ppm, less than 8 ppm, less than 7 ppm, less than 6 ppm, less than 5 ppm, less than 4 ppm, or less than 3 ppm.

[0109] In preferred embodiments, the use of triethanolamine (TEA) and / or triisopropanolamine (TIPA), (ii) ethylene oxide (EO), and (iii) propylene oxide (PO) relates to the production of low-dioxane biodegradable polymers. The term "biodegradable" describes the degradation of the polymers of the present invention under natural conditions, such as those present in natural environments or wastewater treatment plants. In further preferred embodiments, the polymers of the present invention exhibit at least 20%, preferably at least 40%, or more preferably at least 60% biodegradability according to standard OECD 301F within 56 days, preferably within 28 days. For the purposes of this invention, aerobic biodegradation in wastewater according to OECD 301F is expressed as a percentage of theoretical oxygen demand (ThOD measured by elemental analysis of the target compound), which is required for the complete biodegradation of the polymer in the sample. Therefore, the amount of oxygen absorbed by the microbial population during the biodegradation of the test substance (corrected for by blank inoculum, in parallel) is expressed as a percentage of ThOD. The obtained values ​​were preferably measured three times using the OECD 301F manometry method. Oxygen consumption was determined by measuring changes in pressure using an OxiTop® C (Xylem 35 Analytics Germany Sales GmbH & Co KG) measuring device. Further details of the tests performed can be found in the experimental section below. Example

[0110] Example 1: Polymer Production

[0111] Unless otherwise stated, the following methods are used for characterization.

[0112] GPC (Gel Permeation Chromatography):

[0113] The number-average molar mass (Mn) of the obtained polymer was determined by gel permeation chromatography in THF as solvent. The GPC system was calibrated using linear polystyrene standards in the molar mass range of 682–2,520,000 g / mol.

[0114] OH value:

[0115] The hydroxyl value was determined by titration according to ASTM E 1899-97.

[0116] Amine value:

[0117] The amine value was determined by titration with trifluoromethanesulfonic acid.

[0118] Compare with Example 1 (C1)

[0119] In the first step, 65.6 g of N4 amine ((0.5 mol) N4 amine (N,N'-bis-(3-aminopropyl)ethylenediamine) was ethoxylated in a 2.5 L autoclave (inertized with N2) with 1.5 mol of EO (66 g of ethylene oxide) in the presence of 8 mL of water (125°C). The reactor was then heated to 120°C–130°C, and 6.53 g of a 50% (by weight) KOH solution was mixed and dehydrated at 100°C and < 10 mbar for two hours. Subsequently, in a separate step, 352 g of EO (8 mol) was metered over 60 minutes. After 15 minutes, 870 g (15 mol) of propylene oxide was added over 45 minutes. The mixture was stirred for another 30 minutes while the temperature was raised to 148°C to induce further reaction over an additional 30 minutes. Finally, the temperature was lowered to 120°C, and the mixture was stirred for 30 to 45 minutes until a constant pressure of approximately 20 bar was established. The laboratory sample was treated by removing volatile components at 90°C and a pressure gradually reduced to 40 mbar (over approximately 45 minutes), followed by a further 45 minutes at 120°C and 40 mbar. The product was characterized by OH value, amine value, and GPC. This yielded 1331 g of a pale yellow polymer.

[0120] Compare with Example 2 (C2)

[0121] 37 g of poly(ethyleneimine) (Mn 600) was reacted with 0.7 mol (31 g) of ethylene oxide and 6 ml of water (130°C; 35 min), followed by dehydration as described in Comparative Example 1 after the metered addition of 6.90 g of 50% (by weight) KOH. 17.75 mol (780 g) of EO was metered over 90 min at 135°C, and the mixture was allowed to react for 40 min, followed by the metered addition of a total of 11.8 mol (685 g) of PO over a 2 h period. After post-treatment similar to that in Comparative Example 1, 1511 g of a yellow polymer was obtained.

[0122] Compare with Example 3 (C3)

[0123] This comparative example was synthesized in a manner comparable to Comparative Examples 1 and 2 or P1-6, wherein the core is a TEA condensate having a number-average molar mass (Mn) of 8700 g / mol. 83.7 g of the TEA condensate having an average molar mass (Mn) of 8700 g / mol was mixed with 6.5 g of a 50% (by weight) KOH solution and then dehydrated in a 2.5 L autoclave at 100°C and < 10 mbar for two hours. The autoclave was inertized by purging three times with nitrogen and a supply pressure of 2 bar was set. The reactor was then heated to 120°C–130°C, and in the first step, 533 g of EO was metered over 70 minutes. After 15 minutes, 722 g of propylene oxide was added over 45 minutes. The mixture was stirred for another 30 minutes while the temperature was raised to 148°C to induce further reaction over an additional 60 minutes. Finally, the temperature was lowered to 120°C, and the mixture was stirred for 30 to 45 minutes until a constant pressure of approximately 20 bar was established. The laboratory sample was treated by removing volatile components at 90°C and a pressure gradually reduced to 40 mbar (over approximately 45 minutes), followed by a further 45 minutes at 120°C and 40 mbar. The product was characterized by GPC. This yielded 1340 g of colorless polymer.

[0124] Compare with Example 4 (C4)

[0125] This comparative example was synthesized in a manner comparable to Comparative Examples 1 and 2 or P1-6, wherein the comparative polymer is a TEA propoxylate having a 10% EO content in the alkoxy chain. 74.6 g (0.50 mol) of triethanolamine and 5.53 g of a 50% (by weight) KOH solution were mixed and then dehydrated in a 2.5 L autoclave at 100°C and < 10 mbar for two hours. The autoclave was inertized by purging three times with nitrogen and a supply pressure of 2 bar was set. The reactor was then heated to 120°C–130°C, and in the first step, 127 g of EO (2.9 mol) was metered over 25 minutes. After 15 minutes, 1053 g (18.15 mol) of propylene oxide was added over 60 minutes. The mixture was stirred for another 30 minutes while the temperature was raised to 148°C to induce further reaction over an additional 45 minutes. Finally, the temperature was lowered to 120°C, and the mixture was stirred for 30 to 45 minutes until a constant pressure of approximately 20 bar was established. The laboratory sample was treated by removing volatile components at 90°C and a pressure gradually reduced to 40 mbar (over approximately 45 minutes), followed by a further 45 minutes at 120°C and 40 mbar. The product was characterized by OH value, amine value, and GPC. This yielded 1256 g of a pale yellow polymer.

[0126] The polymer P1 of the present invention

[0127] 74.6 g (0.50 mol) of triethanolamine and 5.53 g of 50% (by weight) KOH solution were mixed and then dehydrated in a 2.5 L autoclave at 100°C and < 10 mbar for two hours. The autoclave was inertized by purging with nitrogen three times and a supply pressure of 2 bar was set. The reactor was then heated to 120°C–130°C, and in the first step, 330 g of EO (7.5 mol) was metered over 45 minutes. After 15 minutes, 870 g (15 mol) of propylene oxide was added over 45 minutes. The mixture was stirred for another 30 minutes while the temperature was raised to 148°C to induce further reaction over an additional 30 minutes. Finally, the temperature was lowered to 120°C, and the mixture was stirred for 30 to 45 minutes until a constant pressure of approximately 20 bar was established. The laboratory sample was treated by removing volatile components at 90°C and gradually decreasing pressure to 40 mbar (over approximately 45 minutes), followed by a further 45 minutes at 120°C and 40 mbar. The product was characterized by OH value, amine value, and GPC. This yielded 1271 g of a pale yellow polymer.

[0128] The polymer P2 of this invention

[0129] 74.6 g (0.50 mol) of triethanolamine and 5.53 g of 50% (by weight) KOH solution were mixed and then dehydrated in a 2.5 L autoclave at 100°C and < 10 mbar for two hours. The autoclave was inertized by purging with nitrogen three times and a supply pressure of 2 bar was set. The reactor was then heated to 120°C–130°C, and in the first step, 530 g of EO (12 mol) was metered over 70 minutes. After 15 minutes, 670 g (11.5 mol) of propylene oxide was added over 30 minutes. The mixture was stirred for another 30 minutes while the temperature was raised to 148°C to induce further reaction over an additional 60 minutes. Finally, the temperature was lowered to 120°C, and the mixture was stirred for 30 to 45 minutes until a constant pressure of approximately 20 bar was established. The laboratory sample was treated by removing volatile components at 90°C and gradually decreasing pressure to 40 mbar (over approximately 45 minutes), followed by a further 45 minutes at 120°C and 40 mbar. The product was characterized by OH value, amine value, and GPC. This yielded 1265 g of colorless polymer.

[0130] The polymer P3 of this invention

[0131] 74.6 g (0.50 mol) of triethanolamine and 5.53 g of 50% (by weight) KOH solution were mixed and then dehydrated in a 2.5 L autoclave at 100°C and < 10 mbar for two hours. The autoclave was inertized by purging with nitrogen three times and a supply pressure of 2 bar was set. The reactor was then heated to 120°C–130°C, and in the first step, 580 g of PO (10 mol) was metered over 45 minutes. After another 45 minutes, 530 g (12 mol) of ethylene oxide was added over another 45 minutes. The mixture was stirred for another 30 minutes while the temperature was raised to 148°C to induce further reaction over another 60 minutes. Finally, the temperature was lowered to 120°C, and the mixture was stirred for 30 to 45 minutes until a constant pressure of approximately 20 bar was established. The laboratory sample was treated by removing volatile components at 90°C and a pressure gradually reduced to 40 mbar (over approximately 45 minutes), followed by a further 45 minutes at 120°C and 40 mbar. The product was characterized by OH value, amine value, and GPC. This yielded 1183 g of colorless polymer.

[0132] The polymer P3B of this invention

[0133] 74.6 g (0.50 mol) of triethanolamine and 5.53 g of 50% (by weight) KOH solution were mixed and then dehydrated in a 2.5 L autoclave at 100°C and < 10 mbar for two hours. The autoclave was inertized by purging with nitrogen three times and a supply pressure of 2 bar was set. The reactor was then heated to 120°C–130°C, and in the first step, 353 g (8 mol) of ethylene oxide was added, followed by a metered addition of 1160 g (20 mol) of PO over 60 minutes after 30 minutes. The mixture was stirred for another 45 minutes while the temperature was raised to 148°C to induce further reaction over an additional 60 minutes. Finally, the temperature was lowered to 120°C, and the mixture was stirred for 30–45 minutes until a constant pressure of approximately 20 bar was established. The laboratory sample was treated by removing volatile components at 90°C and gradually decreasing pressure to 40 mbar (over approximately 45 minutes), followed by a further 45 minutes at 120°C and 40 mbar. The product was characterized by OH value, amine value, and GPC. This yielded 1576 g of colorless polymer.

[0134] The polymer P4 of this invention

[0135] 104 g (0.54 mol) of triisopropanolamine and 4.2 g of 50% (by weight) KOH solution were mixed and then dehydrated in a 2.5 L autoclave at 100°C and < 10 mbar for two hours. The autoclave was inertized by purging with nitrogen three times and a supply pressure of 2 bar was set. The reactor was then heated to 120°C–130°C and 708 g (12.2 mol) of propylene oxide was added over 45 minutes, followed by a metered addition of 475 g (10.8 mol) of ethylene oxide over another 45 minutes. The procedure was then the same as for P1–P3. This yielded 1281 g of a pale yellow polymer.

[0136] The polymer P4B of this invention

[0137] 104 g (0.54 mol) of triisopropanolamine and 4.2 g of 50% (by weight) KOH solution were mixed and then dehydrated in a 2.5 L autoclave at 100°C and < 10 mbar for two hours. The autoclave was inertized by purging three times with nitrogen and a supply pressure of 2 bar was set. The reactor was then heated to 120°C–130°C and 402 g (9.1 mol) of ethylene oxide was metered over 45 minutes, followed by 912 g (15.7 mol) of propylene oxide over 60 minutes after an additional 20 minutes. The procedure was then the same as for P1–P3. This yielded 1413 g of a pale yellow polymer.

[0138] The polymer P5 of this invention

[0139] Similar to P1-P4, 100 g of oligomeric TEA (molar mass Mn 680 g / mol, OH value (x)) was reacted with 675 g of EO and 700 g of PO. This yielded 1471 g of a yellow polymer.

[0140] The polymer P6 of this invention

[0141] Similar to P1-P4, 100 g of oligomeric TEA (molar mass Mn 1300 g / mol, OH value (x)) was reacted with 420 g of EO and 950 g of PO. The resulting yellow polymer (1463 g) contained 65% PO.

[0142] Example 2: Washing Test

[0143] Test results:

[0144] The measurement error is + / - 4 Δ - ΔE units. Therefore, any value > 4 (the sum of Δ - ΔE) indicates that the polymer in question makes a direct and visible contribution to the overall cleaning performance of the detergent formulation in question; any value > 4 (the sum of Δ - ΔE) indicates that the corresponding polymer even makes a significant contribution to the overall cleaning performance, i.e., the corresponding polymer leads to a significant improvement in the formulation. All polymers (the polymers of this invention and the comparative polymers) showed considerable cleaning benefits in the case of particulate stains.

[0145] To determine the initial cleaning effect on oily / greasy stains, the cleaning performance of 16 different oily / greasy stains on cotton, cotton-polyester, and polyester fabrics (CFT, Vlaardingen, Netherlands) was measured by measuring the color difference (ΔE) between the washed stain and unstained white fabric using a reflectometer (Mach5 plus, from ColourConsult's multi-zone colorimeter). Each experiment was repeated six times with 16 different circular oily / greasy spots (lipstick, cosmetics, beef fat, fried fat, burnt butter, palm oil, BEY sebum, Tefo sebum, collar stain; all on different fabrics). The obtained data were used to calculate the average ΔE value.

[0146] These ΔE values ​​were used to calculate the so-called “normalized cleaning performance” (Δ-ΔE) for each individual stain. “Normalized cleaning performance” (Δ-ΔE) is the difference in performance between a detergent with the alkoxylated nitrogen-containing polymer or comparative polymer according to the invention and a detergent without any alkoxylated nitrogen-containing polymer or comparative polymer. Table 1 shows the washing test conditions, and Table 2 summarizes the obtained normalized cleaning performance. The normalized cleaning performance shown in Table 2 is the sum of the normalized cleaning performance for all 16 stains. The larger the sum of the Δ-ΔE values, the greater the positive contribution of the alkoxylated nitrogen-containing polymer or comparative polymer of the invention compared to the detergent without any alkoxylated nitrogen-containing polymer or comparative polymer.

[0147] Table 1. Washing conditions used to evaluate the primary cleaning performance on oily / greasey stains.

[0148]

[0149] After the washing experiment, the test fabric was washed twice with water with a hardness of 14°dH, dried overnight at room temperature, and then analyzed.

[0150] Example 3: Detection of dioxane content

[0151] The dioxane content was determined by GC-MS. The results for the comparative polymer and the polymer of the present invention are described in Table 2.

[0152] Example 4: Biodegradability

[0153] The biodegradability of the compound was measured by barometric respiration according to OECD 301F, as described above. The results for the comparative polymer and the polymer of the present invention are described in Table 2.

[0154] Table 2: Results of washing tests, dioxane content, and biodegradability for the comparative polymer and the polymer of the present invention. The expression "wt% EO" refers to the relative mass number of EO in the average molar mass of the corresponding polymer.

[0155] .

Claims

1. An alkoxylated polymer comprising a chain of (i) triethanolamine (TEA) and / or triisopropanolamine (TIPA) units and (ii) epoxide units, The triethanolamine (TEA) and / or triisopropanolamine (TIPA) unit has a number-average molar mass (Mn) of less than 5000 g / mol. The chains of these alkyl oxide units are composed of ethylene oxide (EO) and propylene oxide (PO), and the alkoxylated polymer contains between 15% and 80% EO by weight. The alkoxylated polymer contains 0.5 to 10 mol of EO / triethanolamine (TEA) and / or triisopropanolamine (TIPA) OH groups. The alkoxylated polymer contains 2 to 25 mol of PO / triethanolamine (TEA) and / or triisopropanolamine (TIPA) OH groups, and The alkoxylated polymer has a number-average molar mass (Mn) in the range of 1,000 to 30,000 g / mol.

2. The alkoxylated polymer according to claim 1, wherein, The triethanolamine (TEA) and / or triisopropanolamine (TIPA) unit has a number-average molar mass (Mn) of less than 3000 g / mol, preferably less than 1500 g / mol.

3. The alkoxylated polymer according to claim 1 or 2, wherein, The alkoxylated polymer contains EO in the range of 20% to 50% by weight, preferably in the range of 26% to 45% by weight.

4. The alkoxylated polymer according to any one of claims 1 to 3, wherein, The alkoxylated polymer has 2 to 7 mol, preferably 3 to 6 mol, of EO / triethanolamine (TEA) and / or triisopropanolamine (TIPA) OH groups.

5. The alkoxylated polymer according to any one of claims 1 to 4, wherein, The alkoxylated polymer has 5 to 15 mol, preferably 7 to 10 mol, of PO / triethanolamine (TEA) and / or triisopropanolamine (TIPA) OH groups.

6. The alkoxylated polymer according to any one of claims 1 to 5, wherein, The alkoxylated polymer has a number-average molar mass (Mn) between 1300 and 6000 g / mol, preferably between 1400 and 4500 g / mol.

7. A cleaning composition comprising (i) an alkoxylated polymer according to any one of claims 1 to 6 and (ii) a surfactant.

8. The cleaning composition according to claim 7, wherein, The surfactant is an anionic surfactant.

9. The cleaning composition according to claim 7 or 8, wherein, This cleaning composition is a laundry detergent.

10. Use of the alkoxylated polymer according to any one of claims 1 to 6 for enhancing the primary cleaning power of laundry detergents when washing textiles in aqueous and surfactant-containing detergent solutions, particularly for washing stained textiles.

11. The use according to claim 10, wherein, These stains are surfactant-sensitive or enzyme-sensitive stains.

12. A method, particularly for removing surfactant-sensitive or enzyme-sensitive stains from textiles, comprising contacting an alkoxylated polymer according to any one of claims 1 to 6 with the soiled textiles, particularly in a detergent solution containing water and a surfactant.

13. The method according to claim 12, wherein, The detergent is produced by adding 10 ml to 100 ml, particularly 15 ml to 75 ml, preferably 25 ml to 50 ml of liquid water to 12 liters to 60 liters, particularly 15 liters to 20 liters.

14. The following are uses for the production of low-dioxane from the alkoxylated polymers according to any one of claims 1 to 6: (i) Triethanolamine (TEA) and / or triisopropanolamine (TIPA); (ii) Ethylene oxide (EO); and (iii) Propylene oxide (PO).

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