EP3049508B1 - Cellulose carbamate as soil release agent - Google Patents

Description

The present invention relates to the use of certain soil release agents to enhance the cleaning performance of laundry detergents in laundry.

Detergents contain in addition to the indispensable for the washing process ingredients such as surfactants and builder materials usually further ingredients that can be summarized by the term washing aids and include as different drug groups such as foam regulators, grayness inhibitors, bleach, bleach activators and dye transfer inhibitors. Such adjuvants also include substances which impart soil repellency properties to the laundry fiber and, if present during the wash, aid the soil release properties of the remaining detergent ingredients. The same applies mutatis mutandis to cleaners for hard surfaces. Such soil release agents are often referred to as "soil release" agents or because of their ability to render the treated surface, e.g., the fiber, soil-repellent as "soil repellents". For example, from the US patent US 4,136,038 the soil release ability 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 US 4,000,093 discloses detergents containing from 0.1% to 3% by weight of alkyl cellulose, hydroxyalkyl cellulose or alkyl hydroxyalkyl cellulose and from 5% to 50% by weight surfactant, wherein the surfactant component is substantially consists of C ₁₀ - to C ₁₃ -alkyl sulfate and up to 5 wt .-% C ₁₄ alkyl sulfate and less than 5 wt .-% alkyl sulfate having alkyl radicals of C ₁₅ and higher.

Because of their chemical similarity to polyester fibers in textiles of this material particularly effective soil release agents 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-releasing copolyesters of the type mentioned as well as their use in detergents have been known for a long time.

The polymers known from the prior art have the disadvantage that, in particular for textiles which are not or at least not predominantly made 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 especially greasy soiling on especially such textiles more effective soil release agents.

Surprisingly, it has been found that this object can be achieved by the use of certain cellulose derivatives.

From the international patent application WO 00/18860 A1 is the rebuilding effect of there so-called cellulose esters known, which may also be cellulose carbamates known on textiles. This is believed to be based on the fact that the cellulose esters deposit on the damaged textile sites, react by cleavage of the reactive ester functionality with the fiber and thereby reinforce the damaged areas by 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 on a substrate, such as a fiber, for the substrate. The international patent application WO 01/72937 A1 relates to the reduction of dye losses in the washing of dyed textiles by the use of such cellulose esters. From the international patent application WO 01/72944 A1 the suitability of such cellulose ethers for enhancing the deposition of fragrances on textiles is known, and from the patent application GB 2 360 791 A It is known that they contribute to fabric softness by their deposition on textiles.

• in der R für H oder -C(=O)-NR¹R² steht mit der Maßgabe, dass mindestens 1 der Reste R gleich -C(=O)-NR¹R² ist, und
• R¹ für H oder R² und R² für Aryl-, geradkettige oder verzweigte Alkyl-, Aryl-, Alkylaryl- oder Arylalkylgruppen stehen, die mit einer oder mehreren funktionellen Gruppen, wie Hydroxy-, Carboxy-, Oxy- oder Aminogruppen, 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. Cellulosecarbamate sind durch bekannte Herstellverfahren zugänglich, zum Beispiel durch eine zweistufige Synthese bestehend aus der Umsetzung von Cellulose mit Phenylchloroformat oder Nitrophenylchloroformat, wie beschrieben in Cellulose (2013) 20:339-353 , zu Cellulosephenylcarbonaten oder Cellulosenitrophenylcarbonaten und anschließender Aminolyse der Carbonate mit Aminen des Typs H-NR¹R² zu den entsprechenden Cellulosecarbamaten. Bevorzugte Gruppen - NR¹R² leiten sich ab von Aminoalkoholen wie zum Beispiel 2-Aminoethanol, 3-Aminopropanol, 2-(2-aminoethoxy)ethanol, N-2-(2-hydroxyethyl)ethylendiamin, 2-Amino-1,3-propandiol, 2-Amino-2-methyl-1,3-Propandiol, 2-Amino-2-ethyl-1,3-Propandiol, Tris-(hydroxymethyl)aminomethan, mehrfach alkoxylierten und insbesondere ethoxylierten Aminen, die zum Beispiel unter dem Handelsnamen Jeffamine® erhältlich sind, α-Aminosäuren, β-Aminosäuren, wie zum Beispiel β-Alanin, ω-Aminosäuren, Anilin, das gewünschtenfalls am Ring substituiert sein kann, Benzylamin, das gewünschtenfalls am Ring substituiert sein kann wie beispielsweise p-Aminobenzylamin, Morpholin, N-Amino-Morpholin, N-Aminoalkyl-Morpholin, Ethylendiamin, und Mischungen aus diesen.

The invention relates to the use of cellulose carbamates which contain a substituted anhydroglucose unit of the general formula I

• in the R represents H or -C (= O) -NR ¹ R ² with the proviso that at least 1 of the radicals R is -C (= O) -NR ¹ R ² , and
• R ^{1 is} H or R ² and R ^{2 is} aryl, straight chain or branched alkyl, aryl, alkylaryl or arylalkyl groups substituted with one or more functional groups such as hydroxy, carboxy, oxy or amino groups may be and / or which may be interrupted by heteroatoms such as N, O or S,
• to enhance the cleaning performance of detergents when washing textiles. Cellulose carbamates are obtainable by known preparation methods, for example by a two-step synthesis consisting of the reaction of cellulose with phenyl chloroformate or Nitrophenyl chloroformate as described in Cellulose (2013) 20: 339-353 , to cellulose phenyl carbonates or cellulose nitrophenyl carbonates and subsequent aminolysis of the carbonates with amines of the type H-NR ¹ R ² to the corresponding cellulose carbamates. Preferred groups - NR ¹ R ^{2 are} derived from amino alcohols such as 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, which are described, for example, under US Pat Trade names Jeffamine®, α-amino acids, β-amino acids, such as β-alanine, ω-amino acids, aniline, which may optionally be substituted on the ring, benzylamine, which may optionally be substituted on the ring, such as p-aminobenzylamine, Morpholine, N-amino-morpholine, N-aminoalkyl-morpholine, ethylenediamine, and mixtures of these.

In addition to the substituted anhydroglucose unit of the general formula I, the cellulose carbamate to be used according to the invention contains further 1,4-.beta.-glycosidically linked anhydroglucose units, which may be unsubstituted or likewise correspond to the general formula I. If desired, it is also possible to add anhydroglucose 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, .beta.-aminopropionic, glycolic or malonic acid ester groups. The average degree of substitution, based on the proportion of carbamate groups, in the cellulose carbamate to be used according to the invention is preferably in the range from 0.2 to 2, in particular from 0.4 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.

Another object of the invention is a process for washing textiles, in which a detergent and a soil release agent in the form of a cellulose carbamate as defined above are used. These methods can be carried out manually or optionally with the aid of a conventional household washing machine. It is possible to use the detergent and soil release agent simultaneously or sequentially. The simultaneous application can be particularly advantageous by the use of a detergent containing the soil release agent, perform.

Particularly pronounced is the effect of the active ingredient to be used according to the invention in the case of multiple use, that is to say, in particular for the removal of stains from textiles, which had already been washed and / or post-treated in the presence of the active substance before being soiled. In connection with the aftertreatment it should be pointed out that the designated positive aspect can also be realized by a washing process in which the textile after the actual washing process, with the help of a detergent which may contain a named active ingredient, but in this case also free may be carried out by this, with an aftertreatment agent, for example in the context of a fabric softening step, which contains an active substance to be used according to the invention is brought into contact. In this procedure as well, if desired again a detergent without an active ingredient to be used according to the invention is used in the next washing process, the washing performance-enhancing effect of the active ingredients to be used according to the invention occurs. This is significantly higher than that resulting from the use of a conventional soil release agent. In a particularly preferred embodiment, the addition of the active ingredient essential to the invention takes place in the fabric softening cycle of the textile washing.

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

The use according to the invention can be carried out as part of a washing process by adding the soil release agent to a detergent-containing liquor or preferably incorporating the active ingredient as a component of a detergent into the liquor containing or to be contacted with the object to be cleaned. Further objects of the invention are therefore detergents which contain above-defined cellulose carbamates.

The use according to the invention within the scope of a laundry aftertreatment process can be carried out in such a manner that the rinse liquor is added separately to the rinse liquor which is used after the wash cycle using a particular bleach-containing detergent, or it is incorporated as a component of the laundry aftertreatment agent, in particular a softener. In this aspect of the invention, the laundry detergent used before the laundry aftertreatment agent may also contain, but may be free from, an active ingredient to be used according to the invention.

The washing process is preferably carried out at a temperature of 15 ° C to 60 ° C, more preferably at a temperature of 20 ° C to 40 ° C. 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 cellulose carbamate in the wash liquor is preferably from 0.001 g / l to 1 g / l, in particular from 0.005 g / l to 0.2 g / l.

Agents which contain an active ingredient to be used according to the invention in the form of said cellulose carbamate or are used together or used in the method according to the invention may contain all customary other constituents of such agents which do not undesirably interact 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, these and the following quantities being based on refer to the total amount, unless stated otherwise.

Surprisingly, it has been found that the active ingredient used according to the invention has a positive effect on the action of certain other detergent ingredients and conversely that 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 sulphate and sulphonate type, and with color transfer inhibitors, for example vinylpyrrolidone , Vinylpyridin- or vinylimidazole polymers or copolymers or corresponding Polybetainen on, which is why the use of at least one of said further ingredients together with the invention to be used drug is preferred.

An agent which contains an active substance to be used according to the invention or is used together or is used in the process 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, bleach activator, especially in amounts ranging from 2% to 10% by weight, may in another preferred embodiment also be free of bleach and bleach activator. The bleaches in question are preferably the peroxygen compounds generally used in detergents, such as percarboxylic acids, for example dodecanedioic acid or phthaloylaminoperoxicaproic acid, hydrogen peroxide, alkali metal perborate, which may be in the form of tetra- or monohydrate, percarbonate, perpyrophosphate and persilicate, which are generally used as alkali metal salts, in particular as sodium salts. Such bleaching agents are in detergents containing an active ingredient according to the invention, preferably in amounts of up to 25 wt .-%, in particular up to 15 wt .-% and particularly preferably from 5 wt .-% to 15 wt .-%, each based on total agent, present, in particular percarbonate is used. The optional component of the bleach activators includes the commonly used N- or O-acyl compounds, for example, polyacylated alkylenediamines, in particular tetraacetylethylenediamine, acylated glycolurils, in particular tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, urazoles, diketopiperazines, sulfururamides and cyanurates, moreover carboxylic acid anhydrides, in particular phthalic anhydride, carboxylic acid esters, in particular sodium isononanoylphenolsulphonate, and acylated sugar derivatives, in particular pentaacetylglucose, as well as cationic nitrile derivatives such as trimethylammonium acetonitrile salts. In order to avoid the interaction with the peroxygen compounds, the bleach activators may have been coated or granulated in known manner with encapsulating substances, granulated tetraacetylethylenediamine having weight-average particle sizes of from 0.01 mm to 0.8 mm, granulated 1.5% by means of carboxymethylcellulose. Diacetyl-2,4-dioxohexahydro-1,3,5-triazine, and / or formulated in particulate trialkylammonium acetonitrile is particularly preferred. 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, based in each case on the total agent.

In a preferred embodiment, an agent used according to the invention or used in the process according to the invention comprises 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 of 2 wt .-% to 25 wt .-%.

Another embodiment of such agents comprises the presence of sulfate and / or sulfonate synthetic anionic surfactant, in particular fatty alkyl sulfate, fatty alkyl ether sulfate, sulfo fatty acid ester and / or sulfo fatty acid salt, 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. Of these, preference is given to those whose content of compounds having 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 C atoms, preferably 12 to 18 C 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. Particularly suitable are the derivatives of fatty alcohols, although their branched-chain isomers, in particular so-called oxo alcohols, can be used for the preparation of usable alkoxylates. Are usable Accordingly, the alkoxylates, in particular the ethoxylates, primary alcohols with linear, especially dodecyl, tetradecyl, hexadecyl or octadecyl radicals and mixtures thereof. In addition, suitable alkoxylation products of alkylamines, vicinal diols and carboxamides, which correspond to the said alcohols with respect to the alkyl part, usable. In addition, the ethylene oxide and / or propylene oxide insertion products of fatty acid alkyl esters and Fettsäurepolyhydroxyamide into consideration. So-called alkylpolyglycosides which are suitable for incorporation in the compositions 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 are oligomers or polymers of naturally occurring aldose or ketose monomers, in particular glucose, mannose, fructose, galactose, talose, gulose, altrose, allose, idose, ribose, arabinose, Include xylose and lyxose. The oligomers consisting of such glycosidically linked monomers are characterized not only by the nature of the sugars contained in them by their number, the so-called Oligomerisierungsgrad. The degree of oligomerization n assumes as the value to be determined analytically generally broken numerical values; it is between 1 and 10, with the glycosides preferably used below a value of 1.5, in particular between 1.2 and 1.4. Preferred monomer building block is glucose because of its good availability. The alkyl or alkenyl moiety R ^{12 of} the glycosides preferably also originates from readily available derivatives of renewable raw materials, in particular from fatty alcohols, although their branched-chain isomers, in particular so-called oxoalcohols, can also be used for the preparation of useful glycosides. Accordingly, the primary alcohols having linear octyl, decyl, dodecyl, tetradecyl, hexadecyl or octadecyl radicals and mixtures thereof are particularly suitable. Particularly preferred alkyl glycosides contain a Kokosfettalkylrest, that is, mixtures having substantially R ¹² = dodecyl and R ¹² = tetradecyl.

Nonionic surfactant is used in compositions containing a soil release agent used in the invention, used according to the invention or used in the process according to the invention, preferably in amounts of 1 wt .-% to 30 wt .-%, in particular from 1 wt .-% to 25 Wt .-%, with amounts in the upper part of this range are more likely to be found in liquid detergents and particulate detergents preferably contain rather lower amounts of up to 5 wt .-%.

The agents may instead or additionally contain other surfactants, preferably synthetic 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 total resources. Suitable synthetic anionic surfactants which are particularly suitable for use in such compositions are the alkyl and / or alkenyl sulfates having 8 to 22 C atoms which contain an alkali metal, ammonium or alkyl or hydroxyalkyl-substituted ammonium ion Wear countercation, to name. Preference is given to the derivatives of the fatty alcohols having in particular 12 to 18 carbon atoms and their branched-chain analogs, the so-called oxo alcohols. The alkyl and alkenyl sulfates can be prepared in a known manner by reaction of the corresponding alcohol component with a conventional sulfating reagent, in particular sulfur trioxide or chlorosulfonic acid, and subsequent neutralization with alkali metal, ammonium or alkyl or hydroxyalkyl-substituted ammonium bases. Sulfur-type surfactants which can be used also include the sulfated alkoxylation products of the alcohols mentioned, known as ether sulfates. Such ether sulfates preferably contain from 2 to 30, in particular from 4 to 10, ethylene glycol groups per molecule. Suitable anionic surfactants of the sulfonate type include the α-sulfoesters obtainable by reaction of fatty acid esters with sulfur trioxide and subsequent neutralization, in particular those of fatty acids having 8 to 22 C atoms, preferably 12 to 18 C atoms, and linear alcohols having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, derivative sulfonation, as well as the formal saponification resulting from these sulfo fatty acids.

Other optional surface-active ingredients are soaps, suitable being 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. In particular, those soap mixtures are preferred which are composed of 50% 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, especially in liquid compositions containing 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 compositions may also contain betaines and / or cationic surfactants, which, if present, are preferably used in amounts of from 0.5% by weight to 7% by weight. Among them, the esterquats 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 modulus above 1, monomeric polycarboxylate, polymeric polycarboxylate and mixtures thereof, in particular in amounts ranging from 2.5 wt .-% to 60 wt .-%.

The agent preferably contains from 20% to 55% by weight of water-soluble and / or water-insoluble, organic and / or inorganic builders. The water-soluble organic builder substances include, in particular, those from the class of the polycarboxylic acids, in particular citric acid and sugar acids, and also the polymeric (poly) carboxylic acids, in particular the polycarboxylates obtainable by oxidation of polysaccharides, polymeric acrylic acids, methacrylic acids, Maleic acids and copolymers of these, which may also contain polymerized small amounts of polymerizable substances without carboxylic acid functionality. The relative molecular mass of the homopolymers of unsaturated carboxylic acids is generally between 5000 g / mol and 200,000 g / mol, that of the copolymers between 2000 g / mol and 200,000 g / mol, preferably 50,000 g / mol to 120,000 g / mol, based on the free acid , A particularly preferred acrylic acid-maleic acid copolymer has a molecular weight of 50,000 g / mol to 100,000 g / mol. Suitable, although less preferred, compounds of this class are copolymers of acrylic or methacrylic acid with vinyl ethers, such as vinylmethyl ethers, vinyl esters, ethylene, propylene and styrene, in which the acid content is at least 50% by weight. Terpolymers which contain two carboxylic acids and / or salts thereof as monomers and also vinyl alcohol and / or a vinyl alcohol derivative or a carbohydrate as the third monomer may 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, with maleic acid being particularly preferred. The third monomeric unit is formed in this case of vinyl alcohol and / or preferably an esterified vinyl alcohol. In particular, preferred are vinyl alcohol derivatives which are an ester of short-chain carboxylic acids, for example C ₁ -C ₄ carboxylic acids, with vinyl alcohol. Preferred terpolymers contain from 60 wt .-% to 95 wt .-%, in particular 70 wt .-% to 90 wt .-% of (meth) acrylic acid or (meth) acrylate, particularly preferably acrylic acid or acrylate, and maleic acid or maleate and 5 wt .-% to 40 wt .-%, preferably 10 wt .-% to 30 wt .-% 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. 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 is in the 2-position with an alkyl radical, preferably with 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 from 40% by weight to 60% by weight, in particular from 45 to 55% by weight, of (meth) acrylic acid or (meth) acrylate, particularly preferably acrylic acid or acrylate, from 10% by weight to 30% by weight. %, preferably 15 wt .-% to 25 wt .-% methallylsulfonic acid or Methallylsulfonat and as the third monomer 15 wt .-% to 40 wt .-%, preferably 20 wt .-% to 40 wt .-% of a carbohydrate. This carbohydrate may 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 incorporates predetermined breaking points in the polymer which are responsible for the good biodegradability of the polymer. These terpolymers generally have a 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 preparation of liquid agents, in the form of aqueous solutions, preferably in the form of 30 to 50 percent by weight aqueous solutions. All 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. Quantities close to the stated upper limit are preferably used in pasty or liquid, in particular hydrous, agents.

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 agents, in particular from 1% by weight to 5% by weight, are used as water-insoluble, water-dispersible inorganic builder materials. used. Among these, the detergent-grade crystalline aluminosilicates, especially zeolite NaA and optionally NaX, are preferred. Amounts near the above upper limit are preferably used in solid, particulate agents. In particular, suitable aluminosilicates have no particles with a particle size greater than 30 mm and preferably consist of at least 80% by weight of particles having a size of less than 10 mm. Their calcium binding capacity, according to the information of the German Patent DE 24 12 837 can be determined ranges from 100 to 200 mg CaO per gram. Suitable substitutes or partial substitutes for the said aluminosilicate are crystalline alkali silicates which may be present alone or in a mixture with amorphous silicates. The alkali metal silicates useful as builders in the compositions 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 may be present in amorphous or crystalline form. Preferred alkali metal silicates are the sodium silicates, in particular the amorphous sodium silicates, with a molar ratio of Na ₂ O: SiO ₂ of 1: 2 to 1: 2.8. Such amorphous alkali silicates are commercially available, for example, under the name Portil®. They are preferably added in the course of the production as a solid and not in the form of a solution. The crystalline silicates which may be present alone or in admixture with amorphous silicates, are crystalline layer silicates with the general formula Na ₂ Si _x O _{2x + 1} · are used yH ₂ O, in which x, the so-called module, a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4. Preferred crystalline phyllosilicates are those in which x in the abovementioned general formula assumes the values 2 or 3. In particular, both .beta.- and δ-Natriumdisitikate (Na ₂ Si ₂ O ₅ · yH ₂ O) are preferred. Also prepared from amorphous alkali metal silicates, 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 the composition according to the invention, a crystalline sodium layer silicate with a modulus of 2 to 3 is used, as prepared from sand and soda can be. Crystalline sodium silicates with a modulus in the range from 1.9 to 3.5 are used in a further preferred embodiment of detergents containing an active ingredient used according to the invention. Their content of alkali metal silicates is preferably 1 wt .-% to 50 wt .-% and in particular 5 wt .-% to 35 wt .-%, based on anhydrous active substance. If alkali metal aluminosilicate, in particular zeolite, is present as an additional builder substance, the content of alkali silicate 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, in each case based on anhydrous active substances, is then preferably 4: 1 to 10: 1. In agents 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 especially 1: 1 to 2: 1.

In addition to the said inorganic builder, other water-soluble or water-insoluble inorganic substances may be contained in the compositions which contain an active substance to be used according to the invention together with it or used in the process according to the invention. Suitable in this context are the alkali metal carbonates, alkali metal bicarbonates and alkali metal sulfates and mixtures thereof. Such additional inorganic material may be present in amounts up to 70% by weight.

In addition, the agents may contain other ingredients customary in detergents and cleaners. These optional ingredients 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, in agents which contain an active substance used according to the invention, 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 wt .-%, in particular 0.1 wt .-% to 2 wt .-% complexing agent for Heavy metals, in particular Aminoalkylenphosphonsäuren and their salts and up to 2 wt .-%, in particular 0.1 wt .-% to 1 wt .-% foam inhibitors, wherein said weight fractions refer to the total agent.

Solvents which can be used in particular for liquid agents are, in addition to water, preferably those which are water-miscible. These include the lower alcohols, for example, ethanol, propanol, isopropanol, and the isomeric butanols, glycerol, lower glycols, such as ethylene and propylene glycol, and the derivable from said classes of compounds ether. In such liquid agents, the active compounds used in the invention are usually dissolved or in suspended form.

Optionally present enzymes are preferably selected from the group comprising protease, amylase, lipase, cellulase, hemicellulase, oxidase, peroxidase or mixtures thereof. First and foremost, proteases derived from microorganisms, such as bacteria or fungi, come into question. It can be obtained in a known manner by fermentation processes from suitable microorganisms. Proteases are commercially available, for example, under the names BLAP®, Savinase®, Esperase®, Maxatase®, Optimase®, Alcalase®, Durazym® or Maxapem®. The lipase which 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 usable cellulase may be a recoverable from bacteria or fungi enzyme, which has a pH optimum, preferably in the weakly acidic to slightly alkaline range of 6 to 9.5. Such cellulases are commercially available under the names Celluzyme®, Carezyme® and Ecostone®.

The customary enzyme stabilizers present, if appropriate, in particular in liquid agents include amino alcohols, for example mono-, di-, triethanol- and -propanolamine and mixtures thereof, lower carboxylic acids, boric acid or alkali borates, boric acid-carboxylic acid combinations, 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, especially behenic soap, fatty acid amides, paraffins, waxes, microcrystalline waxes, organopolysiloxanes and mixtures thereof, which moreover can contain microfine, optionally silanated or otherwise hydrophobicized silica. For use in particulate agents, such foam inhibitors are preferably bound to granular, water-soluble carrier substances.

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

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

It is also possible to use a combination of a soil release agent rich in the invention with a soil release polymer of a dicarboxylic acid and an optionally polymeric diol to enhance the cleaning performance of detergents in the washing of textiles. Also within the scope of the inventive composition and the method according to the invention, such combinations are possible with a particular polyester-active soil release polymer.

The known polyester-active soil release polymers which can be used in addition to the active compounds of 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. Preferred soil release polymers include those compounds which are formally accessible by esterification of two monomeric moieties, wherein the first monomer is a dicarboxylic acid HOOC-Ph-COOH and the second monomer is a diol HO- (CHR ¹¹ -) _a OH, also known as polymeric Diol H- (O- (CHR ¹¹ -) _a ) _b OH may be present. Therein, Ph is an o-, m- or p-phenylene radical which can carry 1 to 4 substituents selected from alkyl radicals having 1 to 22 C atoms, sulfonic acid groups, carboxyl groups and mixtures thereof, R ¹¹ denotes hydrogen, an alkyl radical having 1 to 22 C atoms and mixtures thereof, a is a number from 2 to 6 and b is a number from 1 to 300. Preferably, in the polyesters obtainable from these, both monomer diol units -O- (CHR ¹¹ -) _a O- and also polymeric 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. In the polymer diol units, the degree of polymerization b is preferably in the range from 4 to 200, in particular from 12 to 140. The molecular weight or the average molecular weight or the maximum of the molecular weight distribution of preferred soil release polymers 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 underlying the radical Ph is preferably selected from terephthalic acid, isophthalic acid, phthalic acid, trimellitic acid, mellitic acid, the isomers of sulfophthalic acid, sulfoisophthalic acid and sulfoterephthalic acid and mixtures thereof. Unless their acid groups are part of the ester linkages in the polymer, they are preferably in salt form, in particular as alkali or ammonium salt. Among these, the sodium and potassium salts are particularly preferable. If desired, in place of the monomer HOOC-Ph-COOH small proportions, in particular not more than 10 mol% based on the proportion of Ph having the meaning given above, of other acids having at least two carboxyl groups may be included in the soil release-capable 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 C-atoms is selected. Among the latter diols, those of the formula HO-CH ₂ -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 having an average molecular weight in the range from 1000 g / mol to 6000 g / mol.

If desired, these polyesters composed as described above may also be end-capped, alkyl groups having 1 to 22 carbon atoms and esters of monocarboxylic acids being suitable as end groups. The ester groups bonded via end groups 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, lauroleinic 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, levostearic acid, arachidic acid , Gadoleic acid, arachidonic acid, behenic acid, erucic acid, brassidic acid, clupanodonic acid, lignoceric acid, cerotic acid, melissic acid, benzoic acid, which may carry 1 to 5 substituents having a total of up to 25 carbon atoms, in particular 1 to 12 carbon atoms, for example tert-butylbenzoic acid , The end groups may also be based on hydroxymonocarboxylic acids having from 5 to 22 carbon atoms, which include, for example, hydroxyvaleric acid, hydroxycaproic acid, ricinoleic acid, the hydrogenation product of which includes hydroxystearic acid and o-, m-p-hydroxybenzoic acid. The hydroxymonocarboxylic acids may in turn be linked to one another via their hydroxyl group and their carboxyl group and thus be present several times in an end group. Preferably, the number of hydroxymonocarboxylic acid units per end group, that is to say their degree of oligomerization, is 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, used in combination with combination with an essential ingredient of the invention.

The polyester-active soil release 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. However, preferred polymers have a solubility of at least 1 g per liter, in particular at least 10 g per liter, under these conditions.

Preferred laundry aftertreatment compositions which comprise an active substance to be used according to the invention have, as a laundry softening active ingredient, a so-called esterquat, that is to say a quaternized ester of carboxylic acid and aminoalcohol. 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 through 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.

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

in the R ¹ CO for an acyl radical having 6 to 22 carbon atoms, R ² and R ^{3 are} 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 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, arachidic 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. Preferably, technical C _12/18 coconut _fatty acids and, in particular, partially hydrogenated C _16/18 tallow or palm oil fatty acids and also elaidic acid-rich C _16/18 fatty acid cuts are used. To prepare the quaternized esters, the fatty acids and the triethanolamine can generally be used in a molar ratio of 1.1: 1 to 3: 1.

In view of the performance properties of the esterquats, an employment 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 used are technical mixtures of mono-, di- and triesters having an average degree of esterification of 1.5 to 1.9 and are derived from technical C _16/18 tallow or palm oil fatty acid (iodine number 0 to 40) , Quaternized fatty acid triethanolamine ester salts of the formula (IV) in which R ^{1 is} CO for an acyl radical having 16 to 18 carbon atoms, R ^{2 is} R ¹ CO, R ^{3 is} hydrogen, R ^{4 is} a methyl group, m, n and p is 0 and X is 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, suitable esterquats are quaternized ester salts of carboxylic acids with diethanolalkylamines of the formula (V),

in the R ¹ CO for an acyl radical having 6 to 22 carbon atoms, R ^{2 is} hydrogen or R ¹ CO, R ⁴ and R ^{5 are} independently alkyl radicals having 1 to 4 carbon atoms, m and n in total for 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, the quaternized ester salts of carboxylic acids with 1,2-dihydroxypropyldialkylamines of the formula (VI) should be mentioned as a further group of suitable esterquats.

in the R ¹ CO for 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} independently alkyl radicals having 1 to 4 carbon atoms, m and n in total for 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 optimum degree of esterification, the exemplary data given for (IV) apply mutatis mutandis to the esterquats of the formulas (V) and (VI). Usually, the ester quats are in the form of 50 to 90 percent by weight alcoholic Commercially available solutions which can also be easily diluted with water, ethanol, propanol and isopropanol being the usual alcoholic solvents.

Esterquats are preferably used in amounts of from 5% by weight to 25% by weight, in particular from 8% by weight to 20% by weight, in each case based on the total laundry aftertreatment agent. If desired, the laundry aftertreatment agents used in the present invention may additionally contain detergent ingredients listed above, unless they unduly interact negatively with the esterquat. It is preferably a liquid, water-containing agent.

Examples example 1 a) Synthesis of N-ω-2- (2-hydroxyethyl) ethylene cellulose carbamate

35 g of cellulose phenyl carbonate (90 mmol) were added in 250 ml of dry DMF with N-2- (2-hydroxyethyl) ethylenediamine (180 mmol) dissolved in 250 ml of dry DMF. The reaction solution was stirred at room temperature for 30 minutes and then heated to 60 ° C. The mixture was allowed to react at this temperature for 18 hours. The product was made by precipitation in 3 | 2-propanol isolated and filtered off with suction (G3 frit). The cellulose carbamate was washed 3 times with 1.5 l Washed 2-propanol and dissolved without drying in 700 ml of distilled water. The solution was freed from 2-propanol by azeotropic distillation at 80 mbar and then freeze-dried (4 days, -55 ° C, 0.36 mbar).
Yield: 33 g (97%)
FT-IR (KBr): 3312 cm ^-1 v (OH) 2937 cm ^-1 v (CH ₂ ) 1711 cm ^-1 v (C = O)
¹³ C-NMR (400 MHz, DMSO-d ₆ ,): δ [ppm] 156.5 (C = 0) 155.7 (C = 0 ') 103.0 (C-1) 100.4 (C) 1 ') 60.8 (CH ₂ ) 51.8 (CH ₂ ) 49.2 (CH ₂ ) 41.0 (CH ₂ )
EA: C: 43.35% H: 7.31% N: 12.35%
DS: 1.67

b) Synthesis of N-.omega.-hydroxyethyl cellulose carbamate

N-.omega.-hydroxyethyl cellulose carbamate was prepared analogously to the process described under a) from cellulose phenyl carbonate and 2-aminoethanol.
Yield: 28 g (99%)
FT-IR (KBr): 3399 cm ^-1 v (OH) 2945 cm ^-1 -2885 cm ^-1 v (CH ₂ ) 1710 cm ^-1 v (C = O)
¹³ C-NMR (400 MHz, DMSO-d ₆ ,): δ [ppm] 156.5 (C = O) 103.0 (C-1) 100.2 (C-1 ') 60.4 (CH ₂ ) 43.5 (CH ₂ )
EA: C: 42.36% H: 6.34% N: 7.82%
DS: 1.76

c) Synthesis of N-.omega.-hydroxypropylcellulose carbamate

N-hydroxypropyl cellulose carbamate was synthesized from cellulose phenyl carbonate and 3-aminopropanol analogously to the process described under a).
Yield: 26 g (84%)
FT-IR (KBr): 3399 cm ^-1 v (OH) 2945 cm ^-1 -2885 cm ^-1 v (CH ₂ ) 1710 cm ^-1 v (C = O)
¹³ C-NMR (400 MHz, DMSO-d ₆ ,): δ [ppm] 157.5 (C = O) 58.9 (CH ₂ ) 100.2 (C-1 ') 60.4 (CH ₂ ) 43.5 (CH ₂ )
EA: C: 44.36% H: 6.94% N: 7.42%
DS: 1.85

d) Synthesis of N-1,3-ω-hydroxypropan-2-ylcellulose carbamate

35 g of cellulose 4-nitrophenyl carbonate (71 mmol) were added in 250 ml of dry DMF with 2-amino-1,3-propanediol (142 mmol) dissolved in 250 ml of dry DMF. The solution was stirred at room temperature for 30 minutes and then heated to 60 ° C. The reaction mixture was allowed to react at this temperature for 18 hours. The product was made by precipitation in 6 | 2-propanol isolated, filtered off with suction (G3 frit) and washed 3 times with 3 l of 2-propanol. After washing, the wet substance was taken up in 2.2 L of distilled water and completely dissolved at 60 ° C. The cellulose carbamate solution was freed from 2-propanol by azeotropic distillation at 80 mbar and freeze-dried (5 days, -55 ° C., 0.36 mbar).
Yield: 28 g (81%)
FT-IR (KBr): 3416 cm ^-1 v (OH) 2946 cm ^-1 -2883 cm ^-1 v (CH / CH ₂ ) 1708 cm ^-1 v (C = O)
¹³ C-NMR (400 MHz, DMSO-d ₆ ): δ [ppm] = 156.2 (C = O) 60.8 (CH ₂ ) 60.7 (CH ₂ ) 55.2 (CH ₂ ) 37, 5 (CH ₂ ) 31.7 (CH ₂ )
EA: C: 41.42% H: 6.24% N: 5.70%
DS: 1.26

e) Synthesis of N-omega-2- (2-hydroxyethyl) ethylene cellulose carbamate

40 g of cellulose phenyl carbonate (131 mmol) were dissolved in 480 ml of an 11% solution of urea in dry DMF. N-2- (2-hydroxyethyl) ethylenediamine (262 mmol) dissolved in 480 ml of dry DMF was added slowly to the cellulose phenyl carbonate solution. The reaction mixture was stirred at room temperature for 30 minutes and then heated to 60 ° C. After the mixture reacted at this temperature for 18 hours, the product was precipitated by precipitation 2-propanol isolated and filtered off with suction (G3 frit). The precipitation was 3 times with 2 | Washed 2-propanol and without drying in 3 | distilled water until a clear solution was formed. The cellulose carbamate solution was purified by azeotropic distillation at 80 mbar of 2-propanol freed and the pure solid obtained by freeze-drying (5 days, -55 ° C, 0.36 mbar).
Yield: 41 g (99%)
FT-IR (KBr): 3428 cm ^-1 v (OH) 2906 cm ^-1 v (CH ₂ ) 1710 cm ^-1 v (C = O)
¹³ C-NMR (400 MHz, DMSO-ds): δ [ppm] = 156.5 (C = O) 102.7 (C-1) 79.8-73.3 (C2-C5) 60.8 ( CH ₂ ) 49.0 (CH ₂ ) 45.9 (CH ₂ )
EA: C: 43.7% H: 6.84% N: 10.42%
DS: 1.17

f) Synthesis of N-.omega.-2- (2-hydroxyethyl) ethylene-2,3-O-cellulosecarbamate

To a solution of cellulose phenyl carbonate (186 mmol) in 250 mL of dry DMF was added N-2- (2-hydroxyethyl) ethylenediamine (372 mmol) dissolved in 250 mL of dry DMF slowly and the reaction mixture was stirred at room temperature for 30 min. The solution was heated to 60 ° C and held at this temperature for 18 h. The product was eliminated by precipitation in 5 | 2-Propanol isolated, the precipitate was filtered off with suction (G3 frit) and three times with 2 | Washed 2-propanol. The moist product was in 1 | taken up distilled water and the cellulose carbamate freed by azeotropic distillation at 80 mbar of 2-propanol. The pure solid was obtained by freeze-drying (6 days, -55 ° C, 0.36 mbar).
Yield: 31 g (81%)
FT-IR (KBr): 3346 cm ^-1 v (OH) 2889 cm ^-1 v (CH ₂ ) 1712 cm ^-1 v (C = O)
¹³ C-NMR (250 MHz, D ₂ O): δ [ppm] = 158.2 (C = 0 ') 157.5 (C = O) 102.3 (C-1) 100.4 (C-1 ') 78.2-72.9 (C-2-C-5) 59.9 (C-6) 56.5-36.9 (CH ₂ )
EA: C: 41.44% H: 6.47% N: 4.76%
DS: 0.35

Example 2

Table 1 shows the composition (ingredients in percent by weight, in each case based on the total agent) of the inventive detergents M1 to M6 and of the active ingredient free agent V1: Table 1: Compositions V1 M1 M2 M3 M4 M5 M6 C _9-13 Alkylbenzenesulfonate, Na salt 5 5 5 5 5 5 5 Sodium lauryl ether sulfate with 2 EO 6 6 6 6 6 6 6 C _12-14 fatty alcohol with 7 EO 5 5 5 5 5 5 5 C _12-18 fatty acid, Na salt 3 3 3 3 3 3 3 NaOH 2 2 2 2 2 2 2 citric acid 2 2 2 2 2 2 2 phosphonate 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Active ingredient I ^a) - 1 - - 1.5 - - Active ingredient II ^b) - - 1 - - 1.5 - Active substance III ^c) - - - 1 - - 1.5 water on 100 a) N-omega-2- (2-hydroxyethyl) ethylene cellulose carbamate; Example 1 a)
b) N-omega-hydroxyethyl cellulose carbamate; Example 1 b)
c) N-ω-hydroxypropyl cellulose carbamate; Example 1 c)

Means V1, M1, M2 or M3 were tested in a Miele® W 1714 washing machine (cotton washing program, 40 ° C., water hardness 16 ° dH, standardized soil carrier, dosage 70 g of the respective product per wash cycle). In addition to filling laundry to a load of 3.5 kg, the cotton materials listed in Table 2 were used (each 8 textile pieces in the size 20 x 40 cm).

Table 2 shows the difference in the brightness change (delta delta Y value) of the materials after 3 washes with the respective agent M1, M2 or M3 in comparison with 3 washes with the agent V1. Table 2: Brightness change to V1 Textile / Medium M1 M2 M3 WFK 10A 1.6 0.8 1.3 WFK 12A toweling 3.5 2.5 2.3 Terry towel 2.4 1.9 1.1 Krefeld standard 1.5 1.4 nb Doppelripp 3.4 1.6 1.8 EMPA 221 2.8 1.7 nb nb: not determined

Example 3

Polyester clean textiles were washed 3 times in a Miele® W 1514 washing machine at 40 ° C. with water of 16 ° dH with the detergent V1 stated in Example 2 or with the detergents M4, M5 or M6 likewise indicated there, and then air-dried. This was followed by the application of standardized soiling (A: sleeve and collar dirt, B: black shoe polish) to the test textiles and aging of the soiling of 7 days. The thus prepared fabrics were again washed with the detergent V under the above conditions at a capacity of 3.5 kg (clean linen plus polyester test fabrics). The evaluation was carried out colorimetrically; Table 3 shows the mean values of the brightness values (Y values) from 6-fold determinations. Table 3: Brightness value Y Soiling / medium V1 M4 M5 M6 A 49 54.3 54.1 53.1 B 33 42.7 40.7 34.8

Claims (10)

1. The use of cellulose carbamates which contain a substituted anhydroglucose unit of general formula I,

   

   where R represents H or -C(=O)-NR¹R², with the proviso that at least 1 of the groups R is identical to -C(=O)-NR¹R², and

   R¹ represents H or R², and R² represents an aryl, straight-chain or branched alkyl, aryl, alkylaryl or arylalkyl group, which can be substituted with one or more functional groups such as hydroxy, carboxy, oxy or amino groups, and/or which can be interrupted with heteroatoms such as N, O or S,

   for increasing the cleaning performance of washing agents when washing textiles.
2. A method for washing textiles, wherein a washing agent and a cellulose carbamate which contains a substituted anhydroglucose unit of general formula I,

   

   where R represents H or -C(=O)-NR¹R², with the proviso that at least 1 of the groups R is identical to -C(=O)-NR¹R², and

   R¹ represents H or R², and R² represents an aryl, straight-chain or branched alkyl, aryl, alkylaryl or arylalkyl group, which can be substituted with one or more functional groups such as hydroxy, carboxy, oxy or amino 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 concentration of cellulose carbamate used in the washing liquor is from 0.001 g/l to 1 g/l, in particular from 0.005 g/l to 0.2 g/l.
4. The method according to either claim 2 or claim 3, characterized in that said method is carried out using a washing agent which contains the cellulose carbamate.
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 cellulose carbamate.
6. The method according to one of claims 2 to 5, characterized in that the agent contains the cellulose carbamate in quantities of from 0.01 wt.% to 10 wt.%, in particular from 0.1 wt.% to 3 wt.%.
7. The use according to claim 1 or the method according to one of claims 2 to 6, characterized in that, in general formula I, the groups -NR¹R² are derived from amino alcohols, polyalkoxylated amines, α-amino acids, β-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.
8. The use or method according to one of the preceding claims, characterized in that the cellulose carbamate contains, in addition to the substituted anhydroglucose unit of general formula I, further anhydroglucose units which are 1,4-β-glycosidically linked thereto and which can be unsubstituted or correspond to general formula I.
9. The use or method according to one of the preceding claims, characterized in that anhydroglucose groups having other substituents are also present in the cellulose carbamate, 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, β-aminoproprionic acid, glycolic acid or malonic acid ester groups.
10. The use or method according to one of the preceding claims, characterized in that the degree of substitution in the cellulose carbamate is in the range of from 0.2 to 2, in particular from 0.4 to 1.2, based on the proportion of carbamate groups.