WO2023131527A1

WO2023131527A1 - Fucoidans as graying-inhibiting agents

Info

Publication number: WO2023131527A1
Application number: PCT/EP2022/087161
Authority: WO
Inventors: Christian Kropf; Arne Jansen
Original assignee: Henkel Ag & Co. Kgaa
Priority date: 2022-01-07
Filing date: 2022-12-21
Publication date: 2023-07-13
Also published as: DE102022200126A1

Abstract

The aim of the invention is to improve graying inhibition during the washing of textiles. This is achieved substantially by the use of fucoidans.

Description

Fucoidan as graying-inhibiting agents

The present invention relates to the use of certain polymers obtainable from renewable raw materials for preventing textiles from turning gray during washing.

In addition to the ingredients that are essential for the washing process, such as surfactants and builder materials, detergents usually contain other components that can be summarized under the term washing auxiliaries and that include such different groups of active ingredients as foam regulators, bleaching agents, bleach activators and color transfer inhibitors. Such auxiliaries also include substances which are intended to prevent components of the washing liquor from being deposited on the laundry fibers, which lead to a so-called gray haze on the laundry item after the washing process and thus have a negative effect on the overall result of the washing process. Such graying inhibitors also have the task of keeping the dirt detached from the fibers during the washing of textiles suspended in the liquor and thus preventing the dirt from being drawn back onto the textile. Water-soluble colloids, mostly of an organic nature, are suitable for this purpose, for example glue, gelatin, or salts of acidic sulfuric acid esters of cellulose or starch. Water-soluble polyamides containing acidic groups are also suitable for this purpose. Furthermore, soluble starch preparations and starch products other than those mentioned above can be used, for example degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone can also be used. Cellulose ethers such as carboxymethyl cellulose (Na salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof are also often used in amounts of normally 0.1 to 5% by weight, based on the detergent.

Although the cellulose ethers mentioned have a good graying-inhibiting effect, their use in liquid detergents, which generally contain a certain amount of water, is subject to such narrow limits that in practice they essentially cannot be incorporated into them. In addition to their anti-greying effect, which is only relevant when used in the washing process, these cellulose ethers have a comparatively low solubility in surfactant-containing systems and a strong thickening effect on aqueous systems. If they are incorporated in water-based and, in particular, anionic surfactant-containing liquid detergents in the concentrations desired for the graying-inhibiting effect, the result is generally either products that are no longer flowable and pourable, and the user can only handle them with additional effort, for example making them water-soluble or water-insoluble in water-soluble tearable form packaged single dosage portions, can be achieved, or the cellulose ethers, especially after storage, are not completely dissolved in the water-containing liquid detergent or are not evenly dispersed in it, which, in addition to aesthetics that are perceived as unsatisfactory, also leads to non-uniform dosing of the graying inhibitor active ingredient when using the agent containing it leads. International patent application WO 2006/117056 A1 discloses the use of celluloses which carry sulfoalkyl groups bonded via ether, ester or amide functions to prevent redeposition when washing textiles. The international patent application WO 2014/124872 A1 discloses surfactant-containing liquid detergents which contain sulfoethyl cellulose with a degree of substitution of 0.3 to 0.9 as the graying-inhibiting active ingredient.

Surprisingly, it has now been found that a good graying-inhibiting effect can be achieved without unacceptable increases in viscosity or precipitation occurring in aqueous liquid detergents if a polysaccharide derivative defined below is used.

The invention relates to the use of fucoidans to inhibit the graying of textile fabrics during washing.

Fucoidan are polysaccharides found in brown algae. They contain sulfated fucose and optionally galactose, xylose, mannose, glucose, gucuronic acid and rhamnose units. Lim, W.M. Wan Aida in Chapter 3 of Seaweed Polysaccharides, Elsevier 2017.

The use according to the invention can be carried out as part of a washing process in such a way that the graying-inhibiting active ingredient is added to an aqueous liquor containing detergent or, preferably, the active ingredient is introduced as a component of a detergent into the aqueous liquor which contains the textile fabric to be cleaned or which has been brought into contact with it becomes.

A further subject of the invention is a process for washing textiles, in which a detergent containing nonionic surfactant and a graying-inhibiting active ingredient in the form of a fucoidan are used in aqueous washing in an aqueous washing liquor. These procedures can be carried out manually or, if necessary, with the aid of a standard household washing machine. The detergent and the graying-inhibiting active ingredient are used simultaneously. This can be carried out particularly advantageously by using a detergent which contains the graying-inhibiting active ingredient. The method consists essentially in bringing a textile in need of cleaning, or at least the soiled part of its surface, into contact with an aqueous preparation containing the fucoidan and other usual detergent ingredients that are compatible with it, the aqueous preparation for a certain time on the textile or at least allowing the soiled part to act on its surface and removing the aqueous preparation, for example by rinsing the textile with water. The washing process preferably takes place at a temperature of 15.degree. C. to 60.degree. C., particularly preferably at a temperature of 20.degree. C. to 40.degree. The washing process is furthermore preferably carried out at a pH of 6 to 11, particularly preferably at a pH of 7.5 to 9.5. The use concentration of the fucoidan in the wash liquor is preferably 0.0001 g/l to 1 g/l, in particular 0.001 g/l to 0.1 g/l.

Another object of the invention is a surfactant-containing detergent containing fucoidan and nonionic surfactant.

Detergents that contain an active ingredient to be used according to the invention in the form of the fucoidan mentioned or used together with it or used in processes according to the invention can contain all the usual other ingredients of such detergents that do not interact in an undesirable manner with the active ingredient essential to the invention, in particular surfactant. The active ingredient defined above is preferably used in amounts of from 0.05% by weight to 5% by weight, particularly preferably from 0.3% by weight to 2% by weight, with this and the following quantitative data being different refer to the entire funds, unless otherwise stated. An agent according to the invention or used in the method according to the invention or used in the context of the use according to the invention preferably contains water and is liquid; it contains in particular 2% by weight to 92% by weight, particularly preferably 3% by weight to 85% by weight, of water.

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

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

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

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

Nonionic surfactant is used according to the invention in agents that contain a graying-inhibiting active ingredient used according to the invention or are used in the method according to the invention, preferably in amounts of 1% by weight to 30% by weight, in particular from 2% by weight to 25% by weight. %, with amounts in the upper part of this range being more likely to be found in liquid detergents and particulate detergents preferably containing rather lower amounts of up to 5% by weight.

Instead or in addition, the agents can contain other surfactants, preferably synthetic anionic surfactants of the sulfate or sulfonate type, such as alkylbenzenesulfonates, in amounts of preferably up to 20% by weight, in particular from 0.1% by weight to 18% by weight. %, in each case based on the total agent. Synthetic anionic surfactants which are particularly suitable for use in such agents are the alkyl and/or alkenyl sulfates having 8 to 22 carbon atoms which carry an alkali metal, ammonium or alkyl or hydroxyalkyl-substituted ammonium ion as counter cation. The derivatives of fatty alcohols with in particular 12 to 18 carbon atoms and their branched-chain analogues, the so-called oxo alcohols, are preferred. The alkyl and alkenyl sulfates can be prepared in a known manner by reacting the corresponding alcohol component with a customary sulfating agent, in particular sulfur trioxide or chlorosulfonic acid, and subsequent neutralization with alkali metal, ammonium, or alkyl or hydroxyalkyl-substituted ammonium bases. The sulfate-type surfactants that can be used also include the sulfated alkoxylation products of the alcohols mentioned, so-called ether sulfates. Such ether sulfates preferably contain 2 to 30, in particular 4 to 10, ethylene glycol groups per molecule. Suitable anionic surfactants of the sulfonate type include the a-sulfoesters obtainable by reacting fatty acid esters with sulfur trioxide and subsequent neutralization, in particular those derived from fatty acids having 8 to 22 carbon atoms, preferably 12 to 18 carbon atoms, and linear alcohols having 1 up to 6 carbon atoms, preferably 1 to 4 carbon atoms, deriving sulfonation products, and the sulfofatty acids resulting from these by formal hydrolysis.

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

If desired, the agents can also contain betaines, which—if present—are preferably used in amounts of 0.5% by weight to 7% by weight. Among these, ester quats are particularly preferred. Esterquats are quaternized fatty acid triethanolamine ester salts that follow formula (IV),

in which R ¹ CO is an acyl radical having 6 to 22 carbon atoms, R ² and R ³ are each independently hydrogen or R ¹ CO, R ⁴ is an alkyl radical having 1 to 4 carbon atoms or a (CH2CH2Ö) _q H group, m, n and p in total are O 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 technical mixtures thereof , such as those that occur during the pressure splitting of natural fats and oils. Technical C12/18 coconut fatty acids and in particular partially hydrogenated C16/15 tallow or palm fatty acids and C16/18 fatty acid cuts rich in elaidic acid are preferably used. To prepare the quaternized ester, the fatty acids and the triethanolamine can generally be used in a molar ratio of 1.1:1 to 3:1. With regard to the performance properties of the esterquats, a ratio of from 1.2:1 to 2.2:1, preferably from 1.5:1 to 1.9:1, has proven to be particularly advantageous. The esterquats preferably used are technical mixtures of mono-, di- and triesters with an average degree of esterification of 1.5 to 1.9 and are derived from technical Ci6/is tallow or palm fatty acid (iodine number 0 to 40). Quaternized fatty acid triethanolamine ester salts of the formula (IV) in which R ¹ CO represents an acyl radical having 16 to 18 carbon atoms, R ² represents R ¹ CO, R ³ represents hydrogen, R ⁴ represents a methyl group, m, n and p represent 0 and X represents Methyl sulfate is, have proven to be particularly advantageous. In addition to the quaternized carboxylic acid triethanolamine ester salts, quaternized ester salts of carboxylic acids with diethanolalkylamines of the formula (V) can also be used as ester quats,

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

Finally, another group of suitable ester quats are the quaternized ester salts of carboxylic acids with 1,2-dihydroxypropyldialkylamines of the formula (VI),

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

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

Esterquats are preferably used in amounts of 5% by weight to 25% by weight, in particular 8% by weight to 20% by weight, based in each case on the detergent as a whole.

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

The composition preferably contains 20% by weight to 55% by weight of water-soluble and/or water-insoluble, organic and/or inorganic builder. The water-soluble organic builder substances include in particular those from the class of polycarboxylic acids, in particular citric acid and sugar acids, and polymeric (poly)carboxylic acids, in particular the polycarboxylates accessible by oxidation of polysaccharides, polymeric acrylic acids, methacrylic acids, maleic acids and mixed polymers these, which can also contain small proportions of polymerizable substances without carboxylic acid functionality in copolymerized form. The relative molecular mass of the homopolymers of unsaturated carboxylic acids is generally between 5000 g/mol and 200000 g/mol, that of the copolymers between 2000 g/mol and 200000 g/mol, preferably 50000 g/mol to 120000 g/mol, based on the free acid . A particularly preferred acrylic acid-maleic acid copolymer has a relative molecular weight of 50,000 g/mol to 100,000 g/mol. Suitable, although less preferred, compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinyl methyl ethers, vinyl esters, ethylene, propylene and styrene, in which the proportion of the acid is at least 50% by weight. Terpolymers which contain two carboxylic acids and/or their salts as monomers and vinyl alcohol and/or a vinyl alcohol derivative or a carbohydrate as the third monomer can also be used as water-soluble organic builder substances. The first acidic monomer or its salt is derived from a monoethylenically unsaturated Cs-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 C4-Cs-dicarboxylic acid, with maleic acid being particularly preferred. In this case, the third monomeric unit is formed by vinyl alcohol and/or preferably an esterified vinyl alcohol. In particular, preference is given to vinyl alcohol derivatives which are an ester of short-chain carboxylic acids, for example of C 1 -C 4 carboxylic acids, with vinyl alcohol. Preferred terpolymers contain 60% by weight to 95% by weight, in particular 70% by weight to 90% by weight, of (meth)acrylic acid or (meth)acrylate, particularly preferably acrylic acid or acrylate, and maleic acid or maleate as well 5% to 40% by weight, preferably 10% to 30% by weight, of vinyl alcohol and/or vinyl acetate. Very particular preference is given to terpolymers in which the weight ratio of (meth)acrylic acid or (meth)acrylate to maleic acid or maleate is between 1:1 and 4:1, preferably between 2:1 and 3:1 and in particular 2:1 and 2. 5:1 lies. 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 substituted 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. 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 from 20% to 40% by weight of a carbohydrate. This carbohydrate can be, for example, a mono-, di-, oligo- or polysaccharide, with mono-, di- or oligosaccharides being preferred, and sucrose being particularly preferred. Presumably, the use of the third monomer incorporates predetermined breaking points in the polymer, which are responsible for the good biodegradability of the polymer. These terpolymers generally have a relative molecular mass of between 1000 g/mol and 200000 g/mol, preferably between 3000 g/mol and 10000 g/mol. They can be used in the form of aqueous solutions, preferably in the form of 30 to 50 percent by weight aqueous solutions, particularly for the production of liquid compositions. All of the polycarboxylic acids mentioned are generally used in the form of their water-soluble salts, in particular their alkali metal salts.

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

In particular, crystalline or amorphous alkali metal aluminosilicates, in amounts of up to 50% by weight, preferably not more than 40% by weight and in liquid compositions, in particular from 1% by weight to 5% by weight, are used as water-insoluble, water-dispersible inorganic builder materials. deployed. Among these, the crystalline detergent grade aluminosilicates, particularly zeolite NaA and optionally NaX, are preferred. Amounts close to the upper limit mentioned are preferably used in solid, particulate compositions. In particular, suitable aluminosilicates do not have any particles with a particle size of more than 30 μm and preferably consist of at least 80% by weight of particles with a size of less than 10 μm. Your 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 or partial substitutes for the aluminosilicate mentioned are crystalline alkali silicates, alone or in a mixture with amorphous silicates may exist. The alkali metal silicates which can be used as builders in the agents preferably have a molar ratio of alkali metal oxide to SiO 2 below 0.95, in particular from 1:1.1 to 1:12, and can be present in amorphous or crystalline form. Preferred alkali metal silicates are the sodium silicates, in particular the amorphous sodium silicates, with a molar Na2O:SiO2 ratio of 1:2 to 1:2.8. Such amorphous alkali silicates are commercially available, for example, under the name Portil®. During production, they are preferably added as a solid and not in the form of a solution. Crystalline phyllosilicates of the general formula Na2Si _x O2x+i yH2O are preferably used as crystalline silicates, which can be present alone or in a mixture with amorphous silicates, in which x, the so-called modulus, is a number from 1.9 to 4 and y is a number is from 0 to 20 and preferred values for x are 2, 3 or 4. Preferred crystalline layered silicates are those in which x in said general formula takes on the values 2 or 3. In particular, both ß- and 5-sodium disilicates (Na2Si2O5 yH2O) are preferred. Practically anhydrous crystalline alkali metal silicates of the abovementioned general formula, in which x is a number from 1.9 to 2.1, produced from amorphous alkali metal silicates can also be used in agents which contain an active ingredient to be used according to the invention. In a further preferred embodiment of agents according to the invention, a crystalline layered sodium silicate with a modulus of 2 to 3 is used, as can be produced from sand and soda. Crystalline sodium silicates with a modulus in the range from 1.9 to 3.5 are used in a further preferred embodiment of detergents which contain an active ingredient used according to the invention. Their content of alkali metal silicates is preferably 1% by weight to 50% by weight and in particular 5% by weight to 35% by weight, based on anhydrous active substance. If alkali metal aluminosilicate, in particular zeolite, is also present as an additional builder substance, the alkali metal silicate content is preferably 1% by weight to 15% by weight and in particular 2% by weight to 9% 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 detergents which contain both amorphous and crystalline alkali metal silicates, the weight ratio of amorphous alkali metal silicate to crystalline alkali metal silicate is preferably 1:2 to 2:1 and in particular 1:1 to 2:1.

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

A composition which contains an active substance 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 ranging from 3% by weight to 70% by weight, and optionally However, in another preferred embodiment, bleach activator, in particular in amounts in the range from 0.5% by weight to 10% by weight, can also be free of bleach and bleach activator. The bleaches that come into consideration are preferably the peroxygen compounds usually used in detergents, such as percarboxylic acids, for example dodecanediperoic acid or phthaloylaminoperoxicaproic acid, hydrogen peroxide, alkali metal perborate, which can be in the form of tetrahydrate or monohydrate, percarbonate, perpyrophosphate and persilicate, which are generally present as alkali metal salts, in particular as sodium salts. Bleaching agents of this type are present in detergents which contain an active ingredient used according to the invention, preferably in amounts of up to 25% by weight, in particular up to 15% by weight and particularly preferably from 3% by weight to 15% by weight on the entire agent, available, with percarbonate being used in particular. The optional component of the Bleach activators includes the N- or O-acyl compounds commonly used, for example polyacylated alkylenediamines, in particular tetraacetylethylenediamine, acylated glycolurils, in particular tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, urazoles, diketopiperazines, sulfurylamides and cyanurates, as well as carboxylic acid anhydrides, in particular phthalic anhydride, carboxylic acid esters, in particular sodium isononanoylphenol sulfonate, and acylated sugar derivatives, in particular pentaacetyl glucose, and cationic nitrile derivatives such as trimethylammonium acetonitrile salts. To avoid interaction with the peroxygen compounds during storage, the bleach activators may have been coated or granulated in a known manner with encapsulating substances, granulated tetraacetylethylenediamine having weight-average grain sizes of 0.01 mm to 0.8 mm, granulated 1,5- Diacetyl-2,4-dioxohexahydro-1,3,5-triazine and/or trialkylammoniumacetonitrile formulated in particulate form is particularly preferred. Such bleach activators are preferably present in detergents in amounts of up to 8% by weight, in particular from 0.5% by weight to 6% by weight, based in each case on the detergent as a whole.

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

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

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

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

Suitable foam inhibitors include long-chain soaps, in particular behenic soap, fatty acid amides, paraffins, waxes, microcrystalline waxes, organopolysiloxanes and mixtures thereof, which can also contain microfine, optionally silanized or otherwise hydrophobic 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 substance to be used according to the invention is incorporated is particulate and contains up to 25% by weight, in particular 4% by weight to 20% by weight, of bleaching agent, in particular alkali metal percarbonate, up to 15% by weight. -%, in particular 1% to 10% by weight bleach activator, 20% to 55% by weight inorganic builder, up to 10% by weight, in particular 2% to 8% by weight % water-soluble organic builder, 10% to 25% by weight synthetic anionic surfactant, 1% to 5% by weight nonionic surfactant and up to 25% by weight, especially 0.1% by weight up to 25% by weight of inorganic salts, in particular alkali metal carbonate and/or bicarbonate.

In a further preferred embodiment, a composition into which an 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% by weight to 5% by weight, in particular 1% by weight to 4% by weight, organic Builder, in particular polycarboxylate such as citrate, up to 1.5% by weight, in particular 0.1% by weight to 1% by weight, of complexing agent for heavy metals, such as phosphonate, and, in addition to any enzyme present, enzyme stabilizer, colorant and/or or fragrance water and/or water-miscible solvent.

The known polyester-active soil release polymers include copolyesters of dicarboxylic acids, for example adipic acid, phthalic acid or terephthalic acid, diols, for example ethylene glycol or propylene glycol, and polydiols, for example polyethylene glycol or polypropylene glycol. The preferably used dirt-removing 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 can also be used as a polymeric diol H-(O-(CHR ¹¹ -) _a ) _b OH may be present. Ph is an o-, m- or p-phenylene radical which can carry 1 to 4 substituents selected from alkyl radicals having 1 to 22 carbon atoms, sulfonic acid groups, carboxyl groups and mixtures thereof, R ¹¹ is hydrogen, an alkyl radical having 1 to 22 carbon atoms and mixtures thereof, a is a number from 2 to 6 and b is a number from 1 to 300. The polyesters obtainable from these preferably contain both monomer diol units -O-(CHR ¹¹ -) _a O- and polymer diol units --( O-(CHR ¹¹ -) _a )bO- before. The molar ratio of monomer diol units to polymer diol units is preferably from 100:1 to 1:100, in particular from 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-removing 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 present in salt form, in particular as an alkali metal or ammonium salt. Among these, the sodium and potassium salts are particularly preferred. If desired, instead of the HOOC-Ph-COOH monomer, small proportions, in particular not more than 10 mol % based on the proportion of Ph with the meaning given above, of other acids which have at least two carboxyl groups can be present in the soil-removing polyester. These include, for example, alkylene and alkenylenedicarboxylic acids such as malonic acid, succinic acid, fumaric acid, maleic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid. The preferred diols HO-(CHR ¹¹ -) _a OH include those in which R ¹¹ is hydrogen and a is from 2 to 6 and those in which a is 2 and R ¹¹ is selected from hydrogen and the alkyl radicals 1 to 10, in particular 1 to 3 carbon atoms is selected. Among the last-mentioned diols, those of the formula HO-CH2-CHR ¹¹ -OH, in which R ¹¹ has the meaning given above, are particularly preferred. Examples of diol components are ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,2-decanediol, 1,2-dodecanediol and neopentyl glycol. Particularly preferred among the polymeric diols is polyethylene glycol with an average molar mass in the range from 1000 g/mol to 6000 g/mol.

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

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

A washing test was carried out with a liquid detergent that contained neither cellulase nor graying inhibitors in the presence of a standardized soil carrier (Miele® W 1935 washing machine, cotton wash program, 40° C.; water hardness 16° dH; dosage 52.5 g). In addition to filling laundry, the test textiles listed in Table 1 were used for a load of 3.5 kg. After a total of 5 washing cycles, the lightness value Y was measured, which is a measure of the graying resulting from the transfer of dirt from the standardized soil carrier to the test textiles. The higher the Y value, the less gray the test textiles are.

The table below shows the Y values for V1, the abovementioned liquid detergent, and for M1, the abovementioned liquid detergent with the addition of 1% by weight (based on the liquid detergent) of fucoidan obtained by extraction from Fucus Vesiculolus.

Table 1: Y values (brightness) after washing

When using the agent M1, which contains the substance according to the invention, the materials gray significantly less than when using the agent V1.

Claims

patent claims

1 . Use of fucoidans to inhibit the graying of textile fabrics during washing.

2. A process for washing textiles in which a detergent containing nonionic surfactant and a fucoidan are used in an aqueous washing liquor.

3. The method as claimed in claim 2, characterized in that the use concentration of the fucoidan in the wash liquor is 0.0001 g/l to 1 g/l, in particular 0.001 g/l to 0.1 g/l.

4. The method according to claim 2 or 3, characterized in that it is carried out at a temperature in the range from 15 °C to 60 °C, in particular in the range from 20 °C to 40 °C.

5. The method according to any one of claims 2 to 4, characterized in that it is carried out using a detergent containing the fucoidan.

6. Detergent containing nonionic surfactant and fucoidan.

7. Agent according to claim 6, characterized in that it contains the fucoidan in amounts of 0.05% by weight to 5% by weight, in particular from 0.3% by weight to 2% by weight.

8. Agent according to Claim 6 or 7, characterized in that it contains 1% by weight to 30% by weight, in particular 2% by weight to 25% by weight, of nonionic surfactant and/or up to 20% by weight. %, in particular 0.1% by weight to 18% by weight, of further surfactant.

9. Agent according to one of Claims 6 to 8, characterized in that it contains water and is liquid and in particular contains 2% by weight to 92% by weight of water.