Alkoxylated polymer and synthesis thereof with reduced dioxane formation

Abstract

The present application relates to an alkoxylated polymer consisting of (i) triethanolamine (TEA) and / or triisopropanolamine (TIPA) units and (ii) chains of alkylene oxide units, where the components are chosen so as to give rise to a biodegradable polymer with washing power that can be synthesized with reduced dioxane formation. The application is also directed to a cleaning composition comprising the alkoxylated polymer, to the use of the inventive polymer for boosting the primary washing power of washing compositions, to a cleaning method and to the use of (i) triethanolamine (TEA) and / or triisopropanolamine, (ii) ethylene oxide (EO) and (iii) propylene oxide (PO) for low-dioxane production of an alkoxylated polymer.

Description

[0001] Alkoxylated polymer and its synthesis with reduced dioxane formation

[0002] The present application relates to an alkoxylated polymer consisting of (i) triethanolamine (TEA) and / or triisopropanolamine (TIPA) units and (ii) chains of alkylene oxide units, wherein the components are selected to produce a biodegradable polymer with detergency that can be synthesized with reduced dioxane formation. Furthermore, the application is directed to a cleaning composition comprising the alkoxylated polymer, the use of the inventive polymer to enhance the primary detergency of detergents, a cleaning process, 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 an alkoxylated polymer.

[0003] In addition to the ingredients essential for the washing process, such as surfactants and builders, detergents typically contain other components that can be summarized under the term "washing aids" and include such diverse groups of active ingredients as foam regulators, graying inhibitors, bleaching agents, bleach activators, and dye transfer inhibitors. Such adjuvants also include substances whose presence enhances the washing power of surfactants without necessarily having to exhibit pronounced surfactant properties themselves. Such substances are often referred to as washing boosters.

[0004] International patent application WO 2014 / 154508 A1 discloses that applying block copolymers of polyether alcohol (meth)acrylic acid esters and amino alcohol or ammonium alcohol (meth)acrylic acid esters to textiles facilitates the removal of soiling that subsequently settles on the textiles. International patent application WO 2017 / 005793 A1 discloses that polyalkoxylated poly(γ-alkanolamines) and polyalkoxylated poly(γ-alkyleneimines) exhibit advantages in reducing grease residues. However, these alkoxylated polymers are known to be poorly biodegradable after use and to produce significant amounts of dioxane during their synthesis.

[0005] Therefore, there is a need for alkoxylated polymers with good detergency, high biodegradability and whose synthesis is accompanied by reduced dioxane formation.

[0006] EP18190901 A discloses alkoxylated polymers that exhibit satisfactory washing performance and are exclusively propoxylated. The biodegradability of these polymers is not described, but based on comparative tests in the present application, it can be assumed that these purely propoxylated polymers have low biodegradability.

[0007] W02009112379 A describes detergent-active alkoxylated polymers whose alkoxy chains are composed of ethylene oxide and propylene oxide and which contain an amine core of triethanolamine (TEA). The amine cores of these polymers have a weight-average Mw (g / mol) of 5700 to 14300. The present experiments also showed that biodegradability is low for such polymers with a large amine core.

[0008] Surprisingly, it has now been found that certain low molecular weight alkoxylated triethanolamine (TEA) and / or triisopropanolamine polymers, which have specific proportions of ethylene oxide (EO) and propylene oxide (PO), exhibit good washing properties and show significant biodegradation without releasing large amounts of dioxane during their synthesis.

[0009] The polymers are triethanolamine (TEA) and / or triisopropanolamine alkoxylates, wherein the triethanolamine (TEA) and / or triisopropanolamine (TIPA) core has a number average molar mass (Mn) of less than 5000 g / mol, the chains of alkylene oxide units consist of ethylene oxide (EO) and propylene oxide (PO), and the alkoxylated polymer comprises between 15 and 80 wt.% EO, the alkoxylated polymer has 0.5 to 10 mol EO per OH group of TEA and / or TIPA, the alkoxylated polymer has 2 to 25 mol PO per OH group of TEA and / or TIPA, and the alkoxylated polymer has a number average molar mass (Mn) of between 1000 and 30000 g / mol.

[0010] The term "alkoxylated polymers" as used herein refers to the polymers described above. Alternatively, these polymers are also referred to as (amino-based) alkoxylates, polymeric drug, inventive polymers, or polymers of the invention.

[0011] "Triethanolamine" or "TEA", as used interchangeably herein, describes a compound of the formula below:

[0012] "Triisopropanolamine" or "TI PA", as used herein interchangeably, describes a compound of the formula below:

[0013] "Number average molecular weight (Mn)" or "average molecular weight," as used interchangeably herein, refers to the average molecular weight of the inventive polymers, weighted by the number of molecules. The calculation is known to those skilled in the art. The number average molecular weight (Mn) is preferably determined by gel permeation chromatography (GPC), size exclusion chromatography (SEC), or light scattering. In preferred embodiments, the number average molecular weight (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 molecular weight range of 682–2,520,000 g / mol.

[0014] In preferred embodiments, the triethanolamine (TEA) and / or triisopropanolamine (TI PA) core is a pure triethanolamine (TEA) core and the resulting polymer is a TEA alkoxylate. In further preferred embodiments, this TEA core consists of at most 10 TEA units, at most 7 TEA units, at most 5 TEA units, at most 3 TEA units, and in the most preferred form of one TEA unit. or "EO", as used interchangeably herein, describes a compound of the formula below: 2

[0015] "Propylene oxide" or "PO", as used interchangeably herein, describes a compound of the formula below: o

[0016] H3C^

[0017] The alkoxylation of triethanolamine (TEA) and / or triisopropanolamine (TIPA) units is a static reaction that does not produce uniform end products, but rather a set of polymers that are very similar to each other, yet slightly different from each other. The information on quantities and ratios should therefore be understood as static, meaning that the stated quantity or ratio has the highest probability of being present in a set of inventive polymer, but that different quantities and ratios may also be present, although their probability is lower.For the bonding of the alkylene oxide chains to triethanolamine (TEA) and / or triisopropanolamine (TIPA), each of which contains three OH groups and one tertiary amine, this means that at least 70% of the available OH groups, at least 80% of the available OH groups, at least 90% of the available OH groups, at least 95% of the available OH groups, or at least 99% of the available OH groups are reacted with an alkylene oxide. "Available" OH groups in this case refer to the OH groups that are still present after the synthesis of the triethanolamine (TEA) and / or triisopropanolamine (TIPA) core and are not already reacted 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.

[0018] The reaction at the tertiary amine is also to be understood as static, although the probability of reactions here is very low. For the bonding of the alkylene oxide chains to triethanolamine (TEA) and / or triisopropanolamine (TIPA) via the tertiary amine, this means that no more than 10% of the amine groups, no more than 8% of the amine groups, no more than 6% of the amine groups, no more than 4% of the amine groups, no more than 2% of the amine groups, no more than 1% of the amine groups, no more than 0.5% of the amine groups, or no more than 0.1% of the amine groups are reacted with an alkylene oxide. The bond formed here is an amide bond.

[0019] Furthermore, the length / composition of individual alkylene oxide chains is also a static process. The information given here describes the starting amounts and the greatest probability of finding this amount in a given amount of inventive polymer. For example, if alkoxylation is carried out with 5 mol of EO per OH group, most of the alkylene oxide chains in the polymers will have a length of ethylene oxide units. However, the resulting polymers will be heterogeneous, meaning that a smaller number of alkylene oxide chains with 4 EOs, 3 EOs, 2 EOs, 1 EO, or even unreacted OH groups will be found. Likewise, there will be alkylene oxide chains with 7 EOs, 8 EOs, etc. (with decreasing probability). The individual alkylene oxide units are linked together by ether bonds.

[0020] In preferred embodiments, the inventive polymer is directed to variants wherein 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, more preferably between 149 and 680 g / mol.

[0021] The application is directed to one of the polymers described above, wherein the alkoxylated polymers comprise between 15 and 80 wt.%, preferably between 19 and 60 wt.% EO. More preferably, the polymers comprise between 20 and 45 wt.% EO, even more preferably between 21 and 35 wt.% EO.

[0022] Furthermore, the application is directed to one of the previously described polymers, wherein the alkoxylated polymer has 2 to 7 mol, preferably 3 to 6 mol, of EO per OH group of triethanolamine (TEA) and / or triisopropanolamine (TIPA). More preferably, the inventive polymer comprises between 4 and 5 mol of EO per OH group of triethanolamine (TEA) and / or triisopropanolamine (TIPA), in particular triethanolamine (TEA).

[0023] In preferred embodiments, the alkoxylated polymer has 5 to 20 mol, preferably 7 to 15 mol PO per OH group of triethanolamine (TEA) and / or triisopropanolamine (TIPA), more preferably triethanolamine (TEA).

[0024] In preferred embodiments, an alkoxylation step with ethylene oxide (EO) is carried out first, followed by an alkoxylation with propylene oxide (PO).

[0025] Furthermore, in preferred embodiments, the alkoxylated polymer has a number average molecular weight (Mn) between 1300 to 6000 g / mol, preferably 1400 to 4500 g / mol. In further preferred embodiments, the inventive polymer has a single triethanolamine (TEA) or triisopropanolamine (TIPA) unit, more preferably a triethanolamine (TEA) unit, wherein the alkoxylated polymer comprises between 15 to 80 wt.%, 16 to 75 wt.%, 17 to 70 wt.%, 18 to 65 wt.% or 19 to 60 wt.% EO, wherein the alkoxylated polymer has 2 to 7 mol, 3 to 6 mol or 4 to 5 mol EO per OH group of the triethanolamine (TEA) or triisopropanolamine (TIPA) unit and wherein the alkoxylated polymer has 5 to 15 mol or 6 to 14 mol PO per OH group of the triethanolamine (TEA) or triisopropanolamine (TIPA) unit.

[0026] The person skilled in the art understands that the inventive polymers can contain up to a maximum of 3% by weight, up to a maximum of 2% by weight, up to a maximum of 1% by weight, up to a maximum of 0.5% by weight, up to a maximum of 0.3% by weight or up to a maximum of 0.1% by weight of further components, e.g. starting materials.

[0027] The invention further relates to a method for removing, in particular, surfactant- or enzyme-sensitive soiling from textiles, in which a detergent and a polymeric active ingredient are brought into contact with soiled textiles in a particularly aqueous and surfactant-containing wash liquor. This method can be carried out manually or mechanically, for example using a household washing machine. It is possible to apply, in particular, liquid detergents and the polymeric active ingredient simultaneously or sequentially. Simultaneous application can be carried out particularly advantageously by using a detergent that contains the polymeric active ingredient. Surfactant- or enzyme-sensitive soiling is understood to mean soiling that can usually be at least partially removed by surfactants or with the aid of enzymes, such as, for example, soiling from oil, grease (e.g.animal fats such as beef tallow and lard (pork fat), makeup or grass, chocolate mousse, or egg. The polymers used according to the invention contribute to the removability of such soils even in the absence of enzymes or, in particular, in the absence of bleaching agents.

[0028] The cleaning composition according to the invention, the washing use according to the invention and the method according to the invention are preferably realized by adding the polymer consisting of (mono-)amino-based alkoxylate to an agent free of the corresponding polymer or to a washing liquor containing an agent free of the corresponding polymer, wherein the amount of polymer added, based on the total weight of the agent free of the corresponding polymer, is preferably in the range from 0.01 wt.% to 20 wt.%, in particular from 1 wt.% to 15 wt.%. With particular preference, the polymer essential to the invention is used together with, in particular, liquid washing agents which, based on the total weight of the agent, have a surfactant concentration of at least 30 wt.%, preferably in the range from 30 wt.% to 65 wt.% and in particular 50 wt.% to 58 wt.%.It is preferred that the wash liquor be produced by adding 7 ml to 100 ml, in particular 10 ml to 75 ml, preferably 20 ml to 50 ml, of a liquid aqueous detergent to 12 liters to 60 liters, in particular 15 liters to 20 liters, of water. The polymers essential to the invention can be obtained by generally known processes. The starter molecules, TEA and / or TI PA, are reacted with the alkylene oxides ethylene oxide (EO) and propylene oxide (PO) under alkaline catalysis.

[0029] The starting molecule is initially introduced and dehydrated. Then, under alkaline catalysis, for example, using KOH, the epoxides are added in the desired order and amount.

[0030] Suitable procedures and reaction conditions for the alkoxylation are generally known to the person skilled in the art and are described, for example, in the standard work M. lonescu, "Chemistry and technology of polyols for polyurethanes", Rapra Technology, Shrewsbury, UK, page 60 ff.

[0031] In the context of the use according to the invention and the process according to the invention, it is preferred if the concentration of polymer defined above in the aqueous wash liquor, as used, for example, in washing machines but also in hand washing, is 0.001 g / l to 5 g / l, in particular 0.01 g / l to 2 g / l. The process according to the invention and the use according to the invention are preferably carried out at temperatures in the range from 10 °C to 95 °C, in particular in the range from 20 °C to 40 °C. The process according to the invention and the use according to the invention are preferably carried out at pH values ​​in the range from pH 5 to pH 12, in particular from pH 7 to pH 11.

[0032] Detergents usable alongside the polymer in connection with the cleaning composition according to the invention, the washing application according to the invention, or the process according to the invention, which can be present in particular as powdered solids, in densified particle form, as solutions or suspensions, can contain all known ingredients customary in such agents. The agents can contain, in particular, builders, surface-active surfactants, water-miscible organic solvents, enzymes, sequestering agents, electrolytes, pH regulators, polymers with special effects, such as release polymers, dye transfer inhibitors, graying inhibitors, crease-reducing and shape-retaining polymeric active ingredients, and other auxiliaries, such as optical brighteners, foam regulators, dyes, and fragrances.

[0033] The agents may contain one or more surfactants, particularly anionic surfactants, non-ionic surfactants and mixtures thereof, but may also contain cationic and / or amphoteric surfactants.

[0034] All nonionic surfactants known to the person skilled in the art can be used as nonionic surfactants. Preferably, alkoxylated, advantageously ethoxylated, especially primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol are used as nonionic surfactants, in which the alcohol radical can be linear or, preferably, methyl-branched in the 2-position, or can contain linear and methyl-branched radicals in a mixture, as are usually found in oxo alcohol radicals. However, alcohol ethoxylates with linear radicals from alcohols of native origin having 12 to 18 carbon atoms, e.g., from coconut, palm, tallow, or oleyl alcohol, and an average of 2 to 8 moles of EO per mole of alcohol are preferred.Preferred ethoxylated alcohols include, for example, C 12-14 alcohols with 3 EO or 4 EO, C 8-n alcohol with 7 EO, C 11-18 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C 12-14 alcohol with 3 EO and C 12-18 alcohol with 5 EO. The stated degrees of ethoxylation represent statistical mean values, which for a specific product can correspond to a whole or fractional number. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).

[0035] Alternatively or in addition to these non-ionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO, or 40 EO. Alkyl glycosides of the general formula R can also be used as additional non-ionic surfactants. 5 O(G) X be used in the R 5a primary straight-chain or methyl-branched, in particular 2-methyl-branched, aliphatic radical having 8 to 22, preferably 12 to 18, carbon atoms, and G is the symbol representing a glycose unit having 5 or 6 carbon atoms, preferably glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably, x is between 1.2 and 1.4.

[0036] 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.

[0037] Nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N,N-dimethylamine oxide and N-tallowalkyl-N,N-dihydroxyethylamine oxide, and fatty acid alkanolamides can also be used. The amount of these nonionic surfactants is preferably no more than that of the ethoxylated fatty alcohols, in particular no more than half that amount.

[0038] Other suitable surfactants are polyhydroxy fatty acid amides of the formula in which R is an aliphatic acyl radical having 6 to 22 carbon atoms, R 1represents hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z] represents a linear or branched polyhydroxyalkyl radical having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups. Polyhydroxy fatty acid amides are known substances that can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride. The group of polyhydroxy fatty acid amides also includes compounds of the formula in which R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R 1 represents a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R 2represents a linear, branched, or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, with Cu-alkyl or phenyl radicals being preferred, and [Z] represents a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this radical. [Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose, or xylose. The N-alkoxy- or N-aryloxy-substituted compounds can be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as a catalyst.

[0039] Examples of anionic surfactants used include sulfonates and sulfates. Preferred sulfonate-type surfactants are C 8 -alkylbenzenesulfonates, olefinsulfonates, i.e., mixtures of alkene and hydroxyalkanesulfonates, and disulfonates, such as those obtained, for example, from C 12-18 monoolefins with a terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products. Also suitable are alkanesulfonates obtained from C 12-18 alkyls, for example, by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. Esters of α-sulfofatty acids (estersulfonates), for example, the α-sulfonated methyl esters of hydrogenated coconut, palm kernel, or tallow fatty acids, are also suitable.

[0040] Other suitable anionic surfactants are sulfated fatty acid glycerol esters. Fatty acid glycerol esters are understood to be the mono-, di-, and triesters, as well as mixtures thereof, as obtained by esterifying glycerol with 1 to 3 mol of fatty acid or by transesterifying triglycerides with 0.3 to 2 mol of glycerol. Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids with 6 to 22 carbon atoms, for example, caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid, or behenic acid.

[0041] Also suitable are alkyl sulfates of the general formula

[0042] RO-SO3M, in which R is a linear, branched-chain or cyclic saturated hydrocarbon radical having 12 to 18, in particular 12 to 14, carbon atoms and M is a countercation leading to the charge neutralization of the sulfuric acid half ester, in particular a sodium or potassium ion or an ammonium ion of the general formula

[0043] R 1 R 2 R 3 R 4 N + , in the R 1 , R 2 , R 3 , and R 4independently of one another represents hydrogen, an alkyl group having 1 to 4 C atoms, or a hydroxyalkyl group having 2 to 3 C atoms. Preferred R radicals are derived from native C 12 -C 18 fatty alcohols, such as coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl, or stearyl alcohol, or the C 10 -C 20 oxo alcohols or secondary alcohols of these chain lengths. Also preferred are alkyl sulfates of the stated chain length which contain a synthetic, petrochemically produced straight-chain alkyl radical, which have a degradation behavior analogous to that of the corresponding compounds based on oleochemical raw materials. C 12 -C 16 alkyl sulfates and C 12 -C 14 alkyl sulfates are particularly preferred.

[0044] Also suitable are the sulfuric acid monoesters of straight-chain or branched Cz-21 alcohols ethoxylated with 1 to 6 mol of ethylene oxide, such as 2-methyl-branched Cg-n alcohols with an average of 3.5 mol of ethylene oxide (EC) or C12-18 fatty alcohols with 1 to 4 EC.

[0045] Other suitable anionic surfactants include the salts of alkyl sulfosuccinic acid, also known as sulfosuccinates or sulfosuccinic acid esters, which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols. Preferred sulfosuccinates contain C8-11 fatty alcohol residues or mixtures thereof. Particularly preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty alcohols, which, considered individually, are nonionic surfactants. Sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution are particularly preferred. It is also possible to use alk(en)ylsuccinic acid, preferably with 8 to 18 carbon atoms in the alk(en)yl chain, or salts thereof.

[0046] Other anionic surfactants that may be considered include soaps. Suitable examples include saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid, and behenic acid, as well as soap mixtures derived from natural fatty acids, such as coconut, palm kernel, or tallow fatty acids.

[0047] The anionic surfactants, including soaps, can be present in the form of their sodium, potassium, or ammonium salts, as well as soluble salts of organic bases, such as mono-, di-, or triethanolamine. The anionic surfactants are preferably present in the form of their sodium or potassium salts, especially in the form of the sodium salts. Instead of the aforementioned surfactants or in combination with them, cationic and / or amphoteric surfactants can also be used.

[0048] Surfactants are used.

[0049] Cationic compounds of the following formulas can be used as cationic active substances:

[0050] Ri l +

[0051] Ri-N-(CH2) n -T-R2

[0052] (CH2) n -T-R2

[0053] Ri l +

[0054] R3-N-(CH2)HT-R2

[0055] R4 where each group R 1 is independently selected from Ci-6 alkyl, alkenyl or hydroxyalkyl groups; each group R 2 is independently selected from Cs-28-Al ky I - or -alkenyl groups; 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.

[0056] Such surfactants are present in detergents in amounts of preferably 5% to 65% by weight. As explained above, particularly preferred detergents are liquid and have surfactant contents of at least 30% by weight, preferably in the range from 30% to 60% by weight, and in particular from 50% to 58% by weight. Such concentrated liquid detergents are advantageous because they involve lower resource consumption, which is due in particular to their lower transport weight and reduced consumption size. For example, compared to lower concentration detergents, a smaller bottle size and thus less packaging material are required to achieve the same application performance. In addition, such highly concentrated detergents are preferred by consumers because they require little storage space in households.

[0057] Fabric softening compounds can be used to care for textiles and improve their properties, such as a softer feel (softening) and reduced electrostatic charge (increased comfort). The active ingredients in these formulations are quaternary ammonium compounds with two hydrophobic residues, such as disteraryldimethylammonium chloride. However, due to its insufficient biodegradability, this compound is increasingly being replaced by quaternary ammonium compounds containing ester groups in their hydrophobic residues as predetermined breaking points for biodegradation.

[0058] Such "esterquats" with improved biodegradability can be obtained, for example, by esterifying mixtures of methyldiethanolamine and / or triethanolamine with fatty acids and subsequently quaternizing the reaction products with alkylating agents in a conventional manner. Dimethylolethyleneurea is a suitable finishing agent.

[0059] A detergent preferably contains at least one water-soluble and / or water-insoluble, organic and / or inorganic builder. Water-soluble organic builder substances include polycarboxylic acids, in particular citric acid and sugar acids; monomeric and polymeric aminopolycarboxylic acids, in particular methylglycinediacetic acid, nitrilotriacetic acid, and ethylenediaminetetraacetic acid, as well as polyaspartic acid; polyphosphonic acids, in particular aminotris(methylenephosphonic acid), ethylenediaminetetrakis(methylenephosphonic acid), and 1-hydroxyethane-1,1-diphosphonic acid; polymeric hydroxy compounds such as dextrin; and polymeric (poly)carboxylic acids, in particular polycarboxylates obtainable by oxidation of polysaccharides or dextrins; and / or polymeric acrylic acids, methacrylic acids, maleic acids, and copolymers thereof, which may also contain small amounts of polymerizable substances without carboxylic acid functionality.The relative molecular mass of homopolymers of unsaturated carboxylic acids is generally between 5,000 g / mol and 200,000 g / mol, and that of copolymers between 2,000 g / mol and 200,000 g / mol, preferably 50,000 g / mol to 120,000 g / mol, in each case based on the free acid. A particularly preferred acrylic acid-maleic acid copolymer has a relative molecular mass of 50,000 g / mol to 100,000 g / mol. Suitable, albeit less preferred, compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinyl methyl ethers, vinyl esters, ethylene, propylene, and styrene, in which the proportion of acid is at least 50 wt. %. Terpolymers containing two unsaturated acids and / or their salts as monomers and vinyl alcohol and / or an esterified vinyl alcohol or a carbohydrate as the third monomer can also be used as water-soluble organic builder substances.The first acidic monomer or its salt is derived from a monoethylenically unsaturated Ca-Cs-carboxylic acid, preferably from a C3-C4-monocarboxylic acid, in particular from (meth)acrylic acid. The second acidic monomer or its salt can be a derivative of a C^Cs-dicarboxylic acid, with maleic acid being particularly preferred, and / or a derivative of an allylsulfonic acid substituted in the 2-position with an alkyl or aryl radical. Such polymers generally have a relative molecular weight between 1,000 g / mol and 200,000 g / mol. Further preferred copolymers are those containing acrolein and acrylic acid / acrylic acid salts or vinyl acetate as monomers. The organic builder substances can be used, in particular for the production of liquid compositions, in the form of aqueous solutions, preferably in the form of 30 to 50 percent by weight aqueous solutions.All of the acids mentioned are generally used in the form of their water-soluble salts, especially their alkali metal salts. Such organic builders can, if desired, be present in amounts of up to 40 wt.%, in particular up to 25 wt.%, and preferably from 0.5 wt.% to 8 wt.%. Amounts in the upper half of the mentioned ranges are preferably used in paste-like or liquid, especially water-based, compositions.

[0060] Particularly suitable water-soluble inorganic builder materials are polymeric alkali phosphates, which can be present in the form of their alkaline, neutral or acidic sodium or potassium salts. Examples include tetrasodium diphosphate, disodium dihydrogen diphosphate, pentasodium triphosphate, sodium hexametaphosphate, and the corresponding potassium salts or mixtures of sodium and potassium salts. Particularly suitable water-insoluble, water-dispersible inorganic builder materials are crystalline or amorphous alkali aluminosilicates, in amounts of up to 50 wt.%, preferably not more than 40 wt.%, and in liquid compositions, in particular from 1 wt.% to 5 wt.%. Among these, crystalline sodium aluminosilicates of detergent quality, in particular zeolite A, P, and optionally X, are preferred. Amounts close to the stated upper limit are preferably used in solid, particulate compositions.Suitable aluminosilicates, in particular, contain no particles with a grain size larger than 30 μm and preferably consist of at least 80 wt.% particles with a size smaller than 10 μm. Their calcium binding capacity is generally in the range of 100 mg to 200 mg CaO per gram.

[0061] Suitable substitutes or partial substitutes for the aluminosilicate mentioned are crystalline alkali silicates, which can be present alone or in a mixture with amorphous silicates. The alkali silicates usable as builders preferably have a molar ratio of alkali oxide to SiO2 of less than 0.95, in particular from 1:1.1 to 1:12, and can be amorphous or crystalline. Preferred alkali silicates are sodium silicates, in particular amorphous sodium silicates, with a molar ratio Na2O:SiO2 of 1:2 to 1:2.8. The crystalline silicates, which can be present alone or in a mixture with amorphous silicates, are preferably crystalline phyllosilicates of the general formula Na2Si xO2x+iy H2O is used, in which x, the so-called modulus, is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values ​​for x are 2, 3 or 4. Preferred crystalline layered silicates are those in which x in the general formula mentioned assumes the values ​​2 or 3. In particular, both β- and δ-sodium disilicates (Na2Si2O5 y H2O) are preferred. Practically anhydrous crystalline alkali silicates prepared from amorphous alkali silicates of the above general formula, in which x is a number from 1.9 to 2.1, can also be used. In a further preferred embodiment, a crystalline sodium layered silicate with a modulus of 2 to 3 is used, such as can be prepared from sand and soda. Crystalline sodium silicates with a modulus in the range from 1.9 to 3.5 are used in a further preferred embodiment.In a preferred embodiment, a granular compound of alkali metal silicate and alkali metal carbonate is used, as is commercially available, for example, under the name Nabion® 15. If alkali metal aluminosilicate, in particular zeolite, is also present as an additional builder substance, the weight ratio of aluminosilicate to silicate, based in each case on anhydrous active substances, is preferably 1:10 to 10:1. In agents which contain 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 in particular 1:1 to 2:1. Builder substances are preferably present in detergents in amounts of up to 60% by weight, in particular from 0.5% by weight to 40% by weight.

[0062] In a preferred embodiment, the product has a water-soluble builder block. The use of the term "builder block" is intended to express that the product contains no builder substances other than those that are water-soluble, i.e. all builder substances contained in the product are combined in the thus characterized "block", with the exception of those amounts of substances that may be commercially present in small quantities as impurities or stabilizing additives in the other ingredients of the product. The term "water-soluble" is to be understood to mean that the builder block dissolves without residue at the concentration resulting from the amount of the product containing it used under normal conditions. Preferably, at least 15% by weight and up to 55% by weight, in particular 25% to 50% by weight, are used.-% of water-soluble builder block in the detergents. This is preferably composed of the components a) 5 wt.% to 35 wt.% citric acid, alkali metal citrate and / or alkali metal carbonate, which may also be at least partially replaced by alkali metal bicarbonate, b) up to 10 wt.% alkali metal silicate with a modulus in the range of 1.8 to 2.5, c) up to 2 wt.% phosphonic acid and / or alkali metal phosphonate, d) up to 50 wt.% alkali metal phosphate, and e) up to 10 wt.% polymeric polycarboxylate, whereby the amounts refer to the entire detergent. This also applies to all following amounts, unless expressly stated otherwise.

[0063] In a preferred embodiment, the water-soluble builder block contains at least 2 of components b), c), d) and e) in amounts greater than 0 wt.%.

[0064] With regard to component a), in a preferred embodiment, 15% by weight to 25% by weight of alkali metal carbonate, which may be at least partially replaced by alkali metal bicarbonate, and up to 5% by weight, in particular 0.5% by weight to 2.5% by weight of citric acid and / or alkali metal citrate are present. In an alternative embodiment, component a) contains 5% by weight to 25% by weight, in particular 5% by weight to 15% by weight of citric acid and / or alkali metal citrate and up to 5% by weight, in particular 1% by weight to 5% by weight of alkali metal carbonate, which may be at least partially replaced by alkali metal bicarbonate. If both alkali metal carbonate and alkali metal bicarbonate are present, component a) preferably comprises alkali metal carbonate and alkali metal bicarbonate in a weight ratio of 10:1 to 1:1.

[0065] With regard to component b), a preferred embodiment contains 1 wt.% to 5 wt.% of alkali metal silicate with a modulus in the range of 1.8 to 2.5. With regard to component c), a preferred embodiment contains 0.05 wt.% to 1 wt.% of phosphonic acid and / or alkali metal phosphonate. Phosphonic acids also include optionally substituted alkylphosphonic acids, which may also contain multiple phosphonic acid moieties (so-called polyphosphonic acids).They are preferably selected from the hydroxy and / or aminoalkylphosphonic acids and / or their alkali metal salts, such as, for example, dimethylaminomethanediphosphonic acid, 3-aminopropane-1-hydroxy-1,1-diphosphonic acid, 1-amino-1-phenylmethanediphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid, amino-tris(methylenephosphonic acid), N,N,N',N'-ethylenediamine-tetrakis(methylenephosphonic acid) and acylated derivatives of phosphorous acid, which can also be used in any desired mixtures.

[0066] With regard to component d), a preferred embodiment contains 15% to 35% by weight of alkali metal phosphate, especially trisodium polyphosphate. Alkali metal phosphate is the collective term for the alkali metal (especially sodium and potassium) salts of various phosphoric acids, which include metaphosphoric acids (HPO3). nand orthophosphoric acid H3PO4, along with higher molecular weight representatives. Phosphates combine several advantages: They act as alkali carriers, prevent limescale deposits on machine parts and limescale incrustations in fabrics, and also contribute to the cleaning performance. Sodium dihydrogen phosphate, NaH2PO4, exists as a dihydrate (density 1.91). 3 , melting point 60°) and as monohydrate (density 2.04 3Both salts are white, highly soluble powders that lose their water of crystallization upon heating and, at 200°C, convert into the weakly acidic diphosphate (disodium hydrogen diphosphate, Na2H2P20z), and at higher temperatures into sodium trimetaphosphate (Na2PaOg) and Madrell's salt. NaH2PO4 reacts acidically; it is formed when phosphoric acid is adjusted to a pH of 4.5 with sodium hydroxide solution and the mash is sprayed. Potassium dihydrogen phosphate (primary or monobasic potassium phosphate, potassium biphosphate, KDP), KH2PO4, is a white salt with a density of 2.33. 3 , has a melting point of 253°C (decomposition with formation of (KPÜ3)x, potassium polyphosphate) and is readily soluble in water. Disodium hydrogen phosphate (secondary sodium phosphate), Na2HPO4, is a colorless, very readily water-soluble crystalline salt. It exists in anhydrous form and with 2 mol (density 2.066 mg / l). 3 , water loss at 95°), 7 mol (density 1.68 g / l 3, melting point 48° with loss of 5 H2O) and 12 moles of water (density 1.52 3 , melting point 35°C with loss of 5 H2O), becomes anhydrous at 100°C and, upon further heating, converts into the diphosphate Na4P20z. Disodium hydrogen phosphate is produced by neutralizing phosphoric acid with soda solution using phenolphthalein as an indicator. Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K2HPO4, is an amorphous, white salt that is readily soluble in water. Trisodium phosphate, tertiary sodium phosphate, Na3P04, are colorless crystals which, as the dodecahydrate, have a density of 1.62. 3 and a melting point of 73-76°C (decomposition), as decahydrate (corresponding to 19-20% P2O5) a melting point of 100°C and in anhydrous form (corresponding to 39-40% P2O5) a density of 2.536 g 3Trisodium phosphate is readily soluble in water under alkaline conditions and is prepared by evaporating a solution of exactly 1 mol of disodium phosphate and 1 mol of NaOH. Tripotassium phosphate (tertiary or tribasic potassium phosphate), K3PO4, is a white, deliquescent, granular powder with a density of 2.56 g. 3 It has a melting point of 1340°C and is readily soluble in water with an alkaline reaction. It is formed, for example, by heating Thomas slag with coal and potassium sulfate. Despite their higher price, the more soluble, and therefore highly effective, potassium phosphates are often preferred over the corresponding sodium compounds. Tetrasodium diphosphate (sodium pyrophosphate), Na4P20z, exists in anhydrous form (density 2.534 g). 3 , melting point 988°, also given as 880°) and as decahydrate (density 1,815-1,836 3, melting point 94°C with loss of water). These substances are colorless crystals that are soluble in water with an alkaline reaction. Na4P20z is formed by heating disodium phosphate to >200°C or by reacting phosphoric acid with soda in a stoichiometric ratio and dehydrating the solution by spraying. The decahydrate complexes heavy metal salts and hardness-forming substances and therefore reduces the hardness of the water. Potassium diphosphate (potassium pyrophosphate), K4P2O7, exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33 g. 3which is soluble in water, with the pH of a 1% solution being 10.4 at 25°C. Condensation of NaH2PO4 and KH2PO4, respectively, produces higher molecular weight sodium and potassium phosphates, which can be divided into cyclic representatives, sodium and potassium metaphosphates, and chain-like types, sodium and potassium polyphosphates. A variety of names are used, particularly for the latter: fused or calcined phosphates, Graham's salt, Kurrol's salt, and Madrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates. The industrially important pentasodium triphosphate, NasPsO (sodium tripolyphosphate), is a non-hygroscopic, white, water-soluble salt with the general formula NaO-[P(O)(ONa)-O], which crystallizes in the dry state or with 6 H2O. n-Na with n=3. About 17 g of the anhydrous salt dissolves in 100 g of water at room temperature, about 20 g at 60°C, and about 32 g at 100°C. After heating the solution at 100°C for two hours, hydrolysis produces approximately 8% orthophosphate and 15% diphosphate. To produce pentasodium triphosphate, phosphoric acid is reacted with soda solution or caustic soda in a stoichiometric ratio, and the solution is dehydrated by spraying. Like Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentapotassium triphosphate, K5P3O10 (potassium tripolyphosphate), is commercially available as a 50 wt.% solution (>23% P2O5, 25% K2O). There are also sodium potassium tripolyphosphates that can also be used in the present invention. These are formed, for example, when sodium trimetaphosphate is hydrolyzed with KOH:

[0067] (NaPO3)3+ 2 KOH ä Na3K2P30io + H2O

[0068] These can be used in the same way as sodium tripolyphosphate, potassium tripolyphosphate, or mixtures of these two; mixtures of sodium tripolyphosphate and sodium potassium tripolyphosphate, or mixtures of potassium tripolyphosphate and sodium potassium tripolyphosphate, or mixtures of sodium tripolyphosphate and potassium tripolyphosphate and sodium potassium tripolyphosphate can also be used.

[0069] With regard to component e), a preferred embodiment of the composition contains 1.5% by weight to 5% by weight of polymeric polycarboxylate, in particular selected from the polymerization or copolymerization products of acrylic acid, methacrylic acid and / or maleic acid. Among these are the homopolymers of acrylic acid and, among these, those with an average molecular weight in the range of

[0070] 5 000 D to 15 000 D (PA standard) particularly preferred.

[0071] Suitable enzymes for use in the products are those from the class of proteases, lipases, cutinases, amylases, pullulanases, mannanases, cellulases, hemicellulases, xylanases and peroxidases and mixtures thereof, for example amylases such as Termamyl®, Amylase-LT®, Maxamyl®, Duramyl® and / or Purafect® OxAm, lipases such as Lipolase®, Lipomax®, Lumafast®, Lipozym® and / or Lipex®, cellulases such as Celluzyme® and / or Carezyme®. Among the proteases, the subtilisins (EC 3.4.21.62) are particularly preferred. Enzymatic active ingredients derived from fungi or bacteria, such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus, Humicola lanuginosa, Humicola insolens, Pseudomonas pseudoalcaligenes, or Pseudomonas cepacia, are particularly suitable. The enzymes used, if present, can be adsorbed onto carriers and / or embedded in coating substances to protect them against premature inactivation. They are preferably present in detergents in amounts of up to 10% by weight.-%, in particular from 0.2 wt.% to 2 wt.%.

[0072] In a preferred embodiment, the agent contains 5 wt.% to 65 wt.%, in particular 8 to 55 wt.% anionic and / or non-ionic surfactant, up to 60 wt.%, in particular 0.5 to 40 wt.% builder substance and 0.2 wt.% to 5 wt.% enzyme selected from the proteases, lipases, cutinases, amylases, pullulanases, mannanases, cellulases, oxidases and peroxidases and mixtures thereof.

[0073] The organic solvents usable in the detergents, especially when in liquid or pasty form, include alcohols with 1 to 4 carbon atoms, especially methanol, ethanol, isopropanol, and tert-butanol; diols with 2 to 4 carbon atoms, especially ethylene glycol and propylene glycol; and mixtures thereof and the ethers derived from the aforementioned classes of compounds. Such water-miscible solvents are preferably present in the detergents in amounts not exceeding 30% by weight, especially from 6% to 20% by weight.

[0074] Naturally derived polymers that can be used as thickeners in aqueous liquid agents include agar-agar, carrageenan, tragacanth, gum arabic, alginates, pectins, polyoses, guar gum, locust bean gum, starch, dextrins, gelatin and casein, cellulose derivatives such as carboxymethylcellulose, hydroxyethyl and propylcellulose, and polymeric polysaccharide thickeners such as xanthan gum; in addition, fully synthetic polymers such as polyacrylic and polymethacrylic compounds, vinyl polymers, polycarboxylic acids, polyethers, polyimines, polyamides and polyurethanes can also be used as thickeners.

[0075] To adjust a desired pH value that does not arise automatically from the mixing of the other components, the products may contain system- and environmentally compatible acids, in particular citric acid, acetic acid, tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid, and / or adipic acid, but also mineral acids, in particular sulfuric acid, or bases, in particular ammonium or alkali metal hydroxides. Such pH regulators are preferably present in the products in amounts of no more than 20% by weight, in particular between 1.2% and 17% by weight.

[0076] Soil release polymers, often referred to as "soil release" agents or "soil repellents" due to their ability to render the treated surface, for example the fiber, soil-repellent, include nonionic or cationic cellulose derivatives. Particularly polyester-active soil release polymers include copolyesters of dicarboxylic acids, for example adipic acid, phthalic acid, or terephthalic acid, diols, for example ethylene glycol or propylene glycol, and polydiols, for example polyethylene glycol or polypropylene glycol. The preferably used soil release polyesters include compounds that are formally obtainable by esterification of two monomer moieties, where the first monomer is a dicarboxylic acid HOOC-Ph-COOH and the second monomer is a diol HO-(CHR 11 -) a OH, which is also known as the polymeric diol H-(O-(CHR 11 -) a)bOH may be present. Wherein Ph denotes an o-, m- or p-phenylene radical which may bear 1 to 4 substituents selected from alkyl radicals having 1 to 22 C atoms, sulfonic acid groups, carboxyl groups and mixtures thereof, R 11 Hydrogen, an alkyl radical having 1 to 22 C atoms and mixtures thereof, a is a number from 2 to 6 and b is a number from 1 to 300. The polyesters obtainable from these preferably contain both monomer diol units -O-(CHR 11 -) a O- and polymer diol units -(O-(CHR 11 -) a)bO-. The molar ratio of monomer diol units to polymer diol units is preferably 100:1 to 1:100, in particular 10:1 to 1:10. In the polymer diol units, the degree of polymerization b is preferably in the range from 4 to 200, in particular from 12 to 140. The molecular weight or the average molecular weight or the maximum of the molecular weight distribution of preferred soil-release polyesters is in the range from 250 to 100,000, in particular from 500 to 50,000. The acid underlying the radical Ph is preferably selected from terephthalic acid, isophthalic acid, phthalic acid, trimellitic acid, mellitic acid, the isomers of sulfophthalic acid, sulfoisophthalic acid and sulfoterephthalic acid and mixtures thereof. Unless their acid groups are part of the ester bonds in the polymer, they are preferably present in salt form, especially as alkali or ammonium salts. Among these, sodium and potassium salts are particularly preferred.If desired, instead of the monomer HOOC-Ph-COOH, small amounts, in particular not more than 10 mol% based on the proportion of Ph with the meaning given above, of other acids containing at least two carboxyl groups can be present in the soil-release polyester. These include, for example, alkylene and alkenylene dicarboxylic acids such as malonic acid, succinic acid, fumaric acid, maleic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid. Preferred diols include HO-(CHR). 11 -) a OH includes those in which R 11 hydrogen and a is a number from 2 to 6, and those in which a has the value 2 and R 11 is selected from hydrogen and the alkyl radicals having 1 to 10, in particular 1 to 3, carbon atoms. Among the latter, diols are those of the formula HO-CH2-CHR 11 -OH, in the R 11has the abovementioned meaning, is particularly preferred. Examples of diol components are ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,2-decanediol, 1,2-dodecanediol, and neopentyl glycol. Particularly preferred among the polymeric diols is polyethylene glycol with an average molecular weight in the range from 1,000 to 6,000. If desired, these polyesters can also be end-capped, with suitable end groups being alkyl groups having 1 to 22 carbon atoms and esters of monocarboxylic acids. The end groups bound via ester bonds can be based on alkyl, alkenyl and aryl monocarboxylic acids with 5 to 32 C atoms, in particular 5 to 18 C atoms.These include valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, undecenoic acid, lauric acid, lauroleic acid, tridecanoic acid, myristic acid, myristoleic acid, pentadecanoic acid, palmitic acid, stearic acid, petroselinic acid, petroselaidic acid, oleic acid, linoleic acid, linolaidic acid, linolenic acid, eleostearic acid, arachidic acid, gadoleic acid, arachidonic acid, behenic acid, erucic acid, brassidic acid, clupanodonic acid, lignoceric acid, cerotic acid, melissic acid, benzoic acid, which can carry 1 to 5 substituents with a total of up to 25 C atoms, in particular 1 to 12 C atoms, for example tert-butylbenzoic acid. The end groups can also be based on hydroxymonocarboxylic acids with 5 to 22 C atoms, which include, for example, hydroxyvaleric acid, hydroxycaproic acid, ricinoleic acid, its hydrogenation product hydroxystearic acid, and o-, m- and p-hydroxybenzoic acid.The hydroxymonocarboxylic acids can, in turn, be linked to one another via their hydroxyl group and their carboxyl group and thus be present multiple times in an end group. The number of hydroxymonocarboxylic acid units per end group, i.e., their degree of oligomerization, is preferably in the range from 1 to 50, especially from 1 to 10. In a preferred embodiment of the invention, polymers of ethylene terephthalate and polyethylene oxide terephthalate, in which the polyethylene glycol units have molecular weights of 750 to 5000 and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate is 50:50 to 90:10, are used alone or in combination with cellulose derivatives.

[0077] The dye transfer inhibitors suitable for use in textile washing agents include, in particular, polyvinylpyrrolidones, polyvinylimidazoles, polymeric N-oxides such as poly(vinylpyridine N-oxide) and copolymers of vinylpyrrolidone with vinylimidazole and, if appropriate, other monomers.

[0078] The products may contain anti-crease agents, as textile fabrics, especially those made of rayon, wool, cotton, and their blends, can tend to crease because the individual fibers are sensitive to bending, kinking, pressing, and crushing across the fiber direction. These include, for example, synthetic products based on fatty acids, fatty acid esters, fatty acid amides, fatty acid alkylol esters, fatty alcohols, which are usually reacted with ethylene oxide, or products based on lecithin or modified phosphoric acid esters.

[0079] The purpose of graying inhibitors is to keep the dirt detached from the hard surface, and in particular from the textile fiber, suspended in the liquor. Suitable for this purpose are water-soluble colloids, usually of an organic nature, such as starch, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose, or salts of acidic sulfuric acid esters of cellulose or starch. Water-soluble polyamides containing acidic groups are also suitable for this purpose. Starch derivatives other than those mentioned above can also be used, for example aldehyde starches. Preference is given to cellulose ethers, such as carboxymethylcellulose (sodium salt), methylcellulose, hydroxyalkylcellulose, and mixed ethers, such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose, and mixtures thereof, for example in amounts of 0.1 to 5% by weight, based on the agent.

[0080] The agents may contain optical brighteners, among these in particular derivatives of diaminostilbenedisulfonic acid or its alkali metal salts. Suitable examples are salts of 4,4'-bis(2-anilino-4-morpholino-1,3,5-triazinyl-6-amino)stilbene-2,2'-disulfonic acid or similarly structured compounds that carry a diethanolamino group, a methylamino group, an anilino group, or a 2-methoxyethylamino group instead of the morpholino group. Furthermore, brighteners of the substituted diphenylstyryl type may be present, for example the alkali metal salts of 4,4'-bis(2-sulfostyryl)-diphenyl, 4,4'-bis(4-chloro-3-sulfostyryl)-diphenyl, or 4-(4-chlorostyryl)-4'-(2-sulfostyryl)-diphenyl. Mixtures of the above-mentioned optical brighteners may also be used.

[0081] Particularly when used in automatic washing processes, it can be advantageous to add conventional foam inhibitors to the detergents. Suitable foam inhibitors include, for example, soaps of natural or synthetic origin that contain a high proportion of C18-C24 fatty acids. Suitable non-surfactant foam inhibitors include, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica, as well as paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica or bisfatty acid alkylenediamides. Mixtures of different foam inhibitors, for example, those made of silicones, paraffins, or waxes, are also advantageously used. The foam inhibitors, in particular silicone- and / or paraffin-containing foam inhibitors, are preferably bound to a granular, water-soluble or water-dispersible carrier substance.In particular, mixtures of paraffins and bistearylethylenediamide are preferred.

[0082] Suitable peroxygen compounds optionally contained in the agents, particularly agents in solid form, are in particular organic peracids or peracidic salts of organic acids, such as phthalimidopercaproic acid, perbenzoic acid or salts of diperdodecanedioic acid, hydrogen peroxide and inorganic salts which release hydrogen peroxide under the washing conditions, such as perborate, percarbonate and / or persilicate. Hydrogen peroxide can also be generated with the aid of an enzymatic system, i.e. an oxidase and its substrate. If solid peroxygen compounds are to be used, these can be used in the form of powders or granules, which can also be coated in a manner known in principle. Particular preference is given to alkali percarbonate, alkali perborate monohydrate, alkali perborate tetrahydrate or, especially in liquid agents, hydrogen peroxide in the form of aqueous solutions containing 3% to 10% by weight.-% hydrogen peroxide. Peroxygen compounds are preferably present in detergents in amounts of up to 50 wt.%, in particular from 5 wt.% to 30 wt.%.

[0083] In addition, conventional bleach activators which form peroxocarboxylic acids or peroxoimidic acids under perhydrolysis conditions and / or conventional bleach-activating transition metal complexes can be used. The optional component of the bleach activators, which is present in particular in amounts of 0.5% by weight to 6% by weight, comprises the commonly used N- or O-acyl compounds, for example multiply acylated alkylenediamines, in particular tetraacetylethylenediamine, acylated glycolurils, in particular tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, urazoles, diketopiperazines, sulfurylamides and cyanurates, as well as carboxylic acid anhydrides, in particular phthalic anhydride, carboxylic acid esters, in particular sodium isononanoylphenolsulfonate, and acylated sugar derivatives, in particular pentaacetylglucose, and cationic nitrile derivatives such as trimethylammonium acetonitrile salts.To prevent interaction with the peroxygen compounds during storage, the bleach activators can be coated with coating substances or granulated in a known manner. Tetraacetylethylenediamine granulated with carboxymethylcellulose with average particle sizes of 0.01 mm to 0.8 mm, granulated 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine, and / or trialkylammonium acetonitrile formulated in particle form are particularly preferred. In detergents, such bleach activators are preferably present in amounts of up to 8 wt.%, in particular from 2 wt.% to 6 wt.%, based in each case on the total detergent.

[0084] In preferred embodiments, the cleaning compositions comprise the polymer of the invention and a biocide. "Biocides" are known to those skilled in the art and include, among others, 2-phenoxyethanol and 4,4'-dichloro-2-hydroxydiphenyl ether.

[0085] The production of solid detergents is straightforward and can be carried out in a known manner, for example, by spray drying or granulation. For the production of detergents with increased bulk density, particularly in the range of 650 g / l to 950 g / l, a process including an extrusion step is preferred. Detergents in the form of aqueous solutions or solutions containing other conventional solvents are particularly advantageously produced by simply mixing the ingredients, which can be added in bulk or as a solution to an automatic mixer.

[0086] In a preferred embodiment, the agents, especially in concentrated liquid form, are presented as a portion in a fully or partially water-soluble coating. This portioning facilitates dosing for the consumer.

[0087] The detergents can be packaged in foil pouches, for example. Pouches made of water-soluble foil eliminate the need for consumers to tear open the packaging. This allows for convenient dosing of a single portion, sufficient for one wash cycle, by placing the pouch directly into the washing machine or by dropping it into a specific amount of water, for example, in a bucket, bowl, or hand basin. The foil pouch surrounding the wash portion dissolves without leaving any residue when a certain temperature is reached.

[0088] Numerous processes exist in the prior art for producing water-soluble detergent portions, which are also fundamentally suitable for producing agents usable within the scope of the present invention. The most well-known processes are the tubular film process with horizontal and vertical seals. The thermoforming process (deep-drawing process) is also suitable for producing film pouches or dimensionally stable detergent portions. However, the water-soluble casings do not necessarily have to be made of a film material; they can also be dimensionally stable containers, which can be obtained, for example, by means of an injection molding process.

[0089] Furthermore, processes for producing water-soluble capsules from polyvinyl alcohol or gelatin are known, which in principle offer the possibility of providing capsules with a high fill level. The processes are based on the introduction of the water-soluble polymer into a forming cavity. The filling and sealing of the capsules takes place either synchronously or in sequential steps, with the latter being done through a small opening. The capsules are filled, for example, by a filling wedge arranged above two counter-rotating drums that have spherical half-shells on their surface. The drums guide polymer bands that cover the spherical half-shell cavities. Sealing takes place at the positions where the polymer band of one drum meets the polymer band of the opposite drum.At the same time, the filling material is injected into the developing capsule, with the injection pressure of the filling liquid pressing the polymer bands into the spherical half-shell cavities. A process for producing water-soluble capsules, in which filling occurs first and then sealing, is based on the so-called bottle pack. ä -Process. In this process, a tube-like preform is inserted into a two-part cavity. The cavity is closed, sealing the lower tube section. The tube is then inflated to form the capsule shape within the cavity, filled, and finally sealed.

[0090] The shell material used to produce the water-soluble portion is preferably a water-soluble polymeric thermoplastic, particularly preferably selected from the group consisting of (optionally partially acetalized) polyvinyl alcohol, polyvinyl alcohol copolymers, polyvinylpyrrolidone, polyethylene oxide, gelatin, cellulose and derivatives thereof, starch and derivatives thereof, blends and composites, inorganic salts, and mixtures of the materials mentioned, preferably hydroxypropylmethylcellulose and / or polyvinyl alcohol blends. Polyvinyl alcohols are commercially available, for example under the trademark Mowiol® (Clariant). Polyvinyl alcohols particularly suitable for the present invention are, for example, Mowiol® 3-83, Mowiol® 4-88, Mowiol® 5-88, Mowiol® 8-88, and Clariant L648.The water-soluble thermoplastic used to produce the portion may optionally additionally comprise polymers selected from the group comprising acrylic acid-containing polymers, polyacrylamides, oxazoline polymers, polystyrenesulfonates, polyurethanes, polyesters, polyethers, and / or mixtures of the above polymers. It is preferred if the water-soluble thermoplastic used comprises a polyvinyl alcohol whose degree of hydrolysis is 70 mol% to 100 mol%, preferably 80 mol% to 90 mol%, particularly preferably 81 mol% to 89 mol%, and in particular 82 mol% to 88 mol%. It is further preferred that the water-soluble thermoplastic used comprises a polyvinyl alcohol whose molecular weight is in the range from 10,000 g / mol to 100,000 g / mol, preferably from 11,000 g / mol to 90,000 g / mol, particularly preferably from 12,000 g / mol to 80,000 g / mol and in particular from 13,000 g / mol to 70,000 g / mol.It is further preferred if the thermoplastics are present in amounts of at least 50% by weight, preferably at least 70% by weight, particularly preferably at least 80% by weight and in particular at least 90% by weight, in each case based on the weight of the water-soluble polymeric thermoplastic.

[0091] In a further aspect, the present application is directed to the use of (I) triethanolamine (TEA) and / or triisopropanolamine (TIPA); (II) ethylene oxide (EO); and (III) propylene oxide (PO) for the low-dioxane production of a polymer according to the invention. The above-mentioned restrictions also apply to this aspect with respect to the polymer according to the invention. The term "low-dioxane," as used herein, refers to the dioxane content in a (liquid) solution of the inventive polymer. This solution can also be the cleaning composition according to the 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.

[0092] In preferred embodiments, the use of triethanolamine (TEA) and / or triisopropanolamine (TIPA); (II) ethylene oxide (EO); and (III) propylene oxide (PO) is directed to the low-dioxane production of a biodegradable / biodegradable polymer. The term "biodegradable" or "biodegradable," as used synonymously herein, describes the degradation of the inventive polymer under natural conditions, such as those found in naturally occurring environments or sewage treatment plants. In further preferred embodiments, the polymer according to the invention has a biodegradability of at least 20%, preferably at least 40%, or even more preferably at least 60% according to Standard OECD 301 F within 56 days, preferably within 28 days.For the purposes of this invention, aerobic biodegradation in wastewater is expressed according to OECD 301 F as a percentage of the theoretical oxygen demand (ThOD, measured by elemental analysis of the compound of interest) required for the complete biodegradation of the polymer in the sample. Thus, the amount of oxygen uptaken by the microbial population during the biodegradation of the test substance (corrected for uptake by blank inoculum, performed in parallel) is expressed as a percentage of ThOD. The values ​​obtained are preferably measured in triplicate using the manometric respirometry method OECD 301 F. Oxygen consumption is determined by measuring the pressure change in the apparatus using an OxiTop® C (Xylem 35 Analytics Germany Sales GmbH & Co KG). Further details on the tests performed can be found in the experimental section below.

[0093] Examples

[0094] Example 1 : Production of polymers

[0095] Unless otherwise stated, the following methods were used for characterization.

[0096] GPC (Gel Permeation Chromatography): To determine the number-average molecular weight (Mn) of the resulting polymers, gel permeation chromatography was performed in THF as solvent. The GPC system was calibrated with linear polystyrene standards in the molecular weight range of 682–2,520,000 g / mol.

[0097] OH number:

[0098] The hydroxyl number was determined titrimetrically according to ASTM E 1899-97.

[0099] Amine number:

[0100] The amine number was determined by titration with trifluoromethanesulfonic acid.

[0101] Comparative example 1 (Vgl1)

[0102] In a first step, 65.6 g of N4 amine (0.5 mol) of N4 amine (N,N'-bis-(3-aminopropyl)-ethylenediamine) were ethoxylated in a 2.5 l autoclave (inertized with N2) with 1.5 mol of EO and 66 g of ethylene oxide in the presence of 8 ml of water (125°C). The reactor was then heated to 120-130°C, and 6.53 g of 50% (wt%) KOH solution were mixed and dehydrated at 100°C and <10 mbar for two hours. Subsequently, in a further step, 352 g of EO (8 mol) were added over 60 minutes. After 15 minutes, 870 g (15 mol) of propylene oxide were added over 45 minutes. Stirring is continued for a further 30 minutes, during which the temperature is increased to 148°C to allow a further 30 minutes of post-reaction. Finally, the temperature is reduced to 120°C, and stirring is continued for 30 to 45 minutes until a constant pressure of approximately 20 bar is established. The laboratory samples are processed by evaporating the volatile components at 90°C and gradually reducing the pressure to 40 mbar (within approximately 10 minutes).45 minutes) and then removed for a further 45 minutes at 40 mbar at 120°C. The product was characterized by OH number, amine number, and GPC. 1331 g of a light yellow polymer was obtained.

[0103] Comparative example 2 (Vgl2)

[0104] 37 g of polyethyleneimine (Mn600) are reacted with 0.7 mol, 31 g of ethylene oxide, and 6 ml of water (130°C; 35 minutes), followed by dehydration as described in Comparative Example 1 after 6.90 g of 50% (wt.%) KOH are added. 17.75 mol, 780 g of EO, are added at 135°C within 90 minutes, and the reaction is allowed to continue for 40 minutes before a total of 11.8 mol of PO (685 g) is added over a period of 2 h. After workup, which is carried out analogously to Comparative Example 1, 1511 g of a yellow polymer is obtained.

[0105] Comparative example 3 (cf. 3)

[0106] Comparable to Comparative Examples 1 and 2 or P1-6, this comparative example was synthesized, with the core being a TEA condensate with a number-average molecular weight (Mn) of 8700 g / mol. 83.7 g of TEA condensate with an average molecular weight of 8700 g / mol (Mn) and 6.5 g of 50% (wt.%) KOH solution were mixed and then dewatered in a 2.5 l autoclave at 100 °C and <10 mbar for two hours. The autoclave was rendered inert by purging three times with nitrogen, and a pre-pressure of 2 bar was set. The reactor was then heated to 120-130 °C, and in a first step, 533 g of EO were metered in over 70 minutes. After 15 minutes, 722 g of propylene oxide were added over 45 minutes. Stirring is continued for another 30 minutes, during which time the temperature is increased to 148°C for a further 60 minutes of post-reaction. Finally, the temperature is reduced to 120°C and stirring is continued for 30 to 45 minutes until a constant pressure of approximately 20 bar is established.The laboratory samples were processed by removing the volatile components at 90 °C and a pressure gradually reduced to 40 mbar (within approximately 45 minutes), followed by 120 °C at 40 mbar for a further 45 minutes. The product was characterized by GPC, yielding 1340 g of colorless polymer.

[0107] Comparative example 4 (Cf4)

[0108] This comparative example was synthesized in a manner comparable to Comparative Examples 1 and 2 or P1-6, with the comparative polymer being a TEA propoxylate with a 10% EO content in the alkoxy chain. 74.6 g (0.50 mol) of triethanolamine and 5.53 g of 50% (wt%) 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 rendered inert by purging three times with nitrogen, and a pre-pressure of 2 bar was set. The reactor was then heated to 120-130 °C, and in a first step, 127 g of EO (2.9 mol) were metered in over 25 minutes. After 15 minutes, 1053 g (18.15 mol) of propylene oxide were added over 60 minutes. Stirring is continued for another 30 minutes, during which time the temperature is increased to 148°C for a further 45 minutes of post-reaction. Finally, the temperature is reduced to 120°C and stirring is continued for 30 to 45 minutes until a constant pressure of approximately 20 bar is established.The laboratory samples were processed by removing the volatile components at 90 °C and a pressure gradually reduced to 40 mbar (within approximately 45 minutes), followed by 120 °C at 40 mbar for a further 45 minutes. The product was characterized by OH number, amine number, and GPC. 1256 g of a light yellow polymer were obtained.

[0109] Inventive Polymer P1

[0110] 74.6 g (0.50 mol) of triethanolamine and 5.53 g of 50% (wt%) 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 rendered inert by purging three times with nitrogen, and a pre-pressure of 2 bar was set. The reactor was then heated to 120-130 °C, and 330 g of EO (7.5 mol) were metered in over 45 minutes in a first step. After 15 minutes, 870 g (15 mol) of propylene oxide were added over 45 minutes. The mixture was stirred for a further 30 minutes, during which time the temperature was increased to 148 °C to effect a further 30 minutes of post-reaction. Finally, the temperature is reduced to 120°C, and stirring is continued for 30 to 45 minutes until a constant pressure of approximately 20 bar is established. The laboratory samples are processed by removing the volatile components at 90°C, gradually reducing the pressure to 40 mbar (within approximately 45 minutes), and then stirring for a further 45 minutes at 40 mbar at 120°C.The product was characterized by OH number, amine number, and GPC. 1271 g of a light yellow polymer was obtained.

[0111] Inventive Polymer P2

[0112] 74.6 g (0.50 mol) of triethanolamine and 5.53 g of 50% (wt%) 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 rendered inert by purging three times with nitrogen, and a pre-pressure of 2 bar was set. The reactor was then heated to 120-130 °C, and 530 g of EO (12 mol) were metered in over a period of 70 minutes in a first step. After 15 minutes, 670 g (11.5 mol) of propylene oxide were added over a period of 30 minutes. The mixture was stirred for a further 30 minutes, during which time the temperature was increased to 148 °C to effect a post-reaction for a further 60 minutes. Finally, the temperature is reduced to 120°C and the mixture is stirred for 30 to 45 minutes until a constant pressure of approximately 20 bar is established. The laboratory samples are processed by evaporating the volatile components at 90°C and gradually reducing the pressure to 40 mbar (within approximately 1 minute).45 minutes) and then removed for a further 45 minutes at 40 mbar at 120°C. The product was characterized by OH number, amine number, and GPC. 1265 g of colorless polymer was obtained.

[0113] Inventive Polymer P3

[0114] 74.6 g (0.50 mol) of triethanolamine and 5.53 g of 50% (wt%) 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 rendered inert by purging three times with nitrogen, and a pre-pressure of 2 bar was set. The reactor was then heated to 120-130 °C, and 580 g of PO (10 mol) were metered in over a period of 45 minutes in a first step. After a further 45 minutes, 530 g (12 mol) of ethylene oxide were added over a period of 45 minutes. The mixture was stirred for a further 30 minutes, during which time the temperature was increased to 148 °C to effect a further reaction for 60 minutes. Finally, the temperature is reduced to 120°C and the mixture is stirred for 30 to 45 minutes until a constant pressure of approximately 20 bar is established. The laboratory samples are processed by evaporating the volatile components at 90°C and gradually reducing the pressure to 40 mbar (within approximately 1 minute).45 minutes) and then removed for a further 45 minutes at 40 mbar at 120°C. The product was characterized by OH number, amine number, and GPC. 1183 g of colorless polymer were obtained.

[0115] Inventive polymer P3B

[0116] 74.6 g (0.50 mol) of triethanolamine and 5.53 g of 50% (wt.%) 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 rendered inert by purging three times with nitrogen, and a pre-pressure of 2 bar was set. The reactor was then heated to 120-130 °C, and 353 g (8 mol) of ethylene oxide were added in a first step. After 30 minutes, 1160 g of PO (20 mol) were added over a period of 60 minutes. The mixture was stirred for a further 45 minutes, during which time the temperature was increased to 148 °C to allow a further 60 minutes of post-reaction. Finally, the temperature was reduced to 120 °C, and stirring was continued for 30 to 45 minutes until a constant pressure of approximately 20 bar was established. The laboratory samples are processed by removing the volatile components at 90 °C and a pressure successively reduced to 40 mbar (within approximately 45 minutes) and then at 120 °C for a further 45 minutes at 40 mbar.The product was characterized by OH number, amine number, and GPC. 1576 g of colorless polymer were obtained.

[0117] Inventive Polymer P4

[0118] 104 g (0.54 mol) of triisopropanolamine and 4.2 g of 50% (wt%) 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 rendered inert by purging three times with nitrogen, and a pre-pressure of 2 bar was set. The reactor was then heated to 120-130 °C, and 708 g (12.2 mol) of propylene oxide were added over 45 minutes. After a further 15 minutes, 475 g (10.8 mol) of ethylene oxide were added over 45 minutes. The procedure was then as for P1-P3. 1281 g of a light yellow polymer was obtained.

[0119] Inventive polymer P4B

[0120] 104 g (0.54 mol) of triisopropanolamine and 4.2 g of 50% (wt%) 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 rendered inert by purging three times with nitrogen, and a pre-pressure of 2 bar was set. The reactor was then heated to 120-130 °C, and 402 g (9.1 mol) of ethylene oxide were added over 45 minutes. After a further 20 minutes, 912 g (15.7 mol) of propylene oxide were added over 60 minutes. The procedure was then as for P1-P3. 1413 g of a light yellow polymer was obtained.

[0121] Inventive Polymer P5

[0122] 100 g of oligo-TEA, molecular weight Mn 680 g / mol OH number (x), is reacted with 675 g EO and 700 g PO analogously to P1 -P4. 1471 g of yellow polymer is obtained.

[0123] Inventive Polymer P6

[0124] 100g of oligo-TEA, molecular weight Mn 1300g / mol OH number (x), is reacted with 420g EO and 950g PO analogously to P1 -P4. The yellow polymer (1463g) contains 65% PO.

[0125] Example 2: Washing tests

[0126] Test results:

[0127] The measurement error is + / - 4 Delta-Delta-E units. Therefore, any value >4 (sum of Delta Delta E) means that the respective polymer makes a directed and visible contribution to the overall cleaning performance of the respective detergent formulation; any value >4 (sum of Delta Delta E) means that the respective polymer even makes a significant contribution to the overall cleaning performance, i.e., the respective polymer leads to a significant improvement in the formulation. All polymers (inventive and comparative polymers) demonstrate significant cleaning advantages on particulate stains.

[0128] To determine the primary washing effectiveness on oily / greasy stains, the cleaning performance was measured on 16 different oily / greasy stains on cotton, polycotton, and polyester fabrics (OFT, Vlaardingen, Netherlands) by determining the color difference (Delta E) between the stains after washing and unsoiled white fabric using a reflectometer (Mach5 plus, a multi-range colorimeter from ColourConsult). Each experiment with the 16 different circular oily / greasy stains (lipstick, makeup, beef fat, cooking fat, burnt butter, palm oil, Sebum BEY, Sebum Tefo, collar stain; all on different fabrics) was repeated six times. The obtained data were used to calculate the average Delta E value.

[0129] Using these Delta-E values, the so-called "standardized cleaning performance" (Delta-Delta-E) was calculated for each individual stain. The "standardized cleaning performance" (Delta Delta E) is the difference in performance of the detergent containing the alkoxylated nitrogen-containing polymer of the invention or the comparative polymer compared to the detergent without any alkoxylated nitrogen-containing polymer or comparative polymer. Table 1 shows the washing test conditions, and Table 2 summarizes the standardized cleaning performance obtained. The standardized cleaning performance shown in Table 2 is the sum of the standardized cleaning performances of all 16 stains. The larger the sum of the Delta-Delta-E values, the greater the positive contribution of the alkoxylated nitrogen-containing polymer of the invention or the comparative polymers compared to the detergent without any alkoxylated nitrogen-containing polymer or comparative polymer.

[0130] Table 1. Washing conditions for evaluating primary cleaning performance on oily / greasy stains.

[0131] *) After the washing experiment, the test fabrics are washed twice with water of hardness 14 °dH, dried at RT overnight and then measured.

[0132] Example 3: Detection of dioxane content

[0133] The dioxane content was determined by GC-MS. The results for the comparison polymers and the inventive polymers are described in Table 2. Example 4: Biodegradability

[0134] The biodegradability of the compounds was measured as described above using the manometric respirometry method according to OECD 301 F. The results of the comparison polymers and inventive polymers are described in Table 2.

[0135] Table 2: Results of the washing tests, dioxane content, and biodegradability of the comparison polymers and the inventive polymers. The "wt% EO" refers to the relative amount of EO mass to the average molecular weight of the respective polymer.

Claims

Patent claims 1. An alkoxylated polymer consisting of (i) triethanolamine (TEA) and / or triisopropanolamine (TIPA) units and (ii) chains of alkylene oxide units, wherein the triethanolamine (TEA) and / or triisopropanolamine (TIPA) units have a number average molecular weight (Mn) of less than 5000 g / mol, wherein the chains of alkylene oxide units consist of ethylene oxide (EO) and propylene oxide (PO), and the alkoxylated polymer comprises between 15 and 80 wt.% EO, wherein the alkoxylated polymer has 0.5 to 10 mol EO per OH group of triethanolamine (TEA) and / or triisopropanolamine (TIPA), wherein the alkoxylated polymer has 2 to 25 mol PO per OH group of triethanolamine (TEA) and / or triisopropanolamine (TIPA), and wherein the alkoxylated polymer has a number average the molecular weight (Mn) between 1000 and 30000 g / mol.

2. The alkoxylated polymer according to claim 1, wherein the triethanolamine (TEA) and / or triisopropanolamine (TI PA) units have a number average molecular weight (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 comprises between 20 to 50 wt.%, preferably between 26 to 45 wt.% EO.

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 per OH group of triethanolamine (TEA) and / or triisopropanolamine (TIPA).

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 per OH group of triethanolamine (TEA) and / or triisopropanolamine (TI PA).

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

7. A cleaning composition comprising (I) the alkoxylated polymer according to any one of claims 1 to 6 and (II) a surfactant.

8. The cleaning composition of claim 7, wherein the surfactant is an anionic surfactant.

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

10. Use of an alkoxylated polymer according to one of claims 1 to 6 for enhancing the primary detergency of detergents when washing textiles in, in particular, aqueous and surfactant-containing washing liquid against soiling.

11. Use according to claim 10, characterized in that the soils are surfactant- or enzyme-sensitive soils.

12. A process for removing, in particular, surfactant- or enzyme-sensitive soiling from textiles, characterized in that an alkoxylated polymer according to one of claims 1 to 6 is brought into contact with soiled textiles in a washing liquor, in particular an aqueous and surfactant-containing liquor.

13. The process according to claim 12, characterized in that the washing liquor is produced by adding 10 ml to 100 ml, in particular 15 ml to 75 ml, preferably 25 ml to 50 ml of a liquid water-containing washing agent to 12 liters to 60 liters, in particular 15 liters to 20 liters of water.

14. Use of (i) triethanolamine (TEA) and / or triisopropanolamine (TI PA); (ii) ethylene oxide (EO); and (ill) Propylene oxide (PO) for the low-dioxane preparation of an alkoxylated polymer according to any one of claims 1 to 6.

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