EP3810742B1 - Xylose carbamates as soil release agents - Google Patents

Description

The present invention relates to the use of certain soil-removing active ingredients to enhance the cleaning performance of detergents when washing textiles.

In addition to the ingredients that are essential for the washing process, such as surfactants and builder materials, detergents usually contain other components that can be summarized under the term washing auxiliaries and that include such different groups of active ingredients as foam regulators, graying inhibitors, bleaching agents, bleach activators and color transfer inhibitors. Such auxiliaries also include substances which impart dirt-repellent properties to the laundry fiber and which, if present during the washing process, support the dirt-removing ability of the other detergent ingredients. The same applies to cleaning agents for hard surfaces. Such soil-removing substances are often referred to as "soil release" active ingredients or, because of their ability to render the treated surface, for example the fiber, dirt-repellent, as "soil repellents". For example, from the US patent U.S. 4,136,038 the dirt-removing effect of methyl cellulose is known. The European patent application EP 0 213 729 discloses the reduced redeposition when using detergents containing a combination of soap and nonionic surfactant with alkyl hydroxyalkyl cellulose. From the European patent application EP 0 213 730 textile treatment agents are known which contain cationic surfactants and nonionic cellulose ethers with HLB values of 3.1 to 3.8. The US patent specification U.S. 4,000,093 discloses detergents containing 0.1% by weight to 3% by weight of alkyl cellulose, hydroxyalkyl cellulose or alkyl hydroxyalkyl cellulose and 5% by weight to 50% by weight of surfactant, the surfactant component essentially consists of C ₁₀ to C ₁₃ alkyl sulphate and has up to 5% by weight of C ₁₄ alkyl sulphate and less than 5% by weight of alkyl sulphate having alkyl radicals of C ₁₅ and higher. In individual cases, however, it has been observed that the effect of such cellulose derivatives in water-containing liquid detergents can diminish after, in particular, prolonged storage under unfavorable conditions.

Because of their chemical similarity to polyester fibers, particularly effective soil-release agents in textiles made from this material are copolyesters containing dicarboxylic acid units such as terephthalic acid or sulfoisophthalic acid, alkylene glycol units such as ethylene glycol or propylene glycol, and polyalkylene glycol units such as polyethylene glycol. Dirt-removing copolyesters of the type mentioned and their use in detergents have been known for a long time.

The polymers known from the prior art have the disadvantage that, particularly in the case of textiles that do not consist, or at least do not consist predominantly, of polyester, have no or only insufficient effectiveness. However, a large part of today's textiles consists of cotton or cotton-polyester blend fabrics, so that there is a need for more effective soil-removing active ingredients, particularly in the case of greasy stains on textiles of this type in particular.

Surprisingly, it was found that this problem can be solved by using certain xylan derivatives.

From the international patent application WO 00/18860 A1 the reconstruction effect on textiles of so-called cellulose esters, which can also be cellulose carbamates, is known. This is presumably due to the fact that the cellulose esters are deposited on the damaged areas of the textile, react with the fiber by splitting off the reactive ester functionality and thereby reinforce the damaged areas with cellulose. From the international patent application WO 00/18861 A1 it is known that such cellulose esters enhance the affinity of material to be deposited onto a substrate, such as a fiber, for the substrate. The international patent application WO 01/72937 A1 relates to the reduction of dye losses when washing colored textiles through the use of such cellulose esters. From the international patent application WO 01/72944 A1 discloses the suitability of such cellulose ethers for enhancing the deposition of fragrances on fabrics, and from the patent application GB 2 360 791A are known to contribute to fabric softness through their deposition on fabrics. U.S. 2009/318325 A1 discloses substituted xylans, in particular carboxymethylxylan, with a dirt-releasing effect. Ebringerová in Das Papier 46, 1992, 726-732 describes sulfoalkylxylans with antiredepositive properties.

in der R¹ und R² unabhängig voneinander für H oder -C(=O)-NR³R⁴ stehen mit der Maßgabe, dass mindestens 1 der Reste R¹ und R² gleich -C(=O)-NR³R⁴ ist, und

• R³ und R⁴ unabhängig voneinander für -H, Aryl-, geradkettige oder verzweigte Alkyl-, Aryl-, Alkylaryl- oder Arylalkylgruppen stehen, die mit einer oder mehreren funktionellen Gruppen, wie Hydroxy-, Carboxy-, Oxy-, Amino- oder Ammoniumgruppen, substituiert sein können, und/oder die mit Heteroatomen, wie N, O oder S, unterbrochen sein können,
• zur Verstärkung der Reinigungsleistung von Waschmitteln beim Waschen von Textilien.

The invention relates to the use of xylan derivatives which contain a unit of general formula (I),

in which R ¹ and R ² independently represent H or -C(=O)-NR ³ R ⁴ with the proviso that at least 1 of the radicals R ¹ and R ² is -C(=O)-NR ³ R ⁴ is and

• R ³ and R ⁴ independently represent -H, aryl, straight or branched chain alkyl, aryl, alkylaryl or arylalkyl groups substituted with one or more functional groups such as hydroxy, carboxy, oxy, amino or ammonium groups, which can be substituted and/or which can be interrupted with heteroatoms such as N, O or S,
• to enhance the cleaning performance of detergents when washing textiles.

Xylose carbamates of the general formula (I) can be obtained by analogy with known production processes, for example by a two-stage synthesis consisting of the reaction of xylan, which can be obtained from beech or birch wood, for example, with phenyl chloroformate or nitrophenyl chloroformate, based on the by Th. Elschner, K. Ganske and Th. Heinze in Cellulose 20 (2013) 339-353 methods described for cellulose carbamates, to give xylosephenyl carbonates or xylose nitrophenyl carbonates and subsequent aminolysis of the carbonates with amines of the H—NR ³ R ⁴ type to give the corresponding xylose carbamates. Preferred -NR ³ R ⁴ groups are derived from amino alcohols such as, for example, 2-aminoethanol, 3-aminopropanol, 2-(2-aminoethoxy)ethanol, N-2-(2-hydroxyethyl)ethylenediamine, 2-amino-1,3 -propanediol, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-ethyl-1,3-propanediol, tris (hydroxymethyl) aminomethane, polyalkoxylated and in particular ethoxylated amines, for example under the Trade names Jeffamine ^® are available, α-amino acids, β-amino acids such as β-alanine, ω-amino acids, aniline which may be substituted on the ring if desired, benzylamine which may be substituted on the ring if desired such as p-aminobenzylamine, morpholine, N-amino-morpholine, N-aminoalkyl-morpholine, ethylenediamine, and mixtures of these.

In addition to the substituted anhydroxylosic unit of the general formula (I), the xylan derivative to be used according to the invention contains other anhydroxylosic units linked to it, which may be unsubstituted or also correspond to the general formula (I). If desired, anhydroxylose residues with other substituents, for example alkyl groups such as methyl or ethyl groups, hydroxyalkyl groups such as hydroxyethyl or hydroxypropyl groups or oligoethoxyethyl or oligopropoxypropyl groups, carboxyalkyl groups such as carboxymethyl or carboxyethyl groups, aminoalkyl groups such as aminoethyl or trimethylammoniumethyl groups, sulfoalkyl groups such as sulfoethyl or sulfopropyl groups, ester groups such as acetic acid, β-aminopropionic acid, glycolic acid or malonic acid ester groups may be present. From the xylans used for the production, eg beech wood xylans, for example 4-methylglucuronic acid (normally 1% to 20%, on average about 9%) or possibly also glucuronic acid (about 2% to 14%) can be contained in the xylan derivative to be used according to the invention . The average degree of substitution, based on the proportion of carbamate groups, in the xylan derivative to be used according to the invention is preferably in the range from 0.1 to 1.8, in particular 0.2 to 1.2. If other substituents are present in addition to carbamate groups, the average degree of substitution, based on the proportion of such other groups, is preferably below 1 and in particular below the degree of substitution for the carbamate groups. The average degree of polymerization (DP) in the xylan used for the preparation of the xylan derivatives to be used according to the invention is preferably in the range from 20 to 1000, in particular in the range from 70 to 700. Among the xylan derivatives to be used according to the invention are those with a number-average molar mass in the range of 3000 g/mol to 150,000 g/mol, in particular in the range from 30,000 g/mol to 110,000 g/mol, to be determined, for example, by means of size exclusion chromatography (GPC, eg eluent 0.5% LiBr in DMSO, flow rate 0.5 ml/min, JASCO ^® system, pump: PU-980, detector: RI-930, column: PSS Novema 300 and PSS Novema 3000 in series) and Pullulan as a calibration standard, preferred.

Another subject of the invention is a process for washing textiles, in which a detergent and a soil-removing active substance in the form of a xylan derivative defined above are used. These procedures can be carried out manually or, if necessary, with the aid of a standard household washing machine. It is possible to use the detergent and the soil-removing active ingredient simultaneously or in succession. Simultaneous use can be carried out particularly advantageously by using a detergent which contains the active ingredient which has the ability to remove dirt.

The effect of the active ingredient to be used according to the invention is particularly pronounced when it is used several times, ie in particular for removing soiling from textiles which had already been washed and/or aftertreated in the presence of the active ingredient before they were provided with the soiling. In connection with the after-treatment, it should be pointed out that the positive aspect mentioned can also be achieved by a washing process in which the textile is washed after the actual washing process, which is carried out using a detergent that can contain a named active ingredient, but in this case also freely may be carried out by this, is brought into contact with an aftertreatment agent, for example as part of a fabric softening step, which contains an active ingredient to be used according to the invention. With this procedure, too, the washing performance-enhancing effect of the active ingredients to be used according to the invention occurs in the next washing process, even if, if desired, a detergent without an active ingredient to be used according to the invention is used again. This is significantly higher than one resulting from the use of a conventional soil release active ingredient. In a particularly preferred embodiment, the active ingredient essential to the invention is added in the softening cycle of the textile wash.

The active ingredient used according to the invention leads to a significantly better detachment of grease and cosmetic stains in particular on textiles, in particular those made of cotton or cotton-containing fabrics, than is the case when compounds previously known for this purpose are used. Alternatively, significant amounts of surfactants can be saved with the same fat removal capacity.

The use according to the invention can be carried out as part of a washing process in such a way that the soil-removing active ingredient is added to a detergent-containing liquor or, preferably, the active ingredient is introduced as a component of a detergent into the liquor which contains the object to be cleaned or which is brought into contact with it.

The use according to the invention in the context of a laundry after-treatment process can be carried out in such a way that the soil-removing active ingredient is added separately to the rinsing liquor, which is used after the wash cycle carried out using a detergent that contains bleach in particular, or it is introduced as a component of the laundry after-treatment agent, in particular a fabric softener. In this aspect of the invention, the detergent used before the laundry aftertreatment agent can also contain an active ingredient to be used according to the invention, but can also be free of it.

Further objects of the invention are therefore detergents and laundry aftertreatment agents which contain the xylan derivatives defined above.

The washing process preferably takes place at a temperature of 15.degree. C. to 60.degree. C., particularly preferably at a temperature of 20.degree. C. to 40.degree. The washing process is furthermore preferably carried out at a pH of 6 to 11, particularly preferably at a pH of 7.5 to 9.5. The use concentration of the xylan derivative in the wash liquor is preferably 0.001 g/l to 1 g/l, in particular 0.005 g/l to 0.2 g/l.

Agents that contain an active ingredient to be used according to the invention in the form of the xylan derivative mentioned or used together with it or used in methods according to the invention can contain all the usual other components of such agents that do not interact in an undesirable manner with the active ingredient essential to the invention, in particular surfactants. The active ingredient defined above is preferably used in amounts of from 0.01% by weight to 10% by weight, particularly preferably from 0.1% by weight to 3% by weight, with this and the following quantitative data refer to the entire funds, unless otherwise stated. An agent according to the invention or used in the method according to the invention or used in the context of the use according to the invention preferably contains water and is liquid; it contains in particular 2% by weight to 92% by weight, particularly preferably 3% by weight to 85% by weight, of water.

It has surprisingly been found that the active ingredient used according to the invention has a positive effect on the action of certain other detergent ingredients and that, conversely, the effect of the soil release active ingredient is additionally enhanced by certain other detergent ingredients. These effects occur in particular with bleaching agents, with enzymatic active substances, in particular proteases and lipases, with water-soluble inorganic and/or organic builders, in particular based on oxidized carbohydrates or polymeric polycarboxylates, with synthetic anionic surfactants of the sulfate and sulfonate type, and with color transfer inhibitors, for example vinylpyrrolidone , Vinylpyridine or vinylimidazole polymers or copolymers or corresponding polybetaines, which is why the use of at least one of the other ingredients mentioned together with the active ingredient to be used according to the invention is preferred.

A composition which contains an active ingredient to be used according to the invention or is used together with it or is used in the method according to the invention preferably contains peroxygen-based bleaching agents, in particular in amounts ranging from 5% by weight to 70% by weight, and optionally However, in another preferred embodiment, bleach activator, in particular in amounts in the range from 2% by weight to 10% by weight, can also be free of bleach and bleach activator. The bleaches that come into consideration are preferably the peroxygen compounds usually used in detergents, such as percarboxylic acids, for example dodecanediperoic acid or phthaloylaminoperoxicaproic acid, hydrogen peroxide, alkali metal perborate, which can be in the form of tetrahydrate or monohydrate, percarbonate, perpyrophosphate and persilicate, which are generally present as alkali metal salts, in particular as sodium salts. Bleaching agents of this type are present in detergents which contain an active ingredient used according to the invention, preferably in amounts of up to 25% by weight, in particular up to 15% by weight and particularly preferably from 5% by weight to 15% by weight on the entire agent, available, with percarbonate being used in particular. The optionally present component of the bleach activators includes the N- or O-acyl compounds commonly used, for example polyacylated alkylenediamines, in particular tetraacetylethylenediamine, acylated glycolurils, in particular tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, urazoles, diketopiperazines, sulfurylamides and cyanurates, and also carboxylic acid anhydrides , in particular phthalic anhydride, carboxylic acid esters, in particular sodium isononanoylphenol sulfonate, and acylated sugar derivatives, in particular pentaacetyl glucose, and cationic nitrile derivatives such as trimethylammonium acetonitrile salts. To avoid interaction with the peroxygen compounds during storage, the bleach activators may have been coated or granulated in a known manner with encapsulating substances, granulated tetraacetylethylenediamine having weight-average particle sizes of 0.01 mm to 0.8 mm, granulated 1,5- Diacetyl-2,4-dioxohexahydro-1,3,5-triazine and/or trialkylammoniumacetonitrile formulated in particle form is particularly preferred. Such bleach activators are preferably present in detergents in amounts of up to 8% by weight, in particular from 2% by weight to 6% by weight, based in each case on the detergent as a whole.

In a preferred embodiment, an agent used according to the invention or used in the method according to the invention contains nonionic surfactant selected from fatty alkyl polyglycosides, fatty alkyl polyalkoxylates, in particular ethoxylates and/or propoxylates, fatty acid polyhydroxyamides and/or ethoxylation and/or propoxylation products of fatty alkylamines, vicinal diols, fatty acid alkyl esters and /or fatty acid amides and mixtures thereof, in particular in an amount in the range from 2% by weight to 25% by weight.

A further embodiment of such agents comprises the presence of synthetic anionic surfactant of the sulfate and/or sulfonate type, in particular fatty alkyl sulfate, fatty alkyl ether sulfate, sulfofatty acid esters and/or sulfofatty acid disalts, in particular in an amount in the range from 2% to 25% by weight. The anionic surfactant is preferably selected from the alkyl or alkenyl sulfates and/or the alkyl or alkenyl ether sulfates in which the alkyl or alkenyl group has 8 to 22, in particular 12 to 18, carbon atoms. These are usually not individual substances, but cuts or mixtures. Among these, preference is given to those whose proportion of compounds with longer-chain radicals in the range from 16 to 18 carbon atoms is more than 20% by weight.

Suitable nonionic surfactants include the alkoxylates, in particular the ethoxylates and/or propoxylates, of saturated or mono- to polyunsaturated linear or branched-chain alcohols having 10 to 22 carbon atoms, preferably 12 to 18 carbon atoms. The degree of alkoxylation of the alcohols is generally between 1 and 20, preferably between 3 and 10. They can be prepared in a known manner by reacting the corresponding alcohols with the corresponding alkylene oxides. The derivatives of fatty alcohols are particularly suitable, although their branched-chain isomers, in particular so-called oxo alcohols, can also be used for the preparation of useful alkoxylates. Accordingly, the alkoxylates, in particular the ethoxylates, of primary alcohols with linear, in particular dodecyl, tetradecyl, hexadecyl or octadecyl radicals, and mixtures thereof, can be used. Corresponding alkoxylation products of alkylamines, vicinal diols and carboxamides which correspond to the alcohols mentioned with regard to the alkyl part can also be used. The ethylene oxide and/or propylene oxide insertion products of fatty acid alkyl esters and fatty acid polyhydroxyamides also come into consideration. So-called alkyl polyglycosides suitable for incorporation into the agents according to the invention are compounds of the general formula (G) _n -OR ¹² , in which R ¹² is an alkyl or alkenyl radical having 8 to 22 carbon atoms, G is a glycose unit and n is a number between 1 and 10 mean. The glycoside component (G) _n is an oligomer or polymer of naturally occurring aldose or ketose monomers, including in particular glucose, mannose, fructose, galactose, talose, gulose, altrose, allose, idose, ribose, arabinose, xylose and lyxose belong. The oligomers consisting of such glycosidically linked monomers are characterized not only by the type of sugar they contain but also by their number, the so-called degree of oligomerization. The degree of oligomerization n, as a variable to be determined analytically, generally assumes fractional numerical values; it is between 1 and 10, in the case of the glycosides preferably used it is below a value of 1.5, in particular between 1.2 and 1.4. The preferred monomer building block is glucose because it is readily available. The alkyl or alkenyl part R ¹² of the glycosides preferably also originates from easily accessible derivatives of renewable raw materials, in particular from fatty alcohols, although their branched-chain isomers, in particular so-called oxo alcohols, can also be used to produce usable glycosides. Accordingly, the primary alcohols with linear octyl, decyl, dodecyl, tetradecyl, hexadecyl or octadecyl radicals and mixtures thereof can be used in particular. Particularly preferred alkyl glycosides contain one Coconut fatty alkyl radical, ie mixtures with essentially R ¹² = dodecyl and R ¹² = tetradecyl.

Nonionic surfactant is used according to the invention in compositions containing a soil release active ingredient used according to the invention or used in the method according to the invention, preferably in amounts of 1% by weight to 30% by weight, in particular from 1% by weight to 25% by weight % by weight, with amounts in the upper part of this range being more likely to be found in liquid detergents and particulate detergents preferably containing rather lower amounts of up to 5% by weight.

Instead or in addition, the agents can contain other surfactants, preferably synthetic anionic surfactants of the sulfate or sulfonate type, such as alkylbenzenesulfonates, in amounts of preferably not more than 20% by weight, in particular from 0.1% by weight to 18% by weight. %, in each case based on the total agent. Synthetic anionic surfactants which are particularly suitable for use in such agents are the alkyl and/or alkenyl sulfates having 8 to 22 carbon atoms which carry an alkali metal, ammonium or alkyl or hydroxyalkyl-substituted ammonium ion as counter cation. The derivatives of fatty alcohols with in particular 12 to 18 carbon atoms and their branched-chain analogues, the so-called oxo alcohols, are preferred. The alkyl and alkenyl sulfates can be prepared in a known manner by reacting the corresponding alcohol component with a customary sulfating agent, in particular sulfur trioxide or chlorosulfonic acid, and subsequent neutralization with alkali metal, ammonium, or alkyl or hydroxyalkyl-substituted ammonium bases. The sulfate-type surfactants that can be used also include the sulfated alkoxylation products of the alcohols mentioned, so-called ether sulfates. Such ether sulfates preferably contain 2 to 30, in particular 4 to 10, ethylene glycol groups per molecule. Suitable anionic surfactants of the sulfonate type include the α-sulphoesters obtainable by reacting fatty acid esters with sulfur trioxide and subsequent neutralization, in particular those derived from fatty acids having 8 to 22 carbon atoms, preferably 12 to 18 carbon atoms, and linear alcohols having 1 up to 6 carbon atoms, preferably 1 to 4 carbon atoms, deriving sulfonation products, and the sulfofatty acids resulting from these by formal hydrolysis.

• falls vorhanden - vorzugsweise in Mengen von 0,5 Gew.-% bis 7 Gew.-% eingesetzt werden. Unter diesen sind die unten diskutierten Esterquats besonders bevorzugt.

Other optional surfactant ingredients are soaps, with saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid or stearic acid, and soaps derived from natural fatty acid mixtures, for example coconut, palm kernel or tallow fatty acids, being suitable. In particular, those soap mixtures are preferred which are composed of 50% by weight to 100% by weight of saturated C ₁₂ -C ₁₈ fatty acid soaps and up to 50% by weight of oleic acid soap. Preferably, soap is included in amounts of from 0.1% to 5% by weight. However, particularly in liquid agents which contain a polymer used according to the invention, higher amounts of soap, generally up to 20% by weight, can also be present. If desired, the agents can also contain betaines and/or cationic surfactants

• if present - preferably in amounts of 0.5% by weight to 7% by weight. Among these, the ester quats discussed below are particularly preferred.

In a further embodiment, the composition contains water-soluble and/or water-insoluble builder, in particular selected from alkali metal aluminosilicate, crystalline alkali metal silicate with a modulus above 1, monomeric polycarboxylate, polymeric polycarboxylate and mixtures thereof, in particular in amounts ranging from 2.5% by weight to 60 wt%.

The composition preferably contains 20% by weight to 55% by weight of water-soluble and/or water-insoluble, organic and/or inorganic builder. The water-soluble organic builder substances include, in particular, those from the class of polycarboxylic acids, in particular citric acid and sugar acids, and polymeric (poly)carboxylic acids, in particular the polycarboxylates accessible by oxidation of polysaccharides, polymeric acrylic acids, methacrylic acids, maleic acids and mixed polymers of these, which also may contain small proportions of polymerizable substances without carboxylic acid functionality as polymerized units. The relative molecular mass of the homopolymers of unsaturated carboxylic acids is generally between 5000 g/mol and 200000 g/mol, that of the copolymers between 2000 g/mol and 200000 g/mol, preferably 50000 g/mol to 120000 g/mol, based on the free acid . A particularly preferred acrylic acid-maleic acid copolymer has a relative molecular weight of 50,000 g/mol to 100,000 g/mol. Suitable, although less preferred, compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinyl methyl ethers, vinyl esters, ethylene, propylene and styrene, in which the proportion of the acid is at least 50% by weight. Terpolymers which contain two carboxylic acids and/or their salts as monomers and vinyl alcohol and/or a vinyl alcohol derivative or a carbohydrate as the third monomer can also be used as water-soluble organic builder substances. The first acidic monomer or its salt is derived from a monoethylenically unsaturated C ₃ -C ₈ -carboxylic acid and preferably from a C ₃ -C ₄ -monocarboxylic acid, in particular from (meth)acrylic acid. The second acidic monomer or its salt can be a derivative of a C ₄ -C ₈ -dicarboxylic acid, maleic acid being particularly preferred. In this case, the third monomeric unit is formed by vinyl alcohol and/or preferably an esterified vinyl alcohol. In particular, preference is given to vinyl alcohol derivatives which represent an ester of short-chain carboxylic acids, for example of C ₁ -C ₄ -carboxylic acids, with vinyl alcohol. Preferred terpolymers contain 60% by weight to 95% by weight, in particular 70% by weight to 90% by weight, of (meth)acrylic acid or (meth)acrylate, particularly preferably acrylic acid or acrylate, and maleic acid or maleate as well 5% to 40% by weight, preferably 10% to 30% by weight, of vinyl alcohol and/or vinyl acetate. Very particular preference is given to terpolymers in which the weight ratio of (meth)acrylic acid or (meth)acrylate to maleic acid or maleate is between 1:1 and 4:1, preferably between 2:1 and 3:1 and in particular 2:1 and 2. 5:1 lies. Included both the amounts and the weight ratios are based on the acids. The second acidic monomer or its salt can also be a derivative of an allylsulfonic acid which has an alkyl radical in the 2-position, preferably a C ₁ -C ₄ -alkyl radical, or an aromatic radical which is preferably derived from benzene or benzene derivatives , is substituted. Preferred terpolymers contain 40% by weight to 60% by weight, in particular 45 to 55% by weight, of (meth)acrylic acid or (meth)acrylate, particularly preferably acrylic acid or acrylate, 10% by weight to 30% by weight. %, preferably 15% to 25% by weight of methallyl sulfonic acid or methallyl sulfonate and as a third monomer 15% to 40% by weight, preferably 20% to 40% by weight of a carbohydrate. This carbohydrate can be, for example, a mono-, di-, oligo- or polysaccharide, with mono-, di- or oligosaccharides being preferred, and sucrose being particularly preferred. Presumably, the use of the third monomer incorporates predetermined breaking points in the polymer, which are responsible for the good biodegradability of the polymer. These terpolymers generally have a relative molecular mass of between 1000 g/mol and 200000 g/mol, preferably between 3000 g/mol and 10000 g/mol. They can be used in the form of aqueous solutions, preferably in the form of 30 to 50 percent by weight aqueous solutions, particularly for the production of liquid agents. All of the polycarboxylic acids mentioned are generally used in the form of their water-soluble salts, in particular their alkali metal salts.

Such organic builder substances are preferably present in amounts of up to 40% by weight, in particular up to 25% by weight and particularly preferably from 1% by weight to 5% by weight. Amounts close to the upper limit mentioned are preferably used in pasty or liquid, in particular aqueous, compositions.

In particular, crystalline or amorphous alkali metal aluminosilicates, in amounts of up to 50% by weight, preferably not more than 40% by weight and in liquid compositions, in particular from 1% by weight to 5% by weight, are used as water-insoluble, water-dispersible inorganic builder materials. deployed. Among these, the crystalline detergent grade aluminosilicates, particularly zeolite NaA and optionally NaX, are preferred. Amounts close to the upper limit mentioned are preferably used in solid, particulate compositions. In particular, suitable aluminosilicates do not have any particles with a grain size of more than 30 mm and preferably consist of at least 80% by weight of particles with a size of less than 10 mm. Your calcium binding capacity, according to the information in the German patent specification DE 24 12 837 can be determined is in the range from 100 to 200 mg CaO per gram. Suitable substitutes or partial substitutes for the aluminosilicate mentioned are crystalline alkali metal silicates, which can be present alone or in a mixture with amorphous silicates. The alkali metal silicates which can be used as builders in the agents preferably have a molar ratio of alkali metal oxide to SiO ₂ below 0.95, in particular from 1:1.1 to 1:12, and can be present in amorphous or crystalline form. Preferred alkali metal silicates are the sodium silicates, in particular the amorphous sodium silicates, with a molar Na ₂ O:SiO ₂ ratio of 1:2 up to 1:2.8. Such amorphous alkali metal silicates are commercially available, for example, under the name ^Portil® . During production, they are preferably added as a solid and not in the form of a solution. Crystalline phyllosilicates of the general formula Na ₂ Si _x O _2x+1 · yH ₂ O are preferably used as crystalline silicates, which can be present alone or in a mixture with amorphous silicates, in which x, the so-called modulus, is a number of 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 has the value 2 or 3 in the general formula mentioned. In particular, both β- and δ-sodium disilicates (Na ₂ Si ₂ O ₅ .yH ₂ O) are preferred. Practically anhydrous crystalline alkali metal silicates of the abovementioned general formula, in which x is a number from 1.9 to 2.1, produced from amorphous alkali metal silicates can also be used in agents which contain an active ingredient to be used according to the invention. In a further preferred embodiment of agents according to the invention, a crystalline layered sodium silicate with a modulus of 2 to 3 is used, as can be produced from sand and soda. Crystalline sodium silicates with a modulus in the range from 1.9 to 3.5 are used in a further preferred embodiment of detergents which contain an active ingredient used according to the invention. Their content of alkali metal silicates is preferably 1% by weight to 50% by weight and in particular 5% by weight to 35% by weight, based on anhydrous active substance. If alkali metal aluminosilicate, in particular zeolite, is also present as an additional builder substance, the alkali metal silicate content is preferably 1% by weight to 15% by weight and in particular 2% by weight to 8% by weight, based on anhydrous active substance. The weight ratio of aluminosilicate to silicate, based in each case on anhydrous active substances, is then preferably 4:1 to 10:1. In compositions containing 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.

In addition to the inorganic builder mentioned, further water-soluble or water-insoluble inorganic substances can be present in the agents which contain an active ingredient to be used according to the invention, used together with it or used in processes according to the invention. The alkali metal carbonates, alkali metal hydrogen carbonates and alkali metal sulfates and mixtures thereof are suitable in this connection. Such additional inorganic material may be present in amounts up to 70% by weight.

In addition, the detergents can contain other components that are customary in detergents and cleaning agents. These optional components include, in particular, enzymes, enzyme stabilizers, complexing agents for heavy metals, for example aminopolycarboxylic acids, aminohydroxypolycarboxylic acids, polyphosphonic acids and/or aminopolyphosphonic acids, foam inhibitors, for example organopolysiloxanes or paraffins, solvents and optical brighteners, for example stilbenedisulfonic acid derivatives. In agents which contain an active ingredient used according to the invention, up to 1% by weight, in particular 0.01% by weight to 0.5% by weight, is preferably Optical brighteners, in particular compounds from the class of substituted 4,4'-bis-(2,4,6-triamino-s-triazinyl)-stilbene-2,2'-disulfonic acids, up to 5% by weight, in particular 0 1% by weight to 2% by weight of complexing agents for heavy metals, in particular aminoalkylenephosphonic acids and their salts, and up to 2% by weight, in particular 0.1% by weight to 1% by weight, of foam inhibitors the proportions by weight mentioned relate to the entire agent.

In addition to water, solvents which can be used in particular in the case of liquid agents are preferably those which are water-miscible. These include the lower alcohols, for example ethanol, propanol, isopropanol, and the isomeric butanols, glycerol, lower glycols, for example ethylene and propylene glycol, and the ethers which can be derived from the classes of compounds mentioned. The active ingredients used according to the invention are generally present in such liquid agents in dissolved or suspended form.

Optionally present enzymes are preferably selected from the group comprising protease, amylase, lipase, cellulase, hemicellulase, oxidase, peroxidase or mixtures thereof. Protease obtained from microorganisms such as bacteria or fungi is primarily considered. It can be obtained in a known manner from suitable microorganisms by fermentation processes. Proteases are commercially available, for example, under the names ^BLAP® , ^Savinase® , ^Esperase® , ^Maxatase® , ^Optimase® , ^Alcalase® , ^Durazym® or ^Maxapem® . The lipase that can be used can be obtained, for example, from Humicola lanuginosa, from Bacillus species, from Pseudomonas species, from Fusarium species, from Rhizopus species or from Aspergillus species. Suitable lipases are commercially available, for example, under the names ^Lipolase® , ^Lipozym® , ^Lipomax® , ^Lipex® , ^Amano® lipase, Toyo- ^Jozo® lipase, ^Meito® lipase and ^Diosynth® lipase. Suitable amylases are commercially available, for example, under the names ^Maxamyl® , ^Termamyl® , ^Duramyl® and Purafect® ^OxAm . The cellulase that can be used can be an enzyme that can be obtained from bacteria or fungi and has a pH optimum, preferably in the weakly acidic to weakly alkaline range of 6 to 9.5. Such cellulases are commercially available under the names ^Celluzyme® , ^Carezyme® and ^Ecostone® .

The customary enzyme stabilizers that may be present, particularly in liquid agents, include amino alcohols, for example mono-, di-, triethanolamine and -propanolamine and mixtures thereof, lower carboxylic acids, boric acid or alkali metal borates, boric acid-carboxylic acid combinations, boric acid esters, boronic acid derivatives, calcium salts, for example Ca-formic acid combination, magnesium salts, and/or sulphur-containing reducing agents.

Suitable foam inhibitors include long-chain soaps, in particular behenic soap, fatty acid amides, paraffins, waxes, microcrystalline waxes, organopolysiloxanes and mixtures thereof, as well as microfine, optionally silanated or otherwise hydrophobic silica may contain. For use in particulate compositions, such foam inhibitors are preferably bound to granular, water-soluble carrier substances.

In a preferred embodiment, an agent into which the active ingredient to be used according to the invention is incorporated is particulate and contains up to 25% by weight, in particular 5% by weight to 20% by weight, of bleaching agent, in particular alkali metal percarbonate, up to 15% by weight. -%, in particular 1% to 10% by weight of bleach activator, 20% to 55% by weight of inorganic builder, up to 10% by weight, in particular 2% to 8% by weight. % water-soluble organic builder, 10% to 25% by weight synthetic anionic surfactant, 1% to 5% by weight nonionic surfactant and up to 25% by weight, especially 0.1% by weight up to 25% by weight of inorganic salts, in particular alkali metal carbonate and/or bicarbonate.

In a further preferred embodiment, a composition into which the active substance to be used according to the invention is incorporated is liquid and contains 1% by weight to 25% by weight, in particular 5% by weight to 15% by weight, of nonionic surfactant, up to 10% by weight, in particular 0.5% by weight to 8% by weight, synthetic anionic surfactant, 3% by weight to 15% by weight, in particular 5% by weight to 10% by weight, soap, 0 5% by weight to 5% by weight, in particular 1% by weight to 4% by weight, of organic builder, in particular polycarboxylate such as citrate, up to 1.5% by weight, in particular 0.1% by weight % to 1% by weight of complexing agent for heavy metals, such as phosphonate, and in addition to any enzyme, enzyme stabilizer, dye and/or fragrance contained, water and/or water-miscible solvent.

It is also possible to use a combination of a soil-removing active ingredient essential to the invention with a soil-removing polymer made from a dicarboxylic acid and an optionally polymeric diol to enhance the cleaning performance of detergents when washing textiles. Such combinations with a particularly polyester-active soil-removing polymer are also possible within the scope of agents according to the invention and the method according to the invention.

The known polyester-active soil-release polymers that can be used in addition to the active substances essential to the invention 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 dirt-removing polyesters include those compounds that are formally accessible by esterification of two monomer parts, the first monomer being a dicarboxylic acid HOOC-Ph-COOH and the second monomer being a diol HO-(CHR ¹¹ -) _a OH, which can also be used as a polymeric diol H-(O-(CHR ¹¹ -) _a ) _b OH may be present. Ph is an o-, m- or p-phenylene radical which can carry 1 to 4 substituents selected from alkyl radicals having 1 to 22 carbon atoms, sulfonic acid groups, carboxyl groups and mixtures thereof, R ¹¹ hydrogen, an alkyl radical having 1 to 22 carbon 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- as well as polymer diol units -(O-(CHR ¹¹ -) _a ) _b O-. The molar ratio of monomer diol units to polymer diol units is preferably 100:1 to 1:100, in particular 10:1 to 1:10. The degree of polymerization b in the polymer diol units 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 polyesters with soil release properties is in the range from 250 g/mol to 100,000 g/mol, in particular from 500 g/mol to 50,000 g/mol. The acid on which the radical Ph is based is preferably selected from terephthalic acid, isophthalic acid, phthalic acid, trimellitic acid, mellitic acid, the isomers of sulfophthalic acid, sulfoisophthalic acid and sulfoterephthalic acid and mixtures thereof. If their acid groups are not part of the ester bonds in the polymer, they are preferably present in salt form, in particular as an alkali metal or ammonium salt. Among these, the sodium and potassium salts are particularly preferred. If desired, instead of the HOOC-Ph-COOH monomer, small proportions, in particular not more than 10 mol % based on the proportion of Ph with the meaning given above, of other acids which have at least two carboxyl groups can be present in the soil-removing polyester. These include, for example, alkylene and alkenylenedicarboxylic 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 HO-(CHR ¹¹ -) _a OH include those in which R ¹¹ is hydrogen and a is from 2 to 6 and those in which a is 2 and R ¹¹ is selected from hydrogen and the alkyl radicals 1 to 10, in particular 1 to 3 carbon atoms is selected. Among the last-mentioned diols, those of the formula HO-CH ₂ -CHR ¹¹ -OH, in which R ¹¹ has the meaning given above, are particularly preferred. Examples of diol components are ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,2-decanediol, 1, 2-dodecanediol and neopentyl glycol. Particularly preferred among the polymeric diols is polyethylene glycol with an average molar mass in the range from 1000 g/mol to 6000 g/mol.

If desired, these polyesters composed as described above can also be end-capped, suitable end groups being alkyl groups having 1 to 22 carbon atoms and esters of monocarboxylic acids. The end groups bonded via ester bonds can be based on alkyl, alkenyl and aryl monocarboxylic acids having 5 to 32 carbon atoms, in particular 5 to 18 carbon atoms. These include valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, undecenoic acid, lauric acid, lauroleic acid, tridecanoic acid, myristic acid, myristoleic acid, pentadecanoic acid, palmitic acid, stearic acid, petroselinic acid, petroselaidic acid, oleic acid, linoleic acid, linolaidic acid, linolenic acid, eleostearic acid, arachidic acid , gadoleic acid, arachidonic acid, behenic acid, erucic acid, brassidic acid, clupanodonic acid, lignoceric acid, cerotic acid, melissic acid, benzoic acid, the 1st can carry up to 5 substituents with a total of up to 25 carbon atoms, in particular 1 to 12 carbon atoms, for example tert-butylbenzoic acid. The end groups can also be based on hydroxymonocarboxylic acids with 5 to 22 carbon atoms, which include, for example, hydroxyvaleric acid, hydroxycaproic acid, ricinoleic acid, their hydrogenation product hydroxystearic acid and o-, and p-hydroxybenzoic acid. The hydroxymonocarboxylic acids can in turn be connected to one another via their hydroxyl group and their carboxyl group and can therefore be present more than once 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, in particular from 1 to 10. In a preferred embodiment of the invention, polymers of ethylene terephthalate and polyethylene oxide terephthalate in which the polyethylene glycol units have molecular weights of 750 to 5000 and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate is 50:50 to 90:10, used in combination with a combination with an active ingredient essential to the invention.

The polyester-active soil-removing polymers are preferably water-soluble, the term "water-soluble" meaning a solubility of at least 0.01 g, preferably at least 0.1 g, of the polymer per liter of water at room temperature and pH 8. However, polymers which are preferably used have a solubility of at least 1 g per liter, in particular at least 10 g per liter, under these conditions.

Preferred laundry aftertreatment agents which contain an active ingredient to be used according to the invention have a so-called ester quat, ie a quaternized ester of carboxylic acid and amino alcohol, as the laundry softening active ingredient. These are known substances which can be obtained by the relevant methods of preparative organic chemistry, for example by partially esterifying triethanolamine with fatty acids in the presence of hypophosphorous acid, passing air through it and then quaternizing it with dimethyl sulfate or ethylene oxide. The preparation of solid ester quats is also known, in which the quaternization of triethanolamine esters is carried out in the presence of suitable dispersants, preferably fatty alcohols.

in der R¹CO für einen Acylrest mit 6 bis 22 Kohlenstoffatomen, R² und R³ unabhängig voneinander für Wasserstoff oder R¹CO, R⁴ für einen Alkylrest mit 1 bis 4 Kohlenstoffatomen oder eine (CH₂CH₂O)_qH-Gruppe, m, n und p in Summe für 0 oder Zahlen von 1 bis 12, q für Zahlen von 1 bis 12 und X für ein ladungsausgleichendes Anion wie Halogenid, Alkylsulfat oder Alkylphosphat steht. Typische Beispiele für Esterquats, die im Sinne der Erfindung Verwendung finden können, sind Produkte auf Basis von Capronsäure, Caprylsäure, Caprinsäure, Laurinsäure, Myristinsäure, Palmitinsäure, Isostearinsäure, Stearinsäure, Ölsäure, Elaidinsäure, Arachinsäure, Behensäure und Erucasäure sowie deren technische Mischungen, wie sie beispielsweise bei der Druckspaltung natürlicher Fette und Öle anfallen. Vorzugsweise werden technische C_12/18-Kokosfettsäuren und insbesondere teilgehärtete C_16/18-Talg- beziehungsweise Palmfettsäuren sowie elaidinsäure-reiche C_16/18-Fettsäureschnitte eingesetzt. Zur Herstellung der quaternierten Ester können die Fettsäuren und das Triethanolamin in der Regel im molaren Verhältnis von 1,1 : 1 bis 3 : 1 eingesetzt werden. Im Hinblick auf die anwendungstechnischen Eigenschaften der Esterquats hat sich ein Einsatzverhältnis von 1,2 : 1 bis 2,2 : 1, vorzugsweise 1,5 : 1 bis 1,9 : 1 als besonders vorteilhaft erwiesen. Die bevorzugt eingesetzten Esterquats stellen technische Mischungen von Mono-, Di- und Triestern mit einem durchschnittlichen Veresterungsgrad von 1,5 bis 1,9 dar und leiten sich von technischer C_16/18-Talg- bzw. Palmfettsäure (lodzahl 0 bis 40) ab. Quaternierte Fettsäuretriethanolaminestersalze der Formel (IV), in der R¹CO für einen Acylrest mit 16 bis 18 Kohlenstoffatomen, R² für R¹CO, R³ für Wasserstoff, R⁴ für eine Methylgruppe, m, n und p für 0 und X für Methylsulfat steht, haben sich als besonders vorteilhaft erwiesen.Esterquats preferred in the compositions are quaternized fatty acid triethanolamine ester salts which follow the formula (IV),

in which R ¹ CO is an acyl radical having 6 to 22 carbon atoms, R ² and R ³ are each independently hydrogen or R ¹ CO, R ⁴ is an alkyl radical having 1 to 4 carbon atoms or a (CH ₂ CH ₂ O) _q H- Group, m, n and p in total are 0 or numbers from 1 to 12, q is numbers from 1 to 12 and X is a charge-balancing anion such as halide, alkyl sulfate or alkyl phosphate. Typical examples of esterquats that can be used according to the invention are products based on caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, isostearic acid, stearic acid, oleic acid, elaidic acid, arachidic acid, behenic acid and erucic acid, and technical mixtures thereof, such as they occur, for example, in the pressure splitting of natural fats and oils. Technical C _12/18 coconut fatty acids and in particular partially hydrogenated C _16/18 tallow or palm fatty acids and C _16/18 fatty acid cuts rich in elaidic acid are preferably used. To prepare the quaternized ester, the fatty acids and the triethanolamine can generally be used in a molar ratio of from 1.1:1 to 3:1. With regard to the performance properties of the esterquats, a ratio of from 1.2:1 to 2.2:1, preferably from 1.5:1 to 1.9:1, has proven to be particularly advantageous. The esterquats preferably used are technical mixtures of mono-, di- and triesters with an average degree of esterification of 1.5 to 1.9 and are derived from technical C _16/18 tallow or palm fatty acid (iodine number 0 to 40). . Quaternized fatty acid triethanolamine ester salts of the formula (IV) in which R ¹ CO represents an acyl radical having 16 to 18 carbon atoms, R ² represents R ¹ CO, R ³ represents hydrogen, R ⁴ represents a methyl group, m, n and p represent 0 and X represents Methyl sulfate is, have proven to be particularly advantageous.

in der R¹CO für einen Acylrest mit 6 bis 22 Kohlenstoffatomen, R² für Wasserstoff oder R¹CO, R⁴ und R⁵ unabhängig voneinander für Alkylreste mit 1 bis 4 Kohlenstoffatomen, m und n in Summe für 0 oder Zahlen von 1 bis 12 und X für ein ladungsausgleichendes Anion wie Halogenid, Alkylsulfat oder Alkylphosphat steht.In addition to the quaternized carboxylic acid triethanolamine ester salts, quaternized ester salts of carboxylic acids with diethanolalkylamines of the formula (V) are also suitable as ester quats,

in which R ¹ CO is an acyl radical having 6 to 22 carbon atoms, R ² is hydrogen or R ¹ CO, R ⁴ and R ⁵ are each independently alkyl radicals having 1 to 4 carbon atoms, m and n together are 0 or numbers from 1 to 12 and X is a charge-balancing anion such as halide, alkyl sulfate or alkyl phosphate.

in der R¹CO für einen Acylrest mit 6 bis 22 Kohlenstoffatomen, R² für Wasserstoff oder R¹CO, R⁴, R⁶ und R⁷ unabhängig voneinander für Alkylreste mit 1 bis 4 Kohlenstoffatomen, m und n in Summe für 0 oder Zahlen von 1 bis 12 und X für ein ladungsausgleichendes Anion wie Halogenid, Alkylsulfat oder Alkylphosphat steht.Finally, another group of suitable ester quats are the quaternized ester salts of carboxylic acids with 1,2-dihydroxypropyldialkylamines of the formula (VI),

in which R ¹ CO is an acyl radical having 6 to 22 carbon atoms, R ² is hydrogen or R ¹ CO, R ⁴ , R ⁶ and R ⁷ are each independently alkyl radicals having 1 to 4 carbon atoms, m and n together are 0 or numbers from 1 to 12 and X is a charge-balancing anion such as halide, alkyl sulfate or alkyl phosphate.

With regard to the selection of the preferred fatty acids and the optimal degree of esterification, the exemplary statements given for (IV) also apply mutatis mutandis to the esterquats of the formulas (V) and (VI). The esterquats are usually sold in the form of 50 to 90 percent by weight alcoholic solutions, which can also be diluted with water without any problems, the usual alcoholic solvents being ethanol, propanol and isopropanol.

Esterquats are preferably used in amounts of 5% by weight to 25% by weight, in particular 8% by weight to 20% by weight, based in each case on the total laundry aftertreatment agent. If desired, the laundry aftertreatment agents used according to the invention can also contain the detergent ingredients listed above, provided they do not have an unacceptable negative interaction with the ester quat. It is preferably a liquid, water-containing agent.

examples Example 1: Preparation of xylan carbamates a) Synthesis of N-(2-ethoxyethyl)xylancarbamate

• FT-IR (KBr): 3411 cm^-1 (OH); 2974 cm^-1 (CH₂); 2872 cm^-1 (CH₂); 1715 cm^-1 (C=O); 1047 cm^-1 (C-O-C)
• ¹³C-NMR (250 MHz, DMSO-d₆,): δ [ppm] 155,9; 155,6; 155,2 (C=O); 101,7 (C-1); 75,5; 74,1; 71,8; 70,9 (C-2 - C-4); 68,5 (CH₂); 65,4 (CH₂); 62,8 (C-5); 15,1 (CH₃)
• EA: C: 48,84%; H: 7,05%; N: 6,18%
• DS: 1,18

33.9 ml of 2-ethoxyethylamine (323.3 mmol) were added to 25 g of xylan phenyl carbonate (92.1 mmol, DS 1.17) in 750 ml of dry DMF. The reaction solution was stirred at room temperature for 30 minutes. The mixture is then heated to 60° C. and kept at this temperature for 20 hours. The product was precipitated by adding the reaction mixture to 4 l of diethyl ether and filtered off with suction (G3 frit). The xylan carbamate was washed once with 1.5 l of diethyl ether and three times with 1.5 l of ethyl acetate each time and dissolved in 700 ml of distilled water without drying. The solution was freed from the remaining ethyl acetate by azeotropic distillation at 80 mbar and then freeze-dried (4 days, -42° C., 0.25 mbar). Yield: 16.84 g (69%)

• FT-IR (KBr): 3411 cm ^-1 (OH); 2974 cm ^-1 (CH ₂ ); 2872 cm ^-1 (CH ₂ ); 1715 cm ^-1 (C=O); 1047 cm ^-1 (COC)
• ¹³ C-NMR (250 MHz, DMSO-d ₆ ): δ [ppm] 155.9; 155.6; 155.2 (C=O); 101.7 (C-1); 75.5; 74.1; 71.8; 70.9 (C-2 - C-4); 68.5 ( _CH2 ); 65.4 ( _CH2 ); 62.8 (C-5); 15.1 ( _CH3 )
• EA: C: 48.84%; H: 7.05%; N: 6.18%
• DS: 1.18

b) Synthesis of N-(3-(N',N',N'-trimethylammonium iodide)propyl)xylan carbamate

• beschriebenen Verfahren aus Xylanphenylcarbonat (25 g; 130,2 mmol; DS 0,51) und 3-Amino-N,N,N-trimethylpropan-1-aminiumiodid (61,6 g; 252,6 mmol) hergestellt. Ausbeute: 22,67 g (67%)
• FT-IR (KBr): 3443 cm^-1 (OH); 2924 cm^-1 (CH₂); 2881 cm^-1 (CH₂); 1712 cm^-1 (C=O); 1045 cm^-1 (C-O-C
• ¹³C-NMR (250 MHz, DMSO-d₆,): δ [ppm] 156,0; 155,8; 155,4 (C=O); 101,6 (C-1); 75,4; 74,9; 72,3; (C-2 - C-4); 63,5 (CH₂); 62,8 (C-5); 52,3 (CH₃); 37,4 (CH₂), 22,9 (CH₂)
• EA: C: 37,72%; H: 5,86%; N: 5,14%; I: 21,75%
• DS: 0,48

N-(3-(N',N',N'-trimethylammonium iodide)propyl)-xylancarbamate was analogous to that under a)

• method described from xylan phenyl carbonate (25 g; 130.2 mmol; DS 0.51) and 3-amino-N,N,N-trimethylpropane-1-aminium iodide (61.6 g; 252.6 mmol). Yield: 22.67 g (67%)
• FT-IR (KBr): 3443 cm ^-1 (OH); 2924 cm ^-1 (CH ₂ ); 2881 cm ^-1 (CH ₂ ); 1712 cm ^-1 (C=O); 1045 cm ^-1 (COC
• ¹³ C-NMR (250MHz, DMSO-d ₆ ): δ [ppm] 156.0; 155.8; 155.4 (C=O); 101.6 (C-1); 75.4; 74.9; 72.3; (C-2 - C-4); 63.5 ( _CH2 ); 62.8 (C-5); 52.3 ( _CH3 ); 37.4 ( _CH2 ), 22.9 ( _CH2 )
• EA: C: 37.72%; H: 5.86%; N: 5.14%; I: 21.75%
• DS: 0.48

c) Synthesis of N-(2-ethoxyethyl)xylancarbamate

• FT-IR (KBr): 3414 cm^-1 (OH); 2970 cm^-1 (CH₂); 2881 cm^-1 (CH₂); 1719 cm^-1 (C=O); 1043 cm^-1 (C-O-C)
• ¹³C-NMR (250 MHz, DMSO-d₆,): δ [ppm] 155,9; 155,6 (C=O); 101,8 (C-1); 77,5; 75,5; 74,1; 72,7; 72,1; 71,0 (C-2 - C-4); 68,6 (CH₂); 65,4 (CH₂); 62,9 (C-5); 15,1 (CH₃)
• EA: C: 46,29%; H: 6,66%; N: 3,81%;
• DS: 0,52

N-(2-Ethoxyethyl)xylancarbamate was prepared analogously to the process described under a) from xylanphenyl carbonate (25 g; 132.6 mmol; DS 0.48) and 2-ethoxyethylamine (17.02 g; 190.9 mmol). . Yield: 21.86 g (86%)

• FT-IR (KBr): 3414 cm ^-1 (OH); 2970 cm ^-1 (CH ₂ ); 2881 cm ^-1 (CH ₂ ); 1719 cm ^-1 (C=O); 1043 cm ^-1 (COC)
• ¹³ C-NMR (250 MHz, DMSO-d ₆ ): δ [ppm] 155.9; 155.6 (C=O); 101.8 (C-1); 77.5; 75.5; 74.1; 72.7; 72.1; 71.0 (C-2 - C-4); 68.6 ( _CH2 ); 65.4 ( _CH2 ); 62.9 (C-5); 15.1 ( _CH3 )
• EA: C: 46.29%; H: 6.66%; N: 3.81%;
• DS: 0.52

d) Synthesis of N,N-(2-Methoxyethyl)methyl xylancarbamate

• FT-IR (KBr): 3450 cm^-1 (OH); 2926 cm^-1 (CH₂); 1797 cm^-1 (C=O); 1051 cm^-1 (C-O-C)
• ¹³C-NMR (250 MHz, DMSO-d₆,): δ [ppm] 155,3 (C=O); 101,8 (C-1); 75,6; 74,1; 72,9; 72,6 (C-2 - C-4); 69,94 (CH₂); 63,2 (C-5); 62,8 (C-5); 58,1 (CH₃); 47,6 (CH₃), 36,8 (CH₂)
• EA: C: 46,11%; H: 6,35%; N: 2,89%;
• DS: 0,36

N,N-(2-Methoxyethyl)methyl-xylancarbamate was prepared analogously to the process described under a) from xylanphenyl carbonate (30.8 g; 167.76; DS 0.43) and N-(2-methoxyethyl)methylamine (19, 3 g; 216.4 mmol). Yield: 24.22 g (76%)

• FT-IR (KBr): 3450 cm ^-1 (OH); 2926 cm ^-1 (CH ₂ ); 1797 cm ^-1 (C=O); 1051 cm ^-1 (COC)
• ¹³ C-NMR (250 MHz, DMSO-d ₆ ): δ [ppm] 155.3 (C=O); 101.8 (C-1); 75.6; 74.1; 72.9; 72.6 (C-2 - C-4); 69.94 ( _CH2 ); 63.2 (C-5); 62.8 (C-5); 58.1 ( _CH3 ); 47.6 (CH3 ), 36.8 ( _{CH2 )}
• EA: C: 46.11%; H: 6.35%; N: 2.89%;
• DS: 0.36

example 2

Table 1 shows the composition (ingredients in percent by weight, in each case based on the total detergent) of the detergents M1 to M4 according to the invention and of the detergent V1, which is free from a corresponding active ingredient: Table 1: Composition V1 M1 M2 M3 M4 C _9-13 alkyl benzene sulfonate, Na salt 5 5 5 5 5 Sodium Lauryl Ether Sulfate with 2 EO 6 6 6 6 6 C _12-14 fatty alcohol with 7 EO 5 5 5 5 5 C _12-18 fatty acid, Na salt 3 3 3 3 3 NaOH 2 2 2 2 2 citric acid 2 2 2 2 2 phosphonate 0.2 0.2 0.2 0.2 0.2 enzymes, dyes, opt. brighteners, alcohols, boric acid, perfume 7 7 7 7 7 Active substance I ^a) - 1.5 - - - active substance II ^b) - - 1.5 - - Active substance III ^c) - - - 1.5 - Active substance IV ^d) - - - - 1.5 water to 100 a) N-(2-Ethoxyethyl)-xylancarbamate from Example 1 a)
b) N-(3-(N',N',N'-trimethylammonium iodide)propyl)xylancarbamate from example 1 b)
c) N-(2-Ethoxyethyl)xylancarbamate from Example 1 c)
d) N,N-(2-Methoxyethyl)methyl-xylancarbamate from Example 1 d)

Clean textiles made of cotton or polyester were washed 3 times in a ^Miele® W 1935 washing machine at 40° C. with water of 16° dH with the detergents and then air-dried. This was followed by the application of the standardized stains given in Table 2 to the test textiles and the stains were aged for 7 days. The textiles prepared in this way were washed again under the above-mentioned conditions with a load of 3.5 kg (clean load wash plus test textiles) with the detergent previously used in each case. The evaluation was colorimetric; Table 2 gives the mean values of the brightness values (Y values) from 6-fold determinations. Table 2: Brightness value Y soiling / medium V1 M1 M2 M3 M4 Chocolate Ice Cream / Cotton 66.9 68.7 nb 67.9 68.7 makeup / cotton 35.4 36.8 39.7 36.4 nd Lipstick (pink) / cotton 36.1 37.8 39.2 nb 37.7 Motor oil (used) / cotton 66.3 67.8 nb 68.0 68.9 Black shoe polish / polyester 28.4 32.7 37.9 30.9 nb

Claims (10)

1. The use of xylan derivatives which contain a unit of general formula (I),

   

   in which R¹ and R² represent, independently of one another, H or -C(=O)-NR³R⁴, with the proviso that at least 1 of the groups R¹ and R² is equal to -C(=O)-NR³R⁴, and

   R³ and R⁴ represent, independently of one another, -H, aryl, straight-chain or branched alkyl, aryl, alkylaryl or arylalkyl groups, which can be substituted with one or more functional groups such as hydroxy, carboxy, oxy, amino or ammonium groups, and/or which can be interrupted with heteroatoms such as N, O or S,

   for enhancing the cleaning performance of washing agents when washing textiles.
2. A method for washing textiles, wherein a washing agent and a xylan derivative which contains a unit of general formula (I),

   

   in which R¹ and R² represent, independently of one another, H or -C(=O)-NR³R⁴, with the proviso that at least 1 of the groups R¹ and R² is equal to -C(=O)-NR³R⁴, and

   R³ and R⁴ represent, independently of one another, -H, aryl, straight-chain or branched alkyl, aryl, alkylaryl or arylalkyl groups, which can be substituted with one or more functional groups such as hydroxy, carboxy, oxy, amino or ammonium groups, and/or which can be interrupted with heteroatoms such as N, O or S,

   are used.
3. The method according to claim 2, characterized in that the use concentration of the xylan derivative in the wash liquor is 0.001 g/l to 1 g/l, in particular 0.005 g/l to 0.2 g/l.
4. The method according to claim 2 or 3, characterized in that said method is carried out using a washing agent which contains the xylan derivative.
5. The method for washing textiles according to one of claims 2 to 4, characterized in that said method is carried out using a laundry aftertreatment agent, in particular fabric softener, which contains the xylan derivative.
6. A washing agent or laundry aftertreatment agent, containing a xylan derivative which contains a unit of general formula (I),

   

   in which R¹ and R² represent, independently of one another, H or -C(=O)-NR³R⁴, with the proviso that at least 1 of the groups R¹ and R² is equal to -C(=O)-NR³R⁴, and
   R³ and R⁴ represent, independently of one another, -H, aryl, straight-chain or branched alkyl, aryl, alkylaryl or arylalkyl groups, which can be substituted with one or more functional groups such as hydroxy, carboxy, oxy, amino or ammonium groups, and/or which can be interrupted with heteroatoms such as N, O or S.
7. The method according to claim 4 or 5 or the agent according to claim 6, characterized in that the agent contains the xylan derivative in amounts of from 0.01 wt.% to 10 wt.%, in particular from 0.1 wt.% to 3 wt.%.
8. The use according to claim 1 or the method according to one of claims 2 to 5 or 7 or the agent according to claim 6 or 7, characterized in that, in general formula (I), the groups -NR³R⁴ are derived from amino alcohols, polyalkoxylated amines, α-amino acids, ß-amino acids, ω-amino acids, aniline, which can be substituted on the ring if desired, benzylamine, which can be substituted on the ring if desired, morpholine, N-aminomorpholine, N-aminoalkylmorpholine, ethylenediamine, and mixtures thereof.
9. The use, method or agent according to one of the preceding claims, characterized in that the xylan derivative contains, in addition to the substituted anhydroxylose unit of general formula (I), further anhydroxylose units which are linked thereto and which can be unsubstituted or correspond to general formula (I).
10. The use, method or agent according to one of the preceding claims, characterized in that anhydroxylose groups having other substituents are also present in the xylan derivative, said substituents including for example alkyl groups such as methyl or ethyl groups, hydroxyalkyl groups such as hydroxyethyl or hydroxypropyl groups, carboxyalkyl groups such as carboxymethyl or carboxyethyl groups, aminoalkyl groups such as aminoethyl or trimethylammonium ethyl groups, sulfoalkyl groups such as sulfoethyl or sulfopropyl groups, ester groups such as acetic acid, ß-aminopropionic acid, glycolic acid or malonic acid ester groups, and/or in that the degree of substitution in the xylan carbamate, based on the proportion of carbamate groups, is in the range of from 0.1 to 1.8, in particular in the range of from 0.2 to 1.2.