WO2019243072A1

WO2019243072A1 - Pullulan derivatives as soil release agents

Info

Publication number: WO2019243072A1
Application number: PCT/EP2019/064815
Authority: WO
Inventors: Christian Kropf; Antje Gebert-Schwarzwaelder; Christa JUNKES; Thomas Heinze; Lars Gabriel; Christian DEGERING; Brian LAUFS
Original assignee: Henkel Ag & Co. Kgaa
Priority date: 2018-06-20
Filing date: 2019-06-06
Publication date: 2019-12-26
Also published as: DE102018209992A1; EP3810740A1

Abstract

The aim of the invention is to improve the cleaning performance of washing agents during laundering of textiles. This is substantially achieved by the use of carboxy- or sulfo-alkylated pullulan.

Description

Pullulan derivatives as dirt-removing agents

The present invention relates to the use of certain dirt-releasing active substances to enhance the cleaning performance of detergents when washing textiles.

In addition to the ingredients that are indispensable for the washing process, such as surfactants and builder materials, detergents generally contain other ingredients that can be summarized under the term washing aids and which contain different active ingredient groups such as foam regulators, graying inhibitors, bleaching agents, bleach activators and

Color transfer inhibitors include. Such auxiliary substances 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 components. The same applies analogously to cleaning agents for hard surfaces. Such soil release agents are often referred to as "soil release" actives or, because of their ability to make the treated surface, for example the fiber, dirt-repellent, "soil repellents". For example, from US Pat. No. 4,136,038 the The dirt-releasing effect of methyl cellulose is known. European patent application EP 0 213 729 discloses the reduced redeposition when using detergents which contain a combination of soap and nonionic surfactant with alkyl-hydroxyalkyl cellulose. Textile treatment agents are known from European patent application EP 0 213 730. which contain cationic surfactants and nonionic cellulose ethers with HLB values from 3.1 to 3.8 The US Pat. No. 4,000,093 discloses detergents which contain 0.1% by weight to 3% by weight alkyl cellulose, Hydroxyalkyl cellulose or alkyl hydroxyalkyl cellulose and 5 wt .-% to 50 wt .-% surfactant, wob egg the

Surfactant component consists essentially of C10 to Ci3 alkyl sulfate and has up to 5% by weight of C14 alkyl sulfate and less than 5% by weight of alkyl sulfate with alkyl radicals of C15 and higher.

In individual cases, however, it is observed that the effect of such cellulose derivatives in water-containing liquid detergents can deteriorate after particularly long storage under unfavorable conditions.

Because of their chemical similarity to polyester fibers in textiles made from this material, particularly effective dirt-releasing active ingredients are copolyesters

Contain 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. Soil-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 they have no or only inadequate activity, particularly in the case of textiles which do not consist, or at least not predominantly, of polyester. A large part of today's textiles, however, consists of cotton or cotton-polyester blended fabrics, so that there is a need for dirt-releasing active substances which are more effective in the case of greasy soiling on textiles of this type in particular.

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

The invention relates to the use of pullulan derivatives, the modified

Contain anhydroglycoside units of the general formula (I),

in which the radicals R independently of one another are -OH, -0 (CH ₂ ) nC00H, -0 (CH ₂ ) nC00 X ⁺ , -0 (CH ₂ ) mS0 ₃ H, -0 (CH ₂ ) mS03 X ⁺ , n and m independently of one another represent numbers from 1 to 3, preferably n for 1 and / or m for 2, and X ⁺ for a charge-balancing cation, in particular an alkali metal ion such as sodium or potassium and / or

Ammonium ion, where at least some of the radicals R do not represent -OH,

to increase the cleaning performance of detergents when washing textiles.

Pullulan ethers of the general formula (I) can be obtained by reacting pullulan with

Haloalkanoic acids or their salts such as chloroacetic acid or

Sodium chloroacetate or with alkenesulfonic acids or their salts such as, for example

Vinyl sulfonic acid or sodium vinyl sulfonate available, as for example in Glinel K, Paul Sauvage J, Oulyadi H, Huguet J, Determination of substitutes distribution in

carboxymethylpullulans by NMR spectroscopy, Carbohydr Res 328 (2000), 343-354; Bataille I, Huguet J, Müller G, Mocanu G, Carpov A, Associative behavior of hydrophobically modified carboxymethylpullulan derivatives, Int J Bio Macromol 20 (1997), 179-191; Mocanu G, Mihai D, Picton L, LeCerf D, Müller G, Associative pullulan gels and their interaction with biological active substances, Journal of Controlled Release 83 (2002), 41-51; Picton L, Mocanu G, Mihai D, Carpov A, Müller G, Chemically modified exopolysaccharide pullulans: physico-chemical characteristics of ionic derivatives, Carbohydr. Polym. 28: 131-136 (1995); or described in US Pat. No. 5,100,877.

The average degree of substitution (DS), based on the proportion of radicals R which are not —OH, in the pullulan derivative to be used according to the invention is preferably in the range from 0.1 to 1.2, in particular 0.2 to 0.9. The average degree of polymerization (DP) is in the pullulan used for the preparation of the pullulan derivatives to be used according to the invention, based on the simple sugar unit in the general formula (I) with R = -OH, preferably in the range from 100 to 1200, in particular in the range from 200 to 800. Among the

Pullulan derivatives to be used according to the invention are those with a number-average molar mass in the range from 5000 g / mol to 150,000 g / mol, in particular in the range from 30,000 g / mol to 120,000 g / mol, to be determined, for example, by means of size exclusion chromatography (GPC, for example eluent 0.5 % LiBr in DMSO, flow rate 0.5 ml / min, system JASCO®, pump: PU-980, detector: RI-930, column: PSS Novema 300 and PSS Novema 3000 in series) and Pullulan as

Calibration standard, preferred.

The pullulan derivative preferably has no units other than those of the general formula (I).

Another object of the invention is a method for washing textiles, in which a detergent and a dirt-releasing active ingredient are used in the form of a pullulan derivative defined above. These methods can be carried out manually or, if appropriate, using a conventional household washing machine. It is possible to use the detergent and the dirt-releasing active ingredient simultaneously or in succession. The simultaneous use can be carried out particularly advantageously by using a detergent which contains the dirt-releasing active ingredient. The method essentially consists in bringing a textile in need of cleaning or at least the soiled part of its surface into contact with an aqueous preparation which contains the pullulan derivative defined above, the aqueous preparation onto the textile or at least the soiled for a certain time Allow part of its surface to act and remove the aqueous preparation, for example by rinsing the textile with water.

The effect of the active ingredient to be used according to the invention is particularly pronounced when used repeatedly, that is to say 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 soiled. In connection with the Aftertreatment is to be pointed out that the positive aspect described can also be realized by a washing process in which the textile, after the actual washing process, can be free of this with the aid of a detergent which can contain an active ingredient mentioned , is brought into contact with a post-treatment agent, for example in the context of a fabric softening step, which contains an active ingredient to be used according to the invention, in the presence of water. With this procedure too, the washing performance-enhancing effect of the active ingredients to be used according to the invention occurs during the next washing operation, 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 that resulting from the use of a conventional soil release agent. In a particularly preferred embodiment, the active ingredient essential to the invention is added in the softener cycle, in particular the machine one

Textile washing.

The active ingredient used according to the invention leads to a significantly better detachment of, in particular, grease and cosmetic stains on textiles, in particular those made of cotton or cotton-containing fabric, than is the case when using compounds known hitherto for this purpose. Alternatively, significant amounts of surfactants can be saved while maintaining the ability to remove fat.

Furthermore, it was observed that, in the presence of the pullulan derivatives essential to the invention in the washing process, there is less redeposition of dirt already detached from the textile onto the cleaned textile, so that in the presence of an essential component of the invention

Textiles washed with pullulan derivatives turn gray significantly less than those washed in the absence of the pullulan derivative essential to the invention. Another object of the invention is therefore the use of the pullulan derivatives defined above for reducing the graying of textiles, in particular textiles made of cotton or

Cotton included when washing.

The uses according to the invention can be carried out in the course of a washing process in such a way that the dirt-releasing active ingredient is added to a detergent-containing liquor or, preferably, the active ingredient is introduced as a constituent of a detergent into the liquor which contains the article to be cleaned or is brought into contact with it.

The use according to the invention in the context of a laundry aftertreatment process can accordingly take place in such a way that the dirt-releasing active ingredient is added separately to the washing liquor, which is used after the washing step using a detergent, or as a component of the laundry aftertreatment agent, in particular a fabric softener. In this aspect of the invention, this can be done before Laundry aftertreatment detergents used also have a

Contain active ingredient to be used according to the invention, but can also be free of this.

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

The washing process is preferably carried out at a temperature of 15 ° C to 60 ° C, particularly preferably at a temperature of 20 ° C to 40 ° C. The washing process is also preferably carried out at a pH of 6 to 11, particularly preferably at a pH of 7.5 to 9.5. The concentration of the pullulan derivative in the wash liquor is preferably 0.0001 g / l to 1 g / l, in particular 0.001 g / l to 0.2 g / l.

Detergents which contain an active ingredient to be used according to the invention in the form of the pullulan derivative mentioned or used together with it or in

Processes according to the invention can contain all the usual other constituents of such agents which do not interact undesirably with the active substance essential to the invention, in particular surfactant. The active substance 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, this and the following amounts being based on one another draw the entire average unless otherwise stated. Preferably, an inventive or in

Process used according to the invention or within the scope of the inventive

Use agent used watery and liquid; it contains in particular 2% by weight to 92% by weight, particularly preferably 3% by weight to 85% by weight, of water.

Surprisingly, it was found that the active ingredient used according to the invention has a positive influence on the action of certain other detergent ingredients and that, conversely, the action of the soil release active ingredient is additionally enhanced by certain other detergent ingredients. These effects occur in particular in the case of bleaching agents, in the case of enzymatic active substances, in particular proteases and lipases, in the case of water-soluble inorganic and / or organic builders, in particular based on oxidized carbohydrates or polymers

Polycarboxylates, in the case of synthetic anionic surfactants of the sulfate and sulfonate type, and in

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.

An agent which contains an active ingredient to be used according to the invention or is used together with it or is used in the process according to the invention preferably contains peroxygen-based bleaching agents, in particular in amounts in The range from 5% by weight to 70% by weight and, if appropriate, bleach activator, in particular in amounts in the range from 2% by weight to 10% by weight, can, however, also be free of bleaching agent and bleach activator in another preferred embodiment , The bleaches in question are preferably those which are generally used in detergents

Peroxygen compounds such as percarboxylic acids, for example dodecanediperic acid or phthaloylaminoperoxicaproic acid, hydrogen peroxide, alkali perborate, which can be present as tetra- 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 obtained 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 medium, with percarbonate in particular being used. The optional component of the bleach activators includes 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, sulfuryl amides

Cyanurates, also carboxylic anhydrides, in particular phthalic anhydride,

Carboxylic acid esters, especially sodiumisononanoylphenolsulfonate, and acylated sugar derivatives, especially pentaacetylglucose, and cationic nitrile derivatives such as

Trimethylammonioacetonitrile salts. The bleach activators can be used to avoid the

Interaction with the peroxygen compounds during storage in a known manner have been coated or granulated with coating substances, with the aid of

Carboxymethylcellulose granulated tetraacetylethylenediamine with weight-average grain sizes of 0.01 mm to 0.8 mm, granulated 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine, and / or trialkylammonium acetonitrile made up in particle form is particularly preferred. In

Such bleach activators are preferably contained in detergents in amounts of up to 8% by weight, in particular from 2% by weight to 6% by weight, in each case based on the total agent.

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, especially 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 surfactants 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% by weight to 25% by weight. The anionic surfactant from the alkyl or alkenyl sulfates is preferred 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 them, preferred are those whose proportion of compounds with longer-chain radicals in the range from 16 to 18 carbon atoms is over 20% by weight.

The nonionic surfactants in question 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 to prepare alkoxylates which can be used. 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. In addition, the ethylene oxide and / or propylene oxide insertion products of fatty acid alkyl esters and fatty acid polyhydroxyamides are also suitable. 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 C 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 made from naturally occurring aldose or ketose monomers, 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, characterized. The degree of oligomerization n generally takes fractional numerical values as the quantity to be determined analytically; it is between 1 and 10, for the glycosides preferably used below 1, 5, in particular between 1, 2 and 1. The preferred monomer building block is glucose because of its good availability. 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 are particularly useful. Particularly preferred alkyl glycosides contain a coconut fatty alkyl radical, ie mixtures with essentially R ¹² = dodecyl and R ¹² = tetradecyl. Nonionic surfactant is used in agents which contain a soil release active ingredient used according to the invention, are used according to the invention or are used in the process according to the invention, preferably in amounts from 1% by weight to 30% by weight, in particular from 1% by weight to 25 Contain wt .-%, with amounts in the upper part of this range rather in liquid

Detergents are to be found and particulate detergents preferably contain smaller amounts of up to 5% by weight.

Instead, or in addition, the agents can contain further surfactants, preferably synthetic ones

Anionic surfactants of the sulfate or sulfonate type, such as, for example, 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 agents of this type are the alkyl and / or alkenyl sulfates having 8 to 22 carbon atoms and carrying an alkali metal, ammonium or alkyl or hydroxyalkyl-substituted ammonium ion as countercation. The derivatives of fatty alcohols with in particular 12 to 18 carbon atoms and their branched-chain analogs, the so-called oxo alcohols, are preferred. The alkyl and alkenyl sulfates can in a known manner by reaction of the corresponding

Alcohol component with a conventional sulfating agent, in particular sulfur trioxide or chlorosulfonic acid, and subsequent neutralization with alkali, 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 a-sulfoesters obtainable by reacting fatty acid esters with sulfur trioxide and subsequent neutralization, in particular those derived from fatty acids with 8 to 22 C atoms, preferably 12 to 18 C atoms, and linear alcohols with 1 up to 6 carbon atoms, preferably 1 to 4 carbon atoms, derived sulfonation products, and the sulfofatty acids resulting from these by formal saponification.

Soaps are further optional surfactant ingredients, 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. Soap mixtures are particularly preferred which are composed of 50% by weight to 100% by weight of saturated Ci2-Ci8 fatty acid soaps and up to 50% by weight of oleic acid soap. Soap is preferably contained in amounts of 0.1% by weight to 5% by weight. However, in particular in liquid compositions which contain a polymer used according to the invention, higher amounts of soap, as a rule up to 20% by weight, can also be present. If desired, the agents can also contain betaines and / or cationic surfactants which - if present - are preferably used in amounts of 0.5% by weight to 7% by weight. Among them, the ester quats discussed below are particularly preferred.

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

The agent 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, especially citric acid and sugar acids, as well as the polymeric (poly) carboxylic acids, especially those that are accessible through the oxidation of polysaccharides

Polycarboxylates, polymeric acrylic acids, methacrylic acids, maleic acids and copolymers of these, which can also contain small amounts of polymerizable substances without carboxylic acid functionality in copolymerized form. The relative molecular weight 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 50,000 g / mol to 120,000 g / mol, based on 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, 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% 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 C3-Cs carboxylic acid and 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 ₄ -C8 dicarboxylic acid, where

Maleic acid is particularly preferred. In this case, the third monomeric unit is formed from vinyl alcohol and / or preferably an esterified vinyl alcohol. Vinyl alcohol derivatives which contain an ester of short-chain carboxylic acids,

for example of Ci-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.

(Meth) acrylic acid or (meth) acrylate, particularly preferably acrylic acid or acrylate, and

Maleic acid or maleate and 5% by weight to 40% by weight, preferably 10% by weight to 30% by weight, of vinyl alcohol and / or vinyl acetate. Terpolymers in which the weight ratio (meth) acrylic acid or (meth) acrylate to maleic acid are very particularly preferred 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. 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, in the 2-position, has an alkyl radical, 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% by weight to 25% by weight of methallylsulfonic acid or methallylsulfonate and as the third monomer 15% by weight to 40% by weight, preferably 20% by weight to 40% by weight of a carbohydrate. This carbohydrate can be, for example, a mono-, di-, oligo- or polysaccharide, mono-, di- or oligosaccharides being preferred, sucrose being particularly preferred. The use of the third monomer presumably creates predetermined breaking points in the polymer, which are responsible for the good biodegradability of the polymer. These terpolymers generally have a relative molecular weight between 1000 g / mol and 200000 g / mol, preferably between 3000 g / mol and 10000 g / mol. They can be used, in particular for the production of liquid agents, in the form of aqueous solutions, preferably in the form of 30 to 50 percent by weight aqueous solutions. All of the above

Polycarboxylic acids are generally used in the form of their water-soluble salts, especially their alkali 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 paste-like or liquid, in particular water-containing, agents.

In particular, crystalline or amorphous alkali alumosilicates are used as water-insoluble, water-dispersible inorganic builder materials, 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. used. Among these, the crystalline aluminosilicates in detergent quality, in particular zeolite NaA and optionally NaX, are preferred. Amounts close to the upper limit mentioned are preferably used in solid, particulate compositions. Suitable aluminosilicates in particular have no 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. Their calcium binding capacity, which can be determined according to the information in German patent DE 24 12 837, is in the range from 100 to 200 mg CaO per gram. Suitable substitutes respectively

Partial substitutes for the alumosilicate mentioned are crystalline alkali silicates, which can be present alone or in a mixture with amorphous silicates. The usable as builders in the agents

Alkali silicates preferably have a molar ratio of alkali oxide to S1O2 below 0.95, in particular from 1: 1, 1 to 1:12 and can be amorphous or crystalline. Preferred alkali silicates are the sodium silicates, in particular the amorphous sodium silicates, with a Na ₂ 0: SiC> ₂ molar ratio of 1: 2 to 1: 2.8. Such amorphous alkali silicates are

for example commercially available under the name Portil®. They are preferably added as a solid and not in the form of a solution during production. As crystalline silicates, which can be present alone or in a mixture with amorphous silicates

preferably crystalline layered silicates of the general formula Na ₂ Six0 _{2x + i} yH ₂ 0 are 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 2, 3 or 4 are. 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 d-sodium disilicate (Na ₂ Si ₂ 0s yH ₂ 0) are preferred. Even from amorphous

Alkali silicates produced, practically anhydrous crystalline alkali silicates of the above general formula, in which x is a number from 1.9 to 2.1, can 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 alkali silicate content is preferably 1% by weight to 50% by weight and in particular 5% by weight to 35% by weight, based on the anhydrous active substance. If alkali aluminosilicate, in particular zeolite, is also present as an additional builder substance, the alkali 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 which contain both amorphous and crystalline alkali silicates, the weight ratio of amorphous alkali silicate to crystalline alkali silicate is preferably 1: 2 to 2 : 1 and especially 1: 1 to 2: 1.

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

In addition, the agents can contain other constituents customary in washing 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 stilbene disulfonic acid derivatives. Preferably, agents which contain an active ingredient used according to the invention contain up to 1% by weight, in particular 0.01% by weight to 0.5% by weight, of optical brighteners, in particular compounds from the class of the 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 in each case referring to the total 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 those from the named

Classes of derivable ether. In such liquid compositions, the active substances used according to the invention are generally in solution or in suspended form.

Enzymes which may be present 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 suitable. 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, for example, under the names Lipolase®, Lipozym®, Lipomax®, Lipex®, Amano® lipase, Toyo-Jozo® lipase, Meito® lipase and

Diosynth® lipase commercially available. Suitable amylases are commercially available, for example, under the names Maxamyl®, Termamyl®, Duramyl® and Purafect® OxAm. The cellulase which can be used can be an enzyme which can be obtained from bacteria or fungi and which has a pH optimum, preferably in the weakly acidic to weakly alkaline range from 6 to 9.5.

Such cellulases are under the names Celluzyme®, Carezyme® and Ecostone®

commercially available.

Regarding the usual ones, especially those present in liquid funds

Enzyme stabilizers include amino alcohols, for example mono-, di-, triethanol and propanolamine and mixtures thereof, lower carboxylic acids, boric acid or alkali borates, combinations of boric acid and carboxylic acid, boric acid esters, boronic acid derivatives, Calcium salts, for example Ca-formic acid combination, magnesium salts, and / or sulfur-containing reducing agents.

Suitable foam inhibitors include long-chain soaps, in particular beech soap, fatty acid amides, paraffins, waxes, microcrystalline waxes, organopolysiloxanes and mixtures thereof, which are also microfine, optionally silanized or otherwise

May contain hydrophobized silica. 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 percarbonate, up to 15% by weight. %, in particular 1% by weight to 10% by weight of bleach activator, 20% by weight to 55% by weight of inorganic builder, up to 10% by weight, in particular 2% by weight to 8% by weight % water-soluble organic builder, 10% by weight to 25% by weight of synthetic anionic surfactant, 1% by weight to 5% by weight of nonionic surfactant and up to 25% by weight, in particular 0.1% by weight to 25% by weight of inorganic salts, in particular alkali carbonate and / or hydrogen carbonate.

In a further preferred embodiment, an agent into which the active ingredient 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 of synthetic anionic surfactant, 3% by weight to 15% by weight, in particular 5% by weight to 10% by weight of soap, 0 .5% to 5% by weight, in particular 1% by weight to 4% by weight of organic builders, in particular polycarboxylate such as citrate, up to 1.5% by weight, in particular 0.1% by weight % to 1% by weight complexing agent for heavy metals, such as phosphonate, and, in addition to any enzyme, enzyme stabilizer, coloring and / or fragrance, water and / or water-miscible solvent.

It is also possible to use a combination of a dirt-releasing active substance essential to the invention with a dirt-releasing 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 polymer, in particular polyester-active, dirt-releasing polymer, are also possible within the scope of agents according to the invention and the method according to the invention.

The known polyester-active dirt-releasing polymers which can be used in addition to the active ingredients essential to the invention include copolyesters

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 preferred dirt-releasing polyesters include those compounds which 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 is also used as a polymer Diol H- (0- (CHR ¹¹ -) _a ) bOH may be present. Therein, Ph represents an o-, m- or p-phenylene radical, which has 1 to 4 substituents selected from

Alkyl radicals with 1 to 22 carbon atoms, sulfonic acid groups, carboxyl groups and mixtures thereof, R ^{11 can be} hydrogen, an alkyl radical with 1 to 22 carbon atoms and mixtures thereof, a a number from 2 to 6 and b a number from 1 to 300. Both monomer diol units -0- (CHR ¹¹ -) _a 0- and polymer diol units - (O- (CHR ¹¹ -) _a ) bO- are preferably present in the polyesters obtainable from these. 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 dirt-releasing polyesters 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 in salt form, in particular as an alkali or ammonium salt. Among them, 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 dirt-releasing polyester. These include, for example, alkylene and alkenylene dicarboxylic acids such as malonic acid, succinic acid, fumaric acid, maleic acid, glutaric acid, adipic acid,

Pimelic acid, suberic acid, azelaic acid and sebacic acid. The preferred diols HO- (CHR ¹¹ -) _a OH include those in which R ^{11 is} hydrogen and a is a number from 2 to 6, and those in which a is 2 and R ¹¹ is hydrogen and the alkyl radicals 1 to 10, in particular 1 to 3 carbon atoms is selected. Among the latter diols, those of the formula HO-CH2-CHR ¹¹ -OH, in which R ^{11 has} the abovementioned meaning, are particularly preferred. Examples of diol components are ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 8-octanediol, 1, 2-decanediol, 1, 2-dodecanediol and neopentyl glycol. Particularly preferred among the polymeric diols is polyethylene glycol with an average molecular weight in the range from 1000 g / mol to 6000 g / mol.

If desired, these polyesters composed as described above can also be end-capped, the end groups being alkyl groups with 1 to 22 carbon atoms and esters of monocarboxylic acids. The one bound via ester bonds End groups 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, Linolaidinsäure, linolenic acid, eleostearic 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 carbon atoms, in particular 1 to 12 carbon atoms, for example tert-butylbenzoic acid. The end groups can also be based on hydroxymonocarboxylic acids having 5 to 22 carbon atoms, to which, for example, hydroxyvaleric acid, hydroxycaproic acid, ricinoleic acid, and the like

Hydrogenation product include hydroxystearic acid and o-, m- and p-hydroxybenzoic acid. The hydroxymonocarboxylic acids can in turn be linked to one another via their hydroxyl group and their carboxyl group and can therefore be present several times in an end group. The number of hydroxymonocarboxylic acid units per end group, that is to say her, is preferably

Degree of oligomerization, 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 50:50 to 90:10 is used in combination with a combination of an active ingredient essential to the invention.

The polyester-active dirt-releasing polymers are preferably water-soluble, the term “water-soluble” being understood to mean 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. Under these conditions, however, preferred polymers have a solubility of at least 1 g per liter, in particular at least 10 g per liter.

Preferred laundry aftertreatment compositions which contain an active ingredient to be used according to the invention have a so-called ester quat as the fabric softening active ingredient, that is to say a quaternized ester of carboxylic acid and amino alcohol. These are known substances which can be obtained by the relevant methods of preparative organic chemistry, for example by partially esterifying triethanolamine in the presence of hypophosphorous acid with fatty acids, passing air and then quaternizing with dimethyl sulfate or ethylene oxide. The production 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.

Ester quats preferred in the compositions are quaternized fatty acid triethanolamine ester salts which follow the formula (IV) R ⁴

[R ¹ C0- (0CH2CH2) m0CH2CH2-N ⁺ -CH2CH20- (CH2CH ₂ 0) nR ² ] X (IV)

CH2CH20 (CH2CH ₂ 0) _P R ³ in the R ¹ CO for an acyl radical with 6 to 22 carbon atoms, R ² and R ³ independently of one another for hydrogen or R ¹ CO, R ⁴ for an alkyl radical with 1 to 4 carbon atoms or one

(CH ₂ CH ₂ 0) qH group, m, n and p in total for 0 or numbers from 1 to 12, q for numbers from 1 to 12 and X for a charge-balancing anion such as halide, alkyl sulfate or alkyl phosphate. Typical examples of ester quats which can be used in the context of 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, arachic acid, behenic acid and erucic acid and their technical mixtures, such as they occur, for example, in the pressure splitting of natural fats and oils. Technical Ci2 / i8 coconut fatty acids and in particular partially hardened Ci6 / is tallow or palm fatty acids as well as elaidic acid-rich Ci6 / 18 fatty acid cuts are preferably used. For the preparation of the quaternized esters, the fatty acids and the triethanolamine can generally be used in a molar ratio of 1.1: 1 to 3: 1. With regard to the application properties of the esterquats, there has been a change

Use ratio of 1.2: 1 to 2.2: 1, preferably 1.5: 1 to 1.9: 1 has proven to be particularly advantageous. The preferred esterquats 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 Ci6 / is tallow or palm fatty acid (iodine number 0 to 40). quaternierte

Fatty acid triethanolamine ester salts of the formula (IV) in which R ¹ CO for an acyl radical having 16 to 18 carbon atoms, R ² for R ¹ CO, R ³ for hydrogen, R ⁴ for a methyl group, m, n and p for 0 and X for methyl sulfate stands have proven to be particularly advantageous.

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,

R ⁴

[R ¹ C0- (0CH2CH2) m0CH2CH2-N ⁺ -CH2CH20- (CH2CH ₂ 0) nR ² ] C (V)

R ⁵ in R ¹ CO for an acyl radical with 6 to 22 carbon atoms, R ² for hydrogen or R ¹ CO, R ⁴ and R ⁵ independently of one another for alkyl radicals with 1 to 4 carbon atoms, m and n in total represents 0 or numbers from 1 to 12 and X represents a charge-balancing anion such as halide, alkyl sulfate or alkyl phosphate.

Finally, a further group of suitable ester quats are the quaternized ester salts of carboxylic acids with 1,2-dihydroxypropyl dialkylamines of the formula (VI)

R ⁶ 0- (CH ₂ CH ₂ 0) m0CR ¹

[R ⁴ -N ⁺ -CH ₂ CHCH ₂ 0- (CH ₂ CH ₂ 0) _n R ² ] C (VI)

R ⁷ in R ¹ CO for an acyl radical with 6 to 22 carbon atoms, R ² for hydrogen or R ¹ CO, R ⁴ , R ⁶ and R ⁷ independently of one another for alkyl radicals with 1 to 4 carbon atoms, m and n in total for 0 or numbers from 1 to 12 and X represents 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 information given for (IV) also applies analogously to the esterquats of the formulas (V) and (VI). The ester quats usually come in the form 50 to 90

weight percent alcoholic solutions on the market, which can also be easily diluted with water, with ethanol, propanol and isopropanol being the usual alcoholic solvents.

Ester quats are preferably used in amounts of 5% by weight to 25% by weight, in particular 8% by weight to 20% by weight, in each case based on the total laundry aftertreatment agent. If desired, the laundry aftertreatment agents used according to the invention can additionally contain detergent ingredients listed above, provided that they do not interact unreasonably with the esterquat. It is preferably a liquid, water-containing agent.

Examples

Example 1: Preparation of pullulan ethers a) Synthesis of carboxymethylpullulan

82.25 g (308.64 mmol) of an aqueous 15% NaOH solution were slowly added to a suspension of 25 g (154.32 mmol) of pullulan in 750 ml of isopropanol and stirred at room temperature for 1 hour. 35.95 g (308.64 mmol) of sodium monochloroacetate were added, followed by stirring at 55 ° C. for five hours. The

The reaction mixture was decanted and the solid residue was dissolved in 500 ml of distilled water. A solid was precipitated by adding the solution to 5000 ml of methanol and, after filtration with a G3 frit, the precipitate was poured into 80% (v / v) aqueous methanol. After neutralization with dilute acetic acid, the product was washed four times with 700 ml of 80% (v / v) aqueous methanol and once with 700 ml of methanol and dried at 40 ° C. in vacuo. Yield: 35.47 g (90%)

FT-IR (KBr): 3440 cm ¹ (OH); 2924 cm ¹ (CH); 1604 cm ¹ (C = 0); 1419 cm ¹ (CH); 1012 cm ¹ (CO-

C)

¹³ C NMR (250 MHz; D20): d [ppm] 177.9 (C = 0); 98.1 (C-1); 80.9; 76.7; 74.6; 73.8; 72.5; (C-3 - C-5); 71, 4 (CH2); 66.3; 61, 5 (C-6)

EA: C: 38.63%; H: 4.77%

DS = 1, 17 b) Synthesis of carboxymethylpullulan

Carboxymethylpullulan with lower DS was analogous to that described under a)

Process prepared from pullulan (25 g; 154.32 mmol), sodium monochloroacetate (17.98 g; 154.32 mmol) and sodium hydroxide solution (82.25 g; 308.64 mmol). Yield: 24.67 g (89%)

C)

¹³ C NMR (250 MHz; D20): d [ppm] 177.9 (C = 0); 100.4; 99.9; 98.1 (C-1); 77.9; 77.6; 73.5; 73, 1;

71, 7; 70.4; 69.5 (C-3 - C-5); 71, 4 (CH2); 66.6; 60.7; 60.5 (C-6)

EA: C: 41.1 1%; H: 6.16%

DS = 0.28 c) Synthesis of sulfoethylpullulan 19.29 g (37.04 mmol) of an aqueous 25% sodium vinylsulfonate solution were added to a suspension of 2 g (12.35 mmol) of pullulan in 100 ml of isopropanol and the mixture was stirred for 20 minutes at room temperature under a nitrogen atmosphere. 2.96 g (74.0 mmol) of solid NaOH were added. The mixture was reacted for one hour at room temperature and five hours at 80 ° C. After cooling, the liquid phase was decanted, the residue was dissolved in 70 ml of distilled water and slowly added to 700 ml of methanol. The precipitate was suspended in 700 ml of 80% (v / v) aqueous methanol and neutralized with dilute acetic acid. After filtration (G3 frit), the solid residue was washed four times with 150 ml of methanol each time and dried at 60 ° C. in vacuo. Yield: 2.65 g (88%)

FT-IR (KBr): 3370 cm ¹ (OH); 2930 cm ¹ (CH); 1416 cm ¹ (CH); 1 159 cm ¹ (S = 0); 1080 cm ¹ (CO-C); 1039 cm ¹ (S = 0); 755 (CS)

¹³ C NMR (250 MHz; D20): d [ppm] 102.5; 100.9 (C-1); 82.45; 79.9; 75.3; 74.4; 74.2; 73.1; 71, 9; 70.5 (C-3 - C-5); 69.2 (C-6) 68.9 (CH2); 63.4 (C-6); 53.4 (CH ₂ )

EA: C: 33.14%; H: 5.28%; S: 8.31%

DS = 0.63

Example 2: Medium

Table 1 shows the composition (ingredients in percent by weight, in each case based on the total composition) of the detergents M1, M2 and M3 according to the invention and of the agent V1 free of a corresponding active ingredient and the known one in its place

Graying inhibitor containing agent V2 indicated carboxymethyl cellulose:

Table 1: Composition

a) From example 1a

b) From Example 1 b

Example 3: Graying

The agents V1, M1 or M2 were in a Miele® W 1935 washing machine

(Cotton washing program, 40 ° C; water hardness 16 ° dH; standardized dirt carrier; dosage 52.6 g of the respective agent per wash) tested. In addition to filling laundry, the materials listed in Table 2 were used for a load of 3.5 kg (each 8 pieces of textile in the size 20 x 40 cm).

Table 2 below shows the differences in the brightness changes (DDU values) of the materials after 3 washes under the specified conditions with the respective average compared to the change in brightness after 3 washes with the average V1.

Table 2: Differences in brightness change

When using the agents according to the invention, the materials turn gray significantly less than when using the agent which lacks the active ingredient essential to the invention. Example 4: Graying after storage

The procedure of Example 3 was carried out using the freshly prepared agents M3 and V2 and additionally using the same agents that were used for 1 week prior to the washing operations

Room temperature (stirred during the day) had been repeated with the materials listed in Table 3. Table 3 shows the differences in the changes in brightness between the stored and the freshly prepared agent, [Y (after

Graying attempt) - Y (before the graying attempt) - [Y (after the graying attempt) - Y (before the graying attempt).

Table 3: Differences in brightness after storage

It can be seen that the graying-inhibiting effect of the agent V2 decreases significantly more after storage than the graying-inhibiting effect of the agent according to the invention.

Claims

claims

1. Use of pullulan derivatives that have a modified anhydroglycoside unit

contain general formula I,

in which the radicals R independently of one another are -OH, -0 (CH ₂ ) nC00H, -0 (CH ₂ ) nC00 X ⁺ , -0 (CH ₂ ) mS0 ₃ H, -0 (CH ₂ ) mS03 X ⁺ , n and m independently of one another stand for numbers from 1 to 3, and X ^{+ stands} for a charge-balancing cation, in particular an alkali metal and / or ammonium ion, where at least some of the radicals R do not stand for -OH - to enhance cleaning performance Soiling of detergents when washing textiles.

2. Use according to claim 1, characterized in that the textiles had been washed and / or aftertreated in the presence of the active ingredient before they were provided with the soiling.

3. Use of pullulan derivatives that have a modified anhydroglycoside unit

contain general formula (I),

in which the radicals R independently of one another are -OH, -0 (CH ₂ ) nCOOH, -0 (CH ₂ ) nC00 X ⁺ , -0 (CH ₂ ) mS0 ₃ H, -0 (CH ₂ ) mS0 ₃ X ⁺ , n and m independently of one another represent numbers from 1 to 3, and X ^{+ stands} for a charge-balancing cation, in particular an alkali metal and / or ammonium ion, at least some of the radicals R not being —OH— to reduce the Graying of textiles when washing.

4. Process for washing textiles, in which a detergent and a pullulan derivative which contains a modified anhydroglycoside unit of the general formula (I),

in which the radicals R independently of one another are -OH, -0 (CH ₂ ) nC00H, -0 (CH ₂ ) nC00 X ⁺ , -0 (CH ₂ ) mS0 ₃ H, -0 (CH ₂ ) mS03 X ⁺ , n and m independently of one another represent numbers from 1 to 3, and X ^{+ stands} for a charge-balancing cation, in particular an alkali metal and / or ammonium ion, at least some of the radicals R not being —OH— being used.

5. The method according to claim 4, characterized in that the use concentration of the pullulan derivative in the wash liquor is 0.0001 g / l to 1 g / l, in particular 0.001 g / l to 0.2 g / l.

6. The method according to claim 4 or 5, characterized in that it is carried out using a detergent containing the pullulan derivative.

7. A method of washing textiles according to one of claims 4 to 6, characterized

characterized in that it is carried out using a laundry aftertreatment agent, in particular fabric softener, containing the pullulan derivative.

8. washing or laundry aftertreatment agent containing a pullulan derivative, the one

contains modified anhydroglycoside unit of the general formula I,

in which the radicals R independently of one another are -OH, -0 (CH ₂ ) nC00H, -0 (CH ₂ ) nC00 X ⁺ , -0 (CH ₂ ) mS0 ₃ H, -0 (CH ₂ ) mS03 X ⁺ , n and m independently of one another represent numbers from 1 to 3, and X ^{+ stands} for a charge-balancing cation, in particular an alkali metal and / or ammonium ion, at least some of the radicals R not representing -OH.

9. Composition according to claim 8, characterized in that it contains the pullulan derivative in quantities of 0.01% by weight to 10% by weight, in particular from 0.1% by weight to 3% by weight.

10. Use according to one of claims 1 to 3, method according to one of claims 4 to 7, or agent according to claim 8 or 9, characterized in that in the general formula (I) n is 1 and / or m is 2 ; and / or that the average degree of substitution (DS) in the pullulan derivative is in the range from 0.1 to 1.2, in particular in the range from 0.2 to 0.9; and / or the average molecular weight of the pullulan derivative is in the range from 5000 g / mol to 150,000 g / mol, in particular in the range from 30,000 g / mol to 110,000 g / mol.