EP2922941B1 - Use of antiadhesive polymers for microbe-repulsive textile finishing - Google Patents

Use of antiadhesive polymers for microbe-repulsive textile finishing Download PDF

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Publication number
EP2922941B1
EP2922941B1 EP13791992.4A EP13791992A EP2922941B1 EP 2922941 B1 EP2922941 B1 EP 2922941B1 EP 13791992 A EP13791992 A EP 13791992A EP 2922941 B1 EP2922941 B1 EP 2922941B1
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Prior art keywords
alkyl
group
aryl
general formula
cellulose derivative
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EP13791992.4A
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German (de)
French (fr)
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EP2922941A1 (en
Inventor
Paula Barreleiro
Mirko Weide
Martina HUTMACHER
Rainer Simmering
Noelle Wrubbel
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C11D3/225—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin etherified, e.g. CMC
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C11D3/227—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin with nitrogen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/12—Soft surfaces, e.g. textile

Definitions

  • the present invention relates to the use of certain polymers to reduce the adhesion of microorganisms to textiles.
  • Microorganisms such as bacteria, fungi and viruses can colonize household and textile surfaces. Bacteria and fungi can also multiply on such surfaces. This can result in hygiene risks, but also lead to unaesthetic microbial deposits, so-called biofilms. The occurrence of microbially induced, especially bacterially caused bad odors is possible. Garments made of delicate materials such as silk or microfibers can only be washed at 30 ° C or 40 ° C. It is possible that thereby fungi, such as the human pathogenic Candida albicans, and bacteria are not always killed sufficiently. In particular, after a fungal infection can come by such adhering to garments, not killed fungi to a reinfection.
  • biostatics microorganisms
  • biocides used for example in detergents and cleaners enter the wastewater after use and may impair the function of the microbial treatment stages in the sewage treatment plants.
  • selection pressure on the microorganisms for resistance formation is greatly increased, so that after some time new antimicrobial substances must be found that act against resistant microorganisms. It is therefore desirable to have biorepulsive substances instead of biocidal or biostatic substances which prevent the adhesion of the microorganisms without physiologically impairing the microorganisms.
  • the international patent application WO 2006/071452 A2 The use of polyester amides for the temporary or permanent finishing of textile surfaces is known.
  • the international patent application WO 2006/071451 A2 relates to the reduction of the adhesion of microorganisms to textile surfaces by copolymers of 5 wt .-% to 95 wt .-% of anionic vinyl monomer and 5 wt .-% to 95 wt .-% of nonionic hydrophilic vinyl monomer, wherein vinyl monomers having secondary or tertiary amino group or Ammonium group, polyfunctional vinyl monomers, hydrophobic vinyl monomers and / or vinyl monomers having silicone groups can be present in addition.
  • the cellulose derivative of the general formula (I) is preferably selected from the group comprising Trialkylammoniumhydroxypropylcellulose and trialkylammoniumethylcellulose and mixtures thereof.
  • at least one radical R corresponds to the general formula (II) or (III), where m, n and o are greater than 0 and / or the grouping -R 1 is -NR 2 R 3 ( R 4 ) q .
  • the substituents of general formulas (II) and (III) can be introduced by etherification of free hydroxy groups of the cellulose with the corresponding halides, halohydrins or epoxides.
  • Amine-modified cellulose ethers are obtainable by reacting at least one hydroxyl group of cellulose and / or hydroxyl-containing cellulose ethers, for example alkyl, alkylcarboxyalkyl, hydroxyalkyl or alkylhydroxyalkylcellulose ethers, with halogenated alkylamines.
  • Particularly suitable halogenoalkylamines are trialkylamines in which an alkyl group carries a halogen atom, in particular chlorine.
  • 1-diethylamino-2-chloroethane, 2-chloro-N, N-dimethylpropylamine and 3-chloro-N, N-dimethylpropylamine are particularly preferable.
  • this may be present in the usual manner in salt form, for example as hydrochloride.
  • R Cell in the cellulose derivative according to formula (I) are an average of preferably from 0.01 to 1, especially 0.1 to 0.8 of R 1, which the group -NR 2 R 3 (R 4) q wear available that is, averaged over the entire cellulose derivative, preferably every one-hundredth to every, and particularly every tenth to every eighth, of tens of the anhydroglucose units is substituted with a nitrogen atom-bearing group.
  • the cellulose is substituted with a C 8-24 alkyl dialkyl ammonium hydroxypropyl group and / or a C 8-24 alkyl dialkyl ammonium ethyl group.
  • the average molar mass of the cellulose derivatives used according to the invention is preferably in the range of up to 500,000 g / mol.
  • the mean molar masses indicated here and later, if appropriate, for other polymeric ingredients are weight-average molar masses M w , which can in principle be determined by means of gel permeation chromatography with the aid of an RI detector, the measurement being expediently carried out against an external standard.
  • a cellulose derivative used according to the invention has a solubility in water at 25 ° C over the entire range of pH 7 to pH 9, particularly preferably over the entire Range of pH 2 to pH 11, of at least 0.01 g / l, in particular of at least 0.1 g / l and particularly preferably from 1 g / l to 15 g / l on.
  • the cellulose derivatives mentioned are able to furnish textiles in such a way that microbial growth on them is avoided because bacteria, fungi and / or viruses do not adhere or only adhere to a reduced extent on the textile surface treated with them.
  • Another object of the invention is therefore the use of said cellulose derivatives for preventing or reducing the adhesion of microorganisms, in particular of bacteria, fungi and / or viruses, to textiles.
  • an aqueous liquor which contains 1 mg / l to 5000 mg / l, in particular 10 mg / l to 500 mg / l of the cellulose derivative used according to the invention.
  • the use according to the invention can preferably be realized by allowing a detergent containing a said cellulose derivative to act on a textile in the course of a machine or hand washing operation. Further objects of the invention are therefore the use of a detergent containing a said cellulose derivative for preventing the microbial colonization of textile surfaces, and the use of a detergent containing a said cellulose derivative for preventing or reducing the adhesion of microorganisms to textiles.
  • a detergent which is understood here to mean a means for washing laundry or a laundry pre-treatment agent used before the actual washing process, for example a stain remover or a laundry after-wash treatment such as, for example, a fabric softener, preferably contains 0.01% by weight .-% to 2 wt .-%, in particular 0.05 wt .-% to 1.5 wt .-% and particularly preferably 0.5 wt .-% to 1.2 wt .-% of said active ingredient in addition to conventional with this compatible ingredients.
  • agents which may be in the form of particularly pulverulent solids, in densified particle form, as homogeneous solutions or as suspensions or dispersions, may in principle contain all known ingredients customary in such agents besides the cellulose derivative used according to the invention.
  • the detergents may in particular contain builder substances, surface-active surfactants, bleaches, bleach activators and catalysts, water-miscible organic solvents, enzymes, sequestering agents, electrolytes, pH regulators or other auxiliaries, such as optical brighteners, grayness inhibitors, color transfer inhibitors, foam regulators and dyes and fragrances. If they are liquid and hydrous, they preferably have a pH in the range of 8 to 12, especially 9 to 12; otherwise, the pH ranges mentioned apply to 0.47% by weight aqueous solutions of the agents.
  • the agents may contain one or more surfactants, in particular anionic surfactants, nonionic surfactants and mixtures thereof come into question.
  • Suitable nonionic surfactants are in particular alkyl glycosides and ethoxylation and / or propoxylation of alkyl glycosides or linear or branched alcohols each having 12 to 18 carbon atoms in the alkyl moiety and 3 to 20, preferably 4 to 10 alkyl ether groups.
  • ethoxylation and / or propoxylation products of N-alkylamines, vicinal diols, fatty acid esters and fatty acid amides which correspond to said long-chain alcohol derivatives with respect to the alkyl moiety and of alkylphenols having 5 to 12 carbon atoms in the alkyl radical.
  • Suitable anionic surfactants are in particular soaps and those which contain sulfate or sulfonate groups with preferably alkali ions as cations.
  • Usable soaps are preferably the alkali salts of the saturated or unsaturated fatty acids having 12 to 18 carbon atoms. Such fatty acids can also be used in incompletely neutralized form.
  • Useful surfactants of the sulfate type include the salts of the sulfuric acid half-esters of fatty alcohols having 12 to 18 carbon atoms and the sulfation products of said nonionic surfactants having a low degree of ethoxylation.
  • Suitable surfactants of the sulfonate type include linear alkylbenzenesulfonates having 9 to 14 carbon atoms in the alkyl moiety, alkanesulfonates having 12 to 18 carbon atoms, and olefin sulfonates having 12 to 18 carbon atoms, which are formed in the reaction of corresponding monoolefins with sulfur trioxide, and alpha-sulfofatty acid esters resulting from the sulfonation of fatty acid methyl or ethyl esters.
  • Such surfactants are present in detergents in proportions of preferably from 5% by weight to 50% by weight, in particular from 8% by weight to 30% by weight.
  • a detergent preferably contains at least one water-soluble and / or water-insoluble, organic and / or inorganic builder.
  • the water-soluble organic builder substances include polycarboxylic acids, in particular citric acid and sugar acids, monomeric and polymeric aminopolycarboxylic acids, in particular glycinediacetic acid, methylglycinediacetic acid, nitrilotriacetic acid, iminodisuccinates such as ethylenediamine-N, N'-disuccinic acid and hydroxyiminodisuccinates, ethylenediaminetetraacetic acid and polyaspartic acid, polyphosphonic acids, in particular aminotris (methylenephosphonic acid), ethylenediamine tetrakis (methylene-phosphonic acid), Lysintetra (methylenephosphonic acid) and 1-hydroxyethane-1,1-diphosphonic acid, polymeric hydroxy compounds such as dextrin and polymeric (poly) carboxylic acids, especially by oxid
  • the relative average molecular weight of the homopolymers of unsaturated carboxylic acids is generally between 5,000 g / mol and 200,000 g / mol, that of the copolymers between 2,000 g / mol and 200,000 g / mol, preferably 50,000 g / mol to 120,000 g / mol, in each case based on the free acid.
  • a particularly preferred acrylic acid-maleic acid copolymer has a relative average molecular weight of 50,000 to 100,000.
  • 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.
  • vinyl ethers such as vinylmethyl ethers, vinyl esters, ethylene, propylene and styrene
  • terpolymers which contain two unsaturated acids and / or salts thereof as monomers and vinyl alcohol and / or a vinyl alcohol derivative or a carbohydrate as the third monomer.
  • 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.
  • Preferred polymers contain from 60% by weight to 95% by weight, in particular from 70% by weight to 90% by weight, of (meth) acrylic acid or (meth) acrylate, particularly preferably acrylic acid or acrylate, and maleic acid or Maleinate and 5 wt .-% to 40 wt .-%, preferably 10 wt .-% to 30 wt .-% of vinyl alcohol and / or vinyl acetate.
  • 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.
  • 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. Particularly preferred is sucrose.
  • the use of the third monomer presumably incorporates predetermined breaking points into the polymer which are responsible for the good biodegradability of the polymer.
  • These terpolymers generally have a relative average molecular weight between 1,000 g / mol and 200,000 g / mol, preferably between 200 g / mol and 50,000 g / mol.
  • Further preferred copolymers are those which have as monomers acrolein and acrylic acid / acrylic acid salts or vinyl acetate.
  • the organic builder substances 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 of the acids mentioned are generally used in the form of their water-soluble salts, in particular their alkali metal salts.
  • organic builder substances may be present in amounts of up to 40% by weight, in particular up to 25% by weight and preferably from 1% by weight to 8% by weight. Quantities close to the stated upper limit are preferably used in pasty or liquid, in particular hydrous, agents.
  • Suitable water-soluble inorganic builder materials are, in particular, polyphosphates, preferably sodium triphosphate.
  • water-insoluble inorganic builder materials are in particular crystalline or amorphous, water-dispersible alkali metal aluminosilicates, in amounts not exceeding 25 wt .-%, preferably from 3 wt .-% to 20 wt .-% and in particular in amounts of 5 wt .-% to 15 wt. -% used.
  • the detergent-grade crystalline sodium aluminosilicates particularly zeolite A, zeolite P, and zeolite MAP, and optionally zeolite X, are preferred.
  • Amounts near the above upper limit are preferably used in solid, particulate agents.
  • suitable aluminosilicates have no particles with a particle size greater than 30 .mu.m and preferably consist of at least 80% by weight of particles having a size of less than 10 .mu.m.
  • Their calcium binding capacity is generally in the range of 100 to 200 mg CaO per gram.
  • water-soluble inorganic builder materials may be included.
  • polyphosphates such as sodium triphosphate
  • these include in particular the water-soluble crystalline and / or amorphous alkali metal silicate builders.
  • Such water-soluble inorganic builder materials are preferably present in the compositions in amounts of from 1% to 20% by weight, in particular from 5% to 15% by weight.
  • the alkali silicates useful as builder materials preferably have a molar ratio of alkali oxide to SiO 2 below 0.95, in particular from 1: 1.1 to 1:12, and may be amorphous or crystalline.
  • 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.
  • Crystalline silicates which may be present alone or in a mixture with amorphous silicates are preferably crystalline phyllosilicates of the general formula Na 2 Si x O 2 ⁇ + 1 ⁇ y H 2 O is used, in which x, the so-called modulus, is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4.
  • Preferred crystalline phyllosilicates are those in which x in the abovementioned general formula assumes the values 2 or 3.
  • both ⁇ - and ⁇ -Natriumdisitikate Na 2 Si 2 O 5 ⁇ y H 2 O
  • amorphous alkali metal silicates practically anhydrous crystalline alkali metal silicates of the abovementioned general formula in which x is a number from 1.9 to 2.1, can be used in the compositions.
  • a crystalline sodium layer silicate with a modulus of 2 to 3 is used, as can be prepared from sand and soda.
  • Sodium silicates with a modulus in the range 1.9 to 3.5 are used in a further embodiment.
  • a granular compound of alkali silicate and alkali carbonate is used, as is commercially available, for example, under the name Nabion® 15.
  • Suitable bleaching agents are those based on chlorine, in particular alkali hypochlorite, dichloroisocyanuric acid, trichloroisocyanuric acid and salts thereof, but especially those based on peroxygen.
  • Suitable peroxygen compounds are, in particular, organic peracids or persaltic salts of organic acids, such as phthalimidopercaproic acid, perbenzoic acid, monoperoxyphthalic acid, and diperdodecanedioic acid and salts thereof, such as magnesium monoperoxyphthalate, hydrogen peroxide and inorganic salts which release hydrogen peroxide under the conditions of use, such as perborate, percarbonate and / or persilicate, and hydrogen peroxide.
  • Hydrogen peroxide can also be produced by means of an enzymatic system, ie an oxidase and its substrate. If solid peroxygen compounds are to be used, they can be used in the form of powders or granules, which can also be enveloped in a manner known in principle. Particular preference is given to using alkali metal percarbonate, alkali metal perborate monohydrate or hydrogen peroxide in the form of aqueous solutions which contain from 3% by weight to 10% by weight of hydrogen peroxide. If a detergent contains peroxygen compounds, they are present in amounts of preferably up to 25% by weight, more preferably from 1% to 20% and most preferably from 7% to 20% by weight.
  • bleach-activating peroxycarboxylic acid-yielding compound under perhydrolysis conditions it is possible in particular to use compounds which give perbenzoic acid which is optionally substituted under perhydrolysis conditions and / or aliphatic peroxycarboxylic acids having 1 to 12 C atoms, in particular 2 to 4 C atoms, alone or in mixtures.
  • Suitable bleach activators which carry O- and / or N-acyl groups, in particular of the stated C atom number and / or optionally substituted benzoyl groups.
  • polyacylated alkylenediamines in particular tetraacetylethylenediamine (TAED), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates or carboxylates or the sulfonic or carboxylic acids of these, in particular nonanoyl or isononanoyl or lauroylbenzenesulfonate (NOBS or iso-NOBS or LOBS) or decanoyloxybenzoate ( DOBA), whose formal carbonic acid ester derivatives such as 4- (2-decanoyloxyethoxycarbonyloxy)
  • bleach-activating compounds such as nitriles, from which perimide acids form under perhydrolysis conditions may be present.
  • These include in particular aminoacetonitrile derivatives with quaternized nitrogen atom according to the formula in the R 1 is -H, -CH 3 , a C 2-24 -alkyl or alkenyl radical, a substituted C 1-24 -alkyl or C 2-24 -alkenyl radical having at least one substituent from the group -Cl, -Br, -OH, -NH 2 , -CN and -N (+) -CH 2 -CN, an alkyl or alkenylaryl radical having a C 1-24 -alkyl group, or a substituted alkyl- or alkenylaryl radical having at least one, preferably two, optionally substituted C 1-24 alkyl group (s) and optionally further substituents on the aromatic ring, R
  • transition metal complexes are preferably selected from the cobalt, iron, copper, titanium, vanadium, manganese and ruthenium complexes.
  • Suitable ligands in such transition metal complexes are both inorganic and organic compounds, which in addition to carboxylates in particular compounds having primary, secondary and / or tertiary amine and / or alcohol functions, such as pyridine, pyridazine, pyrimidine, pyrazine, imidazole, pyrazole , Triazole, 2,2'-bispyridylamine, tris (2-pyridylmethyl) amine, 1,4,7-triazacyclononane, 1,4,7-trimethyl-1,4,7-triazacyclononane, 1,5,9-trimethyl -1,5,9-triazacyclododecane, (bis ((1-methylimidazol-2-yl) methyl)) - (2-pyridylmethyl)) - (2-pyridyl
  • the inorganic neutral ligands include in particular ammonia and water. If not all coordination sites of the transition metal central atom are occupied by neutral ligands, the complex contains further, preferably anionic and among these in particular mono- or bidentate ligands. These include in particular the halides such as fluoride, chloride, bromide and iodide, and the (NO 2 ) - group, that is a nitro ligand or a nitrito ligand. The (NO 2 ) - group may also be chelated to a transition metal, or it may bridge two transition metal atoms asymmetrically or ⁇ 1 -O-bridge.
  • the transition metal complexes may carry further, generally simpler ligands, in particular mono- or polyvalent anion ligands.
  • anion ligands for example, nitrate, acetate, trifluoroacetate, formate, carbonate, citrate, oxalate, perchlorate and complex anions such as hexafluorophosphate.
  • the anion ligands should provide charge balance between the transition metal central atom and the ligand system.
  • the presence of oxo ligands, peroxo ligands and imino ligands is also possible. In particular, such ligands can also act bridging, so that polynuclear complexes arise.
  • both metal atoms in the complex need not be the same.
  • the use of binuclear complexes in which the two transition metal central atoms have different oxidation numbers is also possible. If anion ligands are missing or the presence of anionic ligands does not result in charge balance in the complex, anionic counterions which neutralize the cationic transition metal complex are present in the transition metal complex compounds to be used according to the invention.
  • anionic counterions include in particular nitrate, hydroxide, hexafluorophosphate, sulfate, chlorate, perchlorate, the halides such as chloride or the anions of carboxylic acids such as formate, acetate, oxalate, benzoate or citrate.
  • transition metal complex compounds that can be used are Mn (IV) 2 ( ⁇ -O) 3 (1,4,7-trimethyl-1,4,7-triazacyclononane) -di-hexafluorophosphate, [N, N'-bis [(2 -hydroxy-5-vinylphenyl) methylene] -1,2-diaminocyclohexane] manganese (III) chloride, [N, N'-bis [(2-hydroxy-5-nitrophenyl) methylene] -1,2 diaminocyclohexane] manganese (III) acetate, [N, N'-bis [(2-hydroxyphenyl) methylene] -1,2-phenylenediamine] manganese (III) acetate, [N, N'-bis [(2-hydroxyphenyl) methylene] -1,2-diaminocyclohexane] manganese (III) chloride, [N, N'-bis [(2-hydroxyphenyl) m
  • Suitable enzymes in the detergents are, in particular, those from the class of the proteases, lipases, cutinases, amylases, pullulanases, xylanases, hemicellulases, cellulases, peroxidases and oxidases or mixtures thereof, the use of protease, amylase, lipase and / or or cellulase is particularly preferred.
  • the proportion is preferably 0.2 wt .-% to 1.5 wt .-%, in particular 0.5 wt .-% to 1 wt .-%.
  • the enzymes can be adsorbed in a customary manner on carriers and / or embedded in coating substances or incorporated as concentrated, as anhydrous liquid formulations.
  • Suitable graying inhibitors or soil release agents are anionic cellulose ethers such as carboxymethyl cellulose and methyl carboxymethyl cellulose.
  • the alkali metal salts in particular the sodium salts are used.
  • Commonly used soil release agents include copolyesters containing dicarboxylic acid units, alkylene glycol units and polyalkylene glycol units.
  • the proportion of graying inhibitors and / or soil-release agents in the compositions is generally not more than 2 wt .-%, and is preferably 0.5 wt .-% to 1.5 wt .-%.
  • detergents may contain, for example, derivatives of diaminostilbenedisulfonic acid or their alkali metal salts.
  • salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazin-6-yl-amino) -stilbene-2,2'-disulphonic acid or similarly constructed compounds which are suitable instead of the morpholino group carry a diethanolamino group, a methylamino group or a 2-methoxyethylamino group.
  • brighteners of the substituted 4,4'-distyryl-diphenyl type may be present, for example, 4,4'-bis (4-chloro-3-sulfostyryl) -diphenyl.
  • mixtures of brighteners can be used.
  • brighteners of the 1,3-diaryl-2-pyrazolines type for example 1- (p-sulfamoylphenyl) -3- (p-chlorophenyl) -2-pyrazoline, and compounds of similar construction are particularly suitable.
  • the content of the composition in optical brighteners or brightener mixtures is generally not more than 1 wt .-%, preferably 0.05 wt .-% to 0.5 wt .-%. In a preferred embodiment, the agent is free of such agents.
  • the customary foam regulators which can be used in detergents include, for example, polysiloxane-silica mixtures, the finely divided silica contained therein preferably being silanated or otherwise rendered hydrophobic.
  • the polysiloxanes can consist of both linear compounds as well as crosslinked polysiloxane resins and mixtures thereof.
  • Further antifoams are paraffin hydrocarbons, in particular microparaffins and paraffin waxes whose melting point is above 40 ° C., saturated fatty acids or soaps having in particular 20 to 22 carbon atoms, for example sodium behenate, and alkali metal salts of phosphoric mono- and / or dialkyl esters in which the alkyl chains each having 12 to 22 carbon atoms.
  • the proportion of foam regulators may preferably be from 0.2% by weight to 2% by weight.
  • the agents may contain water as a solvent.
  • organic solvents which can be used in the compositions, in particular if they are in liquid or pasty form, are alcohols having 1 to 4 C atoms, in particular methanol, ethanol, isopropanol and tert-butanol, diols having 2 to 4 C atoms, in particular ethylene glycol and propylene glycol, and mixtures thereof and the derivable from said classes of compounds ethers.
  • Such water-miscible solvents are present in the compositions in amounts of preferably not more than 20% by weight, in particular from 1% by weight to 15% by weight.
  • the agents can system and environmentally acceptable acids, in particular citric acid, acetic acid, tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid and / or adipic acid, but also, mineral acids, in particular sulfuric acid or alkali metal hydrogen sulfates, or bases, in particular ammonium or alkali metal hydroxides.
  • Such pH regulators are preferably not more than 10 wt .-%, in particular from 0.5 wt .-% to 6 wt .-%, included.
  • compositions presents no difficulties and can be carried out in a manner known in the art, for example by spray-drying or granulation, thermally-sensitive ingredients optionally being added separately later.
  • compositions in the form of aqueous or other conventional solvent-containing solutions are particularly advantageously prepared by simply mixing the ingredients, which can be added in bulk or as a solution in an automatic mixer.
  • the agents are preferably in the form of powdered, granular or tablet-shaped preparations which are compacted in a manner known per se, for example by mixing, granulating, roll compacting and / or by spray-drying the thermally stable components and admixing the more sensitive components, to which in particular enzymes, bleaching agents and bleach-activating agents are to be expected.
  • a process comprising an extrusion step is preferred.
  • a tablet thus produced has a weight of 15 g to 40 g, in particular from 20 g to 30 g, with a diameter of 35 mm to 40 mm.
  • the cellulose derivative Polyquaternium-67 (quaternized hydroxyethylcellulose with cationic substitution by trimethylammonium and dimethyldodecylammonium, Softcat® SX 400 H) was forcibly applied in 1% strength solution to cotton lobes, the lobules were dried and then treated with the test bacterium Pseudomonas aeruginosa. For this purpose, the test bacteria were previously cultivated overnight on TSA agar medium and then washed away with the tryptone-NaCl from the agar plates. There were dilution steps in tryptone-NaCl. The final dilution step was carried out in PBS buffer (1-fold).

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Description

Die vorliegende Erfindung betrifft die Verwendung von bestimmten Polymeren zur Verminderung der Anhaftung von Mikroorganismen auf Textilien.The present invention relates to the use of certain polymers to reduce the adhesion of microorganisms to textiles.

Mikroorganismen, wie Bakterien, Pilze und Viren können sich auf Oberflächen im Haushalt und auf Textilien ansiedeln. Bakterien und Pilze können sich auf solchen Oberflächen auch vermehren. Dies kann Hygienerisiken zur Folge haben, aber auch zu unästhetischen mikrobiellen Belägen, sogenannten Biofilmen, führen. Auch das Auftreten mikrobiell bedingter, insbesondere bakteriell bedingter schlechter Gerüche ist möglich. Kleidungsstücke aus empfindlichen Materialien wie etwa Seide oder Mikrofasern können zudem nur bei 30°C oder 40 °C gewaschen werden. Es ist möglich, dass dadurch Pilze, wie beispielsweise die humanpathogene Candida albicans, und Bakterien nicht immer in ausreichendem Maße abgetötet werden. Insbesondere nach einer Pilzinfektion kann es durch solche auf Kleidungsstücken haftenden, nicht abgetöteten Pilze zu einer Reinfektion kommen.Microorganisms such as bacteria, fungi and viruses can colonize household and textile surfaces. Bacteria and fungi can also multiply on such surfaces. This can result in hygiene risks, but also lead to unaesthetic microbial deposits, so-called biofilms. The occurrence of microbially induced, especially bacterially caused bad odors is possible. Garments made of delicate materials such as silk or microfibers can only be washed at 30 ° C or 40 ° C. It is possible that thereby fungi, such as the human pathogenic Candida albicans, and bacteria are not always killed sufficiently. In particular, after a fungal infection can come by such adhering to garments, not killed fungi to a reinfection.

Um die Reinfektion durch an der Kleidung oder anderen textilen Oberflächen wie Möbelpolster oder Gardinen haftenden Mikroorganismen zu verhindern, wurden bisher vor allem antimikrobielle Substanzen eingesetzt, die entweder das Wachstum der Mikroorganismen hemmen (Biostatika) oder diese abtöten (Biozide). Nachteilig ist daran, dass solche zum Beispiel in Wasch- und Reinigungsmitteln verwendeten Biozide oder Biostatika nach dem Gebrauch ins Abwasser gelangen und die mikrobiellen Klärstufen in den Kläranlagen in ihrer Funktion beeinträchtigen können. Zudem wird der Selektionsdruck auf die Mikroorganismen zur Resistenzbildung stark erhöht, so dass nach einiger Zeit neue antimikrobielle Substanzen gefunden werden müssen, die gegen resistent gewordene Mikroorganismen wirken. Es ist daher wünschenswert, anstelle von biozid oder biostatisch wirkenden Substanzen biorepulsiv wirkende Substanzen zur Verfügung zu haben, welche die Adhäsion der Mikroorganismen verhindern, ohne die Mikroorganismen physiologisch zu beeinträchtigen.In order to prevent reinfection by adhering to clothing or other textile surfaces such as furniture upholstery or curtains microorganisms, so far mainly antimicrobial substances have been used, either inhibit the growth of microorganisms (biostatics) or kill them (biocides). The disadvantage is that such biocides or biostats used for example in detergents and cleaners enter the wastewater after use and may impair the function of the microbial treatment stages in the sewage treatment plants. In addition, the selection pressure on the microorganisms for resistance formation is greatly increased, so that after some time new antimicrobial substances must be found that act against resistant microorganisms. It is therefore desirable to have biorepulsive substances instead of biocidal or biostatic substances which prevent the adhesion of the microorganisms without physiologically impairing the microorganisms.

Aus der internationalen Patentanmeldung WO 2006/071452 A2 ist die Verwendung von Polyesteramiden zur temporären oder permanenten Ausrüstung von textilen Oberflächen bekannt. Die internationale Patentanmeldung WO 2006/071451 A2 betrifft die Verminderung der Anhaftung von Mikroorganismen an textilen Oberflächen durch Copolymere aus 5 Gew.-% bis 95 Gew.-% anionischem Vinylmonomer und 5 Gew.-% bis 95 Gew.-% nichtionischem hydrophilem Vinylmonomer, wobei Vinylmonomere mit sekundärer oder tertiärer Aminogruppe oder Ammoniumgruppe, polyfunktionale Vinylmonomere, hydrophobe Vinylmonomere und/oder Vinylmonomere mit Silikogruppen zusätzlich anwesend sein können. Aus der internationalen Patentanmeldung WO 2006/077049 A2 sind Polymere und Copolymere aus den Gruppen der Polyester, Polysaccharide, Polyether, Polyurethane, Polyharnstoffe und Polyamide oder deren Mischpolymere bekannt, die zur Verminderung oder Verhinderung der Adhäsion von Mikroorganismen an Textilien geeignet sind.From the international patent application WO 2006/071452 A2 The use of polyester amides for the temporary or permanent finishing of textile surfaces is known. The international patent application WO 2006/071451 A2 relates to the reduction of the adhesion of microorganisms to textile surfaces by copolymers of 5 wt .-% to 95 wt .-% of anionic vinyl monomer and 5 wt .-% to 95 wt .-% of nonionic hydrophilic vinyl monomer, wherein vinyl monomers having secondary or tertiary amino group or Ammonium group, polyfunctional vinyl monomers, hydrophobic vinyl monomers and / or vinyl monomers having silicone groups can be present in addition. From the international patent application WO 2006/077049 A2 Polymers and copolymers from the groups of polyesters, polysaccharides, polyethers, polyurethanes, polyureas and polyamides or their copolymers are known, which are suitable for reducing or preventing the adhesion of microorganisms to textiles.

Überraschend wurde gefunden, dass auf Oberflächen, die mit bestimmten Cellulosederivaten in Kontakt gebracht wurden, das Anhaften von Mikroorganismen unterbunden wird oder zumindest deutlich reduziert ist.Surprisingly, it has been found that on surfaces which have been brought into contact with certain cellulose derivatives, the adhesion of microorganisms is prevented or at least significantly reduced.

Gegenstand der Erfindung ist die Verwendung von Cellulosederivaten der allgemeinen Formel (I),

        ((R-O-)3RCell)y     (I)

in der RCell den Rest einer Anhydroglukose-Einheit bedeutet, der Polymerisationsgrad y eine Zahl von 1000 und 5000 ist und jeder der Reste R der allgemeinen Formel (II) oder (III) entspricht,

        -(CaH2a-O)m-(CbH2b-O)n-(CcH2c)o-R1     (II)

Figure imgb0001
in denen

  • a und b unabhängig voneinander für 2 oder 3 stehen,
  • c eine Zahl von 1 bis 10 ist,
  • m, n und p unabhängig voneinander für eine Zahl von 0 bis 10 stehen,
  • o für 0 oder 1 steht,
  • R1 für Wasserstoff, einen C1-18-Alkyl-, Alkylaryl-, Arylalkyl- oder Arylrest oder die Gruppe -NR2R3(R4)q Ys steht, wobei R1 für Wasserstoff steht, wenn o = 0 ist,
  • R2, R3 und R4 unabhängig voneinander für Wasserstoff, einen C1-18-Alkyl-, Alkylaryl-, Arylalkyl- oder Arylrest stehen,
  • q für 0 oder 1 steht,
  • Y für ein Anion steht, und
  • s eine Zahl größer oder gleich Null ist derart, dass das Gesamtmolekül der Formel (I) keine Ladung aufweist,
  • mit der Maßgabe, dass in mindestens einem der Reste R m, n und o größer 0 ist und/oder die Gruppierung -R1 für -NR2R3(R4)q steht,
  • zur Verhinderung der mikrobiellen Besiedelung, insbesondere der Besiedelung durch Bakterien, Pilze und/oder Viren, von textilen Oberflächen.
The invention relates to the use of cellulose derivatives of the general formula (I),

((RO-) 3 R Cell ) y (I)

in which R Cell is the radical of an anhydroglucose unit, the degree of polymerization y is a number of 1000 and 5000, and each of the radicals R corresponds to the general formula (II) or (III),

- (C a H 2a -O) m - (C b H 2b -O) n - (C c H 2c ) o -R 1 (II)

Figure imgb0001
 in which
  • a and b independently represent 2 or 3,
  • c is a number from 1 to 10,
  • m, n and p independently of one another represent a number from 0 to 10,
  • o is 0 or 1,
  • R 1 is hydrogen, a C 1-18 alkyl, alkylaryl, arylalkyl or aryl radical or the group -NR 2 R 3 (R 4 ) q Y s , where R 1 is hydrogen when o = 0 .
  • R 2 , R 3 and R 4 independently of one another represent hydrogen, a C 1-18 -alkyl, alkylaryl, arylalkyl or aryl radical,
  • q is 0 or 1,
  • Y stands for an anion, and
  • s is a number greater than or equal to zero such that the total molecule of formula (I) has no charge,
  • with the proviso that in at least one of the radicals R m, n and o is greater than 0 and / or the group -R 1 is -NR 2 R 3 (R 4 ) q ,
  • for the prevention of microbial colonization, in particular the colonization by bacteria, fungi and / or viruses, of textile surfaces.

Das Cellulosederivat der allgemeinen Formel (I) wird vorzugsweise ausgewählt aus der Gruppe umfassend Trialkylammoniumhydroxypropylcellulose und Trialkylammoniumethylcellulose sowie Mischungen aus diesen. In dem Cellulosederivat der allgemeinen Formel (I) entspricht mindestens 1 Rest R der allgemeinen Formel (II) oder (III), wobei m, n und o größer 0 sind und/oder die Gruppierung -R1 steht für -NR2R3(R4)q.The cellulose derivative of the general formula (I) is preferably selected from the group comprising Trialkylammoniumhydroxypropylcellulose and trialkylammoniumethylcellulose and mixtures thereof. In the cellulose derivative of the general formula (I), at least one radical R corresponds to the general formula (II) or (III), where m, n and o are greater than 0 and / or the grouping -R 1 is -NR 2 R 3 ( R 4 ) q .

Die Substituenten der allgemeinen Formeln (II) und (III) können durch Veretherung freier Hydroxygruppen der Cellulose mit den entsprechenden Halogeniden, Halohydrinen oder Epoxiden eingeführt werden. Amin-modifizierte Celluloseether sind durch Reaktion mindestens einer Hydroxylgruppe von Cellulose und/oder hydroxylgruppenhaltigen Celluloseethern, beispielsweise Alkyl-, Alkylcarboxyalkyl-, Hydroxyalkyl- oder Alkylhydroxyalkylcelluloseethern, mit Halogen-Alkylaminen zugänglich. Als Halogen-Alkylamine kommen dabei insbesondere Trialkylamine in Betracht, bei denen eine Alkylgruppe ein Halogenatom, insbesondere Chlor, trägt. Unter diesen sind 1-Diethylamino-2-Chlorethan, 2-Chlor-N,N-dimethylpropylamin und 3-Chlor-N,N-dimethylpropylamin besonders bevorzugt. Um bei Einsatz von Halogen-Alkylaminen eine nukleophile Reaktion des Amin-Stickstoffs zu vermeiden, kann dieser in üblicher Weise in Salzform, beispielsweise als Hydrochlorid, vorliegen. Falls gewünscht kann man durch anschließende Neutralisation die freien Amine (q = 0) erhalten. Aus diesen können durch Umsetzung mit beispielsweise Alkylhalogeniden oder -sulfaten die Derivate mit quaternärem Stickstoffatom (q = 1) erhalten werden. Pro Gruppierung RCell in dem Cellulosederivat nach Formel (I) sind durchschnittlich vorzugsweise 0,01 bis 1, insbesondere 0,1 bis 0,8 von Resten R1, welche die Gruppierung -NR2R3(R4)q tragen, vorhanden, das heißt gemittelt über das gesamte Cellulosederivat ist vorzugsweise jede einhundertste bis jede, insbesondere jede zehnte bis jede achte von zehnen der Anydroglukoseeinheiten mit einer ein Stickstoffatom tragenden Gruppe substituiert. In einer bevorzugten Ausführungsform ist die Cellulose mit einer C8-24-Alkyldialkylammoniumhydroxypropylgruppe und/oder einer C8-24-Alkyldialkylammoniumethylgruppe substituiert.The substituents of general formulas (II) and (III) can be introduced by etherification of free hydroxy groups of the cellulose with the corresponding halides, halohydrins or epoxides. Amine-modified cellulose ethers are obtainable by reacting at least one hydroxyl group of cellulose and / or hydroxyl-containing cellulose ethers, for example alkyl, alkylcarboxyalkyl, hydroxyalkyl or alkylhydroxyalkylcellulose ethers, with halogenated alkylamines. Particularly suitable halogenoalkylamines are trialkylamines in which an alkyl group carries a halogen atom, in particular chlorine. Among them, 1-diethylamino-2-chloroethane, 2-chloro-N, N-dimethylpropylamine and 3-chloro-N, N-dimethylpropylamine are particularly preferable. In order to avoid a nucleophilic reaction of the amine nitrogen when using haloalkylamines, this may be present in the usual manner in salt form, for example as hydrochloride. If desired, the free amines (q = 0) can be obtained by subsequent neutralization. From these, by reacting with, for example, alkyl halides or sulfates, the derivatives having a quaternary nitrogen atom (q = 1) can be obtained. Per moiety R Cell in the cellulose derivative according to formula (I) are an average of preferably from 0.01 to 1, especially 0.1 to 0.8 of R 1, which the group -NR 2 R 3 (R 4) q wear available that is, averaged over the entire cellulose derivative, preferably every one-hundredth to every, and particularly every tenth to every eighth, of tens of the anhydroglucose units is substituted with a nitrogen atom-bearing group. In a preferred embodiment, the cellulose is substituted with a C 8-24 alkyl dialkyl ammonium hydroxypropyl group and / or a C 8-24 alkyl dialkyl ammonium ethyl group.

Die mittlere Molmasse der erfindungsgemäß eingesetzten Cellulosederivate liegt vorzugsweise im Bereich bis zu 500000 g/mol. Bei den hier und später gegebenenfalls für andere polymere Inhaltsstoffe angegebenen mittleren Molmassen handelt es sich um gewichtsmittlere Molmassen Mw, die grundsätzlich mittels Gelpermeationschromatographie mit Hilfe eines RI-Detektors bestimmbar sind, wobei die Messung zweckmäßig gegen einen externen Standard erfolgt.The average molar mass of the cellulose derivatives used according to the invention is preferably in the range of up to 500,000 g / mol. The mean molar masses indicated here and later, if appropriate, for other polymeric ingredients are weight-average molar masses M w , which can in principle be determined by means of gel permeation chromatography with the aid of an RI detector, the measurement being expediently carried out against an external standard.

Vorzugsweise weist ein erfindungsgemäß eingesetztes Cellulosederivat eine Löslichkeit in Wasser bei 25°C über den gesamten Bereich von pH 7 bis pH 9, besonders bevorzugt über den gesamten Bereich von pH 2 bis pH 11, von mindestens 0,01 g/l, insbesondere von mindestens 0,1 g/l und besonders bevorzugt von 1 g/l bis 15 g/l auf.Preferably, a cellulose derivative used according to the invention has a solubility in water at 25 ° C over the entire range of pH 7 to pH 9, particularly preferably over the entire Range of pH 2 to pH 11, of at least 0.01 g / l, in particular of at least 0.1 g / l and particularly preferably from 1 g / l to 15 g / l on.

Die genannten Cellulosederivate sind in der Lage, Textilien so auszurüsten, dass mikrobielles Wachstum auf ihnen vermieden wird, weil Bakterien, Pilze und/oder Viren auf der mit ihnen behandelten Textiloberfläche nicht oder nur vermindert anhaften. Ein weiterer Gegenstand der Erfindung ist daher die Verwendung der genannten Cellulosederivate zur Verhinderung oder Verminderung des Adhäsion von Mikroorganismen, insbesondere von Bakterien, Pilze und/oder Viren, an Textilien.The cellulose derivatives mentioned are able to furnish textiles in such a way that microbial growth on them is avoided because bacteria, fungi and / or viruses do not adhere or only adhere to a reduced extent on the textile surface treated with them. Another object of the invention is therefore the use of said cellulose derivatives for preventing or reducing the adhesion of microorganisms, in particular of bacteria, fungi and / or viruses, to textiles.

Vorzugsweise setzt man zur Behandlung der Textiloberfläche eine wässrige Flotte ein, die 1 mg/l bis 5000 mg/l, insbesondere 10 mg/l bis 500 mg/l des erfindungsgemäß verwendeten Cellulosederivats enthält.For the treatment of the textile surface, preference is given to using an aqueous liquor which contains 1 mg / l to 5000 mg / l, in particular 10 mg / l to 500 mg / l of the cellulose derivative used according to the invention.

Die erfindungsgemäße Verwendung kann vorzugsweise so realisiert werden, dass man ein Waschmittel, welches ein genanntes Cellulosederivat enthält, im Rahmen eines maschinellen oder mit der Hand ausgeführten Waschvorgangs auf ein Textil einwirken lässt. Weitere Gegenstände der Erfindung sind daher die Verwendung eines Waschmittels, das ein genanntes Cellulosederivat enthält, zur Verhinderung der mikrobiellen Besiedelung von textilen Oberflächen, und die Verwendung eines Waschmittels, das ein genanntes Cellulosederivat enthält, zur Verhinderung oder Verminderung des Adhäsion von Mikroorganismen an Textilien.The use according to the invention can preferably be realized by allowing a detergent containing a said cellulose derivative to act on a textile in the course of a machine or hand washing operation. Further objects of the invention are therefore the use of a detergent containing a said cellulose derivative for preventing the microbial colonization of textile surfaces, and the use of a detergent containing a said cellulose derivative for preventing or reducing the adhesion of microorganisms to textiles.

Ein Waschmittel, worunter hier ein Mittel zum Waschen von Wäsche oder ein vor dem eigentlichen Waschvorgang zum Einsatz kommendes Wäschevorbehandlungsmittel wie zum Beispiel ein Fleckentfernungsmittel oder ein nach dem eigentlichen Waschvorgang zum Einsatz kommendes Wäschenachbehandlungsmittel wie zum Beispiel ein Weichspülmittel verstanden wird, enthält vorzugsweise 0,01 Gew.-% bis 2 Gew.-%, insbesondere 0,05 Gew.-% bis 1,5 Gew.-% und besonders bevorzugt 0,5 Gew.-% bis 1,2 Gew.-% des genannten Wirkstoffs neben üblichen, mit diesem verträglichen Inhaltsstoffen. Diese Mittel, die als insbesondere pulverförmige Feststoffe, in nachverdichteter Teilchenform, als homogene Lösungen oder als Suspensionen beziehungsweise Dispersionen vorliegen können, können außer dem erfindungsgemäß verwendeten Cellulosederivat im Prinzip alle bekannten und in derartigen Mitteln üblichen Inhaltsstoffe enthalten. Die Waschmittel können insbesondere Buildersubstanzen, oberflächenaktive Tenside, Bleichmittel, Bleichaktivatoren und- katalysatoren, wassermischbare organische Lösungsmittel, Enzyme, Sequestrierungsmittel, Elektrolyte, pH-Regulatoren oder weitere Hilfsstoffe, wie optische Aufheller, Vergrauungsinhibitoren, Farbübertragungsinhibitoren, Schaumregulatoren sowie Farb- und Duftstoffe, enthalten. Wenn sie flüssig und wasserhaltig sind, weisen sie vorzugsweise einen pH-Wert im Bereich von 8 bis 12, insbesondere 9 bis 12 auf; ansonsten gelten die genannten pH-Wert-Bereiche für 0,47 gew.-%ige wässrige Lösungen der Mittel.A detergent, which is understood here to mean a means for washing laundry or a laundry pre-treatment agent used before the actual washing process, for example a stain remover or a laundry after-wash treatment such as, for example, a fabric softener, preferably contains 0.01% by weight .-% to 2 wt .-%, in particular 0.05 wt .-% to 1.5 wt .-% and particularly preferably 0.5 wt .-% to 1.2 wt .-% of said active ingredient in addition to conventional with this compatible ingredients. These agents, which may be in the form of particularly pulverulent solids, in densified particle form, as homogeneous solutions or as suspensions or dispersions, may in principle contain all known ingredients customary in such agents besides the cellulose derivative used according to the invention. The detergents may in particular contain builder substances, surface-active surfactants, bleaches, bleach activators and catalysts, water-miscible organic solvents, enzymes, sequestering agents, electrolytes, pH regulators or other auxiliaries, such as optical brighteners, grayness inhibitors, color transfer inhibitors, foam regulators and dyes and fragrances. If they are liquid and hydrous, they preferably have a pH in the range of 8 to 12, especially 9 to 12; otherwise, the pH ranges mentioned apply to 0.47% by weight aqueous solutions of the agents.

Durch den Einsatz der genannten Cellulosederivate in einem Waschmittel wird bei dessen Anwendung sowohl die Adhäsion von Mikroorganismen an Textilien inhibiert oder zumindest verringert als auch ein leichteres Ablösen von mikrobiellen Verschmutzungen von den Textilien erreicht.Through the use of said cellulose derivatives in a detergent, both the adhesion of microorganisms to textiles is inhibited or at least reduced and easier detachment of microbial contaminants from the textiles is achieved.

Die Mittel können ein oder mehrere Tenside enthalten, wobei insbesondere anionische Tenside, nichtionische Tenside und deren Gemische in Frage kommen. Geeignete nichtionische Tenside sind insbesondere Alkylglykoside und Ethoxylierungs- und/oder Propoxylierungsprodukte von Alkylglykosiden oder linearen oder verzweigten Alkoholen mit jeweils 12 bis 18 C-Atomen im Alkylteil und 3 bis 20, vorzugsweise 4 bis 10 Alkylethergruppen. Weiterhin sind entsprechende Ethoxylierungs- und/oder Propoxylierungsprodukte von N-Alkyl-aminen, vicinalen Diolen, Fettsäureestern und Fettsäureamiden, die hinsichtlich des Alkylteils den genannten langkettigen Alkoholderivaten entsprechen, sowie von Alkylphenolen mit 5 bis 12 C-Atomen im Alkylrest brauchbar.The agents may contain one or more surfactants, in particular anionic surfactants, nonionic surfactants and mixtures thereof come into question. Suitable nonionic surfactants are in particular alkyl glycosides and ethoxylation and / or propoxylation of alkyl glycosides or linear or branched alcohols each having 12 to 18 carbon atoms in the alkyl moiety and 3 to 20, preferably 4 to 10 alkyl ether groups. Also suitable are ethoxylation and / or propoxylation products of N-alkylamines, vicinal diols, fatty acid esters and fatty acid amides which correspond to said long-chain alcohol derivatives with respect to the alkyl moiety and of alkylphenols having 5 to 12 carbon atoms in the alkyl radical.

Geeignete anionische Tenside sind insbesondere Seifen und solche, die Sulfat- oder SulfonatGruppen mit bevorzugt Alkaliionen als Kationen enthalten. Verwendbare Seifen sind bevorzugt die Alkalisalze der gesättigten oder ungesättigten Fettsäuren mit 12 bis 18 C-Atomen. Derartige Fettsäuren können auch in nicht vollständig neutralisierter Form eingesetzt werden. Zu den brauchbaren Tensiden des Sulfat-Typs gehören die Salze der Schwefelsäurehalbester von Fettalkoholen mit 12 bis 18 C-Atomen und die Sulfatierungsprodukte der genannten nichtionischen Tenside mit niedrigem Ethoxylierungsgrad. Zu den verwendbaren Tensiden vom Sulfonat-Typ gehören lineare Alkylbenzolsulfonate mit 9 bis 14 C-Atomen im Alkylteil, Alkansulfonate mit 12 bis 18 C-Atomen, sowie Olefinsulfonate mit 12 bis 18 C-Atomen, die bei der Umsetzung entsprechender Monoolefine mit Schwefeltrioxid entstehen, sowie alpha-Sulfofettsäureester, die bei der Sulfonierung von Fettsäuremethyl- oder -ethylestern entstehen.Suitable anionic surfactants are in particular soaps and those which contain sulfate or sulfonate groups with preferably alkali ions as cations. Usable soaps are preferably the alkali salts of the saturated or unsaturated fatty acids having 12 to 18 carbon atoms. Such fatty acids can also be used in incompletely neutralized form. Useful surfactants of the sulfate type include the salts of the sulfuric acid half-esters of fatty alcohols having 12 to 18 carbon atoms and the sulfation products of said nonionic surfactants having a low degree of ethoxylation. Suitable surfactants of the sulfonate type include linear alkylbenzenesulfonates having 9 to 14 carbon atoms in the alkyl moiety, alkanesulfonates having 12 to 18 carbon atoms, and olefin sulfonates having 12 to 18 carbon atoms, which are formed in the reaction of corresponding monoolefins with sulfur trioxide, and alpha-sulfofatty acid esters resulting from the sulfonation of fatty acid methyl or ethyl esters.

Derartige Tenside sind in Waschmitteln in Mengenanteilen von vorzugsweise 5 Gew.-% bis 50 Gew.-%, insbesondere von 8 Gew.-% bis 30 Gew.-%, enthalten.Such surfactants are present in detergents in proportions of preferably from 5% by weight to 50% by weight, in particular from 8% by weight to 30% by weight.

Ein Waschmittel enthält vorzugsweise mindestens einen wasserlöslichen und/oder wasserunlöslichen, organischen und/oder anorganischen Builder. Zu den wasserlöslichen organischen Buildersubstanzen gehören Polycarbonsäuren, insbesondere Citronensäure und Zuckersäuren, monomere und polymere Aminopolycarbonsäuren, insbesondere Glycindiessigsäure, Methylglycindiessigsäure, Nitrilotriessigsäure, Iminodisuccinate wie Ethylendiamin-N,N'-dibernsteinsäure und Hydroxyiminodisuccinate, Ethylendiamintetraessigsäure sowie Polyasparaginsäure, Polyphosphonsäuren, insbesondere Aminotris(methylenphosphonsäure), Ethylendiamintetrakis(methylen-phosphonsäure), Lysintetra(methylenphosphonsäure) und 1-Hydroxyethan-1,1-diphosphonsäure, polymere Hydroxyverbindungen wie Dextrin sowie polymere (Poly-)carbonsäuren, insbesondere durch Oxidation von Polysacchariden zugängliche Polycarboxylate, polymere Acrylsäuren, Methacrylsäuren, Maleinsäuren und Mischpolymere aus diesen, die auch geringe Anteile polymerisierbarer Substanzen ohne Carbonsäurefunktionalität einpolymerisiert enthalten können. Die relative mittlere Molekülmasse der Homopolymeren ungesättiger Carbonsäuren liegt im allgemeinen zwischen 5 000 g/mol und 200 000 g/mol, die der Copolymeren zwischen 2 000 g/mol und 200 000 g/mol, vorzugsweise 50 000 g/mol bis 120 000 g/mol, jeweils bezogen auf freie Säure. Ein besonders bevorzugtes Acrylsäure-Maleinsäure-Copolymer weist eine relative mittlere Molekülmasse von 50 000 bis 100 000 auf. Geeignete, wenn auch weniger bevorzugte Verbindungen dieser Klasse sind Copolymere der Acrylsäure oder Methacrylsäure mit Vinylethern, wie Vinylmethylethern, Vinylester, Ethylen, Propylen und Styrol, in denen der Anteil der Säure mindestens 50 Gew.-% beträgt. Als wasserlösliche organische Buildersubstanzen können auch Terpolymere eingesetzt werden, die als Monomere zwei ungesättigte Säuren und/oder deren Salze sowie als drittes Monomer Vinylalkohol und/ oder ein Vinylalkohol-Derivat oder ein Kohlenhydrat enthalten. Das erste saure Monomer beziehungsweise dessen Salz leitet sich von einer monoethylenisch ungesättigten C3-C8-Carbonsäure und vorzugsweise von einer C3-C4-Monocarbonsäure, insbesondere von (Meth)-acrylsäure ab. Das zweite saure Monomer beziehungsweise dessen Salz kann ein Derivat einer C4-C8-Dicarbonsäure sein, wobei Maleinsäure besonders bevorzugt ist. Die dritte monomere Einheit wird in diesem Fall von Vinylalkohol und/oder vorzugsweise einem veresterten Vinylalkohol gebildet. Insbesondere sind Vinylalkohol-Derivate bevorzugt, welche einen Ester aus kurzkettigen Carbonsäuren, beispielsweise von C1-C4-Carbonsäuren, mit Vinylalkohol darstellen. Bevorzugte Polymere enthalten dabei 60 Gew.-% bis 95 Gew.-%, insbesondere 70 Gew.-% bis 90 Gew.-% (Meth)acrylsäure bzw. (Meth)acrylat, besonders bevorzugt Acrylsäure bzw. Acrylat, und Maleinsäure bzw. Maleinat sowie 5 Gew.-% bis 40 Gew.-%, vorzugsweise 10 Gew.-% bis 30 Gew.-% Vinylalkohol und/oder Vinylacetat. Ganz besonders bevorzugt sind dabei Polymere, in denen das Gewichtsverhältnis von (Meth)acrylsäure beziehungsweise (Meth)acrylat zu Maleinsäure beziehungsweise Maleinat zwischen 1:1 und 4:1, vorzugsweise zwischen 2:1 und 3:1 und insbesondere 2:1 und 2,5:1 liegt. Dabei sind sowohl die Mengen als auch die Gewichtsverhältnisse auf die Säuren bezogen. Das zweite saure Monomer beziehungsweise dessen Salz kann auch ein Derivat einer Allylsulfonsäure sein, die in 2-Stellung mit einem Alkylrest, vorzugsweise mit einem C1-C4-Alkylrest, oder einem aromatischen Rest, der sich vorzugsweise von Benzol oder Benzol-Derivaten ableitet, substituiert ist. Bevorzugte Terpolymere enthalten dabei 40 Gew.-% bis 60 Gew.-%, insbesondere 45 bis 55 Gew.-% (Meth)acrylsäure beziehungsweise (Meth)acrylat, besonders bevorzugt Acrylsäure beziehungsweise Acrylat, 10 Gew.-% bis 30 Gew.-%, vorzugsweise 15 Gew.-% bis 25 Gew.-% Methallylsulfonsäure bzw. Methallylsulfonat und als drittes Monomer 15 Gew.-% bis 40 Gew.-%, vorzugsweise 20 Gew.-% bis 40 Gew.-% eines Kohlenhydrats. Dieses Kohlenhydrat kann dabei beispielsweise ein Mono-, Di-, Oligo- oder Polysaccharid sein, wobei Mono-, Di- oder Oligosaccharide bevorzugt sind. Besonders bevorzugt ist Saccharose.A detergent preferably contains at least one water-soluble and / or water-insoluble, organic and / or inorganic builder. The water-soluble organic builder substances include polycarboxylic acids, in particular citric acid and sugar acids, monomeric and polymeric aminopolycarboxylic acids, in particular glycinediacetic acid, methylglycinediacetic acid, nitrilotriacetic acid, iminodisuccinates such as ethylenediamine-N, N'-disuccinic acid and hydroxyiminodisuccinates, ethylenediaminetetraacetic acid and polyaspartic acid, polyphosphonic acids, in particular aminotris (methylenephosphonic acid), ethylenediamine tetrakis (methylene-phosphonic acid), Lysintetra (methylenephosphonic acid) and 1-hydroxyethane-1,1-diphosphonic acid, polymeric hydroxy compounds such as dextrin and polymeric (poly) carboxylic acids, especially by oxidation of polysaccharides accessible polycarboxylates, polymeric acrylic acids, methacrylic acids, maleic acids and copolymers thereof, which also small proportions Polymerizable substances without carboxylic acid functionality may contain polymerized. The relative average molecular weight of the homopolymers of unsaturated carboxylic acids is generally between 5,000 g / mol and 200,000 g / mol, that of the copolymers between 2,000 g / mol and 200,000 g / mol, preferably 50,000 g / mol to 120,000 g / mol, in each case based on the free acid. A particularly preferred acrylic acid-maleic acid copolymer has a relative average molecular weight of 50,000 to 100,000. 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. As water-soluble organic builders, it is also possible to use terpolymers which contain two unsaturated acids and / or salts thereof as monomers and vinyl alcohol and / or a vinyl alcohol derivative or a carbohydrate as the third monomer. 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 polymers contain from 60% by weight to 95% by weight, in particular from 70% by weight to 90% by weight, of (meth) acrylic acid or (meth) acrylate, particularly preferably acrylic acid or acrylate, and maleic acid or Maleinate 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 polymers 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. Particularly preferred is sucrose.

Durch den Einsatz des dritten Monomers werden vermutlich Sollbruchstellen in das Polymer eingebaut, die für die gute biologische Abbaubarkeit des Polymers verantwortlich sind. Diese Terpolymere weisen im Allgemeinen eine relative mittlere Molekülmasse zwischen 1 000 g/mol und 200 000 g/mol, vorzugsweise zwischen 200 g/mol und 50 000 g/mol auf. Weitere bevorzugte Copolymere sind solche, die als Monomere Acrolein und Acrylsäure/Acrylsäuresalze beziehungsweise Vinylacetat aufweisen. Die organischen Buildersubstanzen können, insbesondere zur Herstellung flüssiger Mittel, in Form wässriger Lösungen, vorzugsweise in Form 30- bis 50-gewichtsprozentiger wässriger Lösungen eingesetzt werden. Alle genannten Säuren werden in der Regel in Form ihrer wasserlöslichen Salze, insbesondere ihre Alkalisalze, eingesetzt.The use of the third monomer presumably incorporates predetermined breaking points into the polymer which are responsible for the good biodegradability of the polymer. These terpolymers generally have a relative average molecular weight between 1,000 g / mol and 200,000 g / mol, preferably between 200 g / mol and 50,000 g / mol. Further preferred copolymers are those which have as monomers acrolein and acrylic acid / acrylic acid salts or vinyl acetate. The organic builder substances 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 of the acids mentioned are generally used in the form of their water-soluble salts, in particular their alkali metal salts.

Derartige organische Buildersubstanzen können gewünschtenfalls in Mengen bis zu 40 Gew.-%, insbesondere bis zu 25 Gew.-% und vorzugsweise von 1 Gew.-% bis 8 Gew.-% enthalten sein. Mengen nahe der genannten Obergrenze werden vorzugsweise in pastenförmigen oder flüssigen, insbesondere wasserhaltigen, Mitteln eingesetzt.If desired, such organic builder substances may be present in amounts of up to 40% by weight, in particular up to 25% by weight and preferably from 1% by weight to 8% by weight. Quantities close to the stated upper limit are preferably used in pasty or liquid, in particular hydrous, agents.

Als wasserlösliche anorganische Buildermaterialien kommen insbesondere Polyphosphate, vorzugsweise Natriumtriphosphat, in Betracht. Als wasserunlösliche anorganische Buildermaterialien werden insbesondere kristalline oder amorphe, wasserdispergierbare Alkalialumosilikate, in Mengen nicht über 25 Gew.-%, vorzugsweise von 3 Gew.-% bis 20 Gew.-% und insbesondere in Mengen von 5 Gew.-% bis 15 Gew.-% eingesetzt. Unter diesen sind die kristallinen Natriumalumosilikate in Waschmittelqualität, insbesondere Zeolith A, Zeolith P sowie Zeolith MAP und gegebenenfalls Zeolith X, bevorzugt. Mengen nahe der genannten Obergrenze werden vorzugsweise in festen, teilchenförmigen Mitteln eingesetzt. Geeignete Alumosilikate weisen insbesondere keine Teilchen mit einer Korngröße über 30 µm auf und bestehen vorzugsweise zu wenigstens 80 Gew.-% aus Teilchen mit einer Größe unter 10 µm. Ihr Calciumbindevermögen liegt in der Regel im Bereich von 100 bis 200 mg CaO pro Gramm.Suitable water-soluble inorganic builder materials are, in particular, polyphosphates, preferably sodium triphosphate. As water-insoluble inorganic builder materials are in particular crystalline or amorphous, water-dispersible alkali metal aluminosilicates, in amounts not exceeding 25 wt .-%, preferably from 3 wt .-% to 20 wt .-% and in particular in amounts of 5 wt .-% to 15 wt. -% used. Among these, the detergent-grade crystalline sodium aluminosilicates, particularly zeolite A, zeolite P, and zeolite MAP, and optionally zeolite X, 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 .mu.m and preferably consist of at least 80% by weight of particles having a size of less than 10 .mu.m. Their calcium binding capacity is generally in the range of 100 to 200 mg CaO per gram.

Zusätzlich oder alternativ zum genannten wasserunlöslichen Alumosilikat und Alkalicarbonat können weitere wasserlösliche anorganische Buildermaterialien enthalten sein. Zu diesen gehören neben den Polyphosphaten wie Natriumtriphosphat insbesondere die wasserlöslichen kristallinen und/oder amorphen Alkalisilikat-Builder. Derartige wasserlösliche anorganische Buildermaterialien sind in den Mitteln vorzugsweise in Mengen von 1 Gew.-% bis 20 Gew.-%, insbesondere von 5 Gew.-% bis 15 Gew.-% enthalten. Die als Buildermaterialien brauchbaren Alkalisilikate weisen vorzugsweise ein molares Verhältnis von Alkalioxid zu SiO2 unter 0,95, insbesondere von 1:1,1 bis 1:12 auf und können amorph oder kristallin vorliegen. Bevorzugte Alkalisilikate sind die Natriumsilikate, insbesondere die amorphen Natriumsilikate, mit einem molaren Verhältnis Na2O:SiO2 von 1:2 bis 1:2,8. Als kristalline Silikate, die allein oder im Gemisch mit amorphen Silikaten vorliegen können, werden vorzugsweise kristalline Schichtsilikate der allgemeinen Formel Na2SixO2x+1·y H2O eingesetzt, in der x, das sogenannte Modul, eine Zahl von 1,9 bis 4 und y eine Zahl von 0 bis 20 ist und bevorzugte Werte für x 2, 3 oder 4 sind. Bevorzugte kristalline Schichtsilikate sind solche, bei denen x in der genannten allgemeinen Formel die Werte 2 oder 3 annimmt. Insbesondere sind sowohl β- als auch δ-Natriumdisitikate (Na2Si2O5 · y H2O) bevorzugt. Auch aus amorphen Alkalisilikaten hergestellte, praktisch wasserfreie kristalline Alkalisilikate der obengenannten allgemeinen Formel, in der x eine Zahl von 1,9 bis 2,1 bedeutet, können in den Mitteln eingesetzt werden. In einer weiteren bevorzugten Ausführungsform wird ein kristallines Natriumschichtsilikat mit einem Modul von 2 bis 3 eingesetzt, wie es aus Sand und Soda hergestellt werden kann. Natriumsilikate mit einem Modul im Bereich von 1,9 bis 3,5 werden in einer weiteren Ausführungsform eingesetzt. In einer bevorzugten Ausgestaltung solcher Mittel setzt man ein granulares Compound aus Alkalisilikat und Alkalicarbonat ein, wie es zum Beispiel unter dem Namen Nabion® 15 im Handel erhältlich ist.In addition to or as an alternative to said water-insoluble aluminosilicate and alkali carbonate, further water-soluble inorganic builder materials may be included. In addition to the polyphosphates, such as sodium triphosphate, these include in particular the water-soluble crystalline and / or amorphous alkali metal silicate builders. Such water-soluble inorganic builder materials are preferably present in the compositions in amounts of from 1% to 20% by weight, in particular from 5% to 15% by weight. The alkali silicates useful as builder materials preferably have a molar ratio of alkali oxide to SiO 2 below 0.95, in particular from 1: 1.1 to 1:12, and may be amorphous or crystalline. 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. Crystalline silicates which may be present alone or in a mixture with amorphous silicates are preferably crystalline phyllosilicates of the general formula Na 2 Si x O 2 × + 1 × y H 2 O is used, in which x, the so-called modulus, is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4. Preferred crystalline phyllosilicates are those in which x in the abovementioned general formula assumes the values 2 or 3. In particular, both β- and δ-Natriumdisitikate (Na 2 Si 2 O 5 · y H 2 O) is preferred. Also prepared from amorphous alkali metal silicates, practically anhydrous crystalline alkali metal silicates of the abovementioned general formula in which x is a number from 1.9 to 2.1, can be used in the compositions. In a further preferred embodiment, a crystalline sodium layer silicate with a modulus of 2 to 3 is used, as can be prepared from sand and soda. Sodium silicates with a modulus in the range 1.9 to 3.5 are used in a further embodiment. In a preferred embodiment of such agents, a granular compound of alkali silicate and alkali carbonate is used, as is commercially available, for example, under the name Nabion® 15.

Als Bleichmittel kommen solche auf Chlorbasis, wie insbesondere Alkalihypochlorit, Dichlorisocyanursäure, Trichlorisocyanursäure und deren Salze, insbesondere aber auch solche auf Persauerstoffbasis in Frage. Als geeignete Persauerstoffverbindungen kommen insbesondere organische Persäuren beziehungsweise persaure Salze organischer Säuren, wie Phthalimidopercapronsäure, Perbenzoesäure, Monoperoxyphthalsäure, und Diperdodecandisäure sowie deren Salze wie Magnesiummonoperoxyphthalat, Wasserstoffperoxid und unter den Einsatzbedingungen Wasserstoffperoxid abgebende anorganische Salze, wie Perborat, Percarbonat und/oder Persilikat, und Wasserstoffperoxid-Einschlußverbindungen, wie H2O2-Harnstoffaddukte, in Betracht. Wasserstoffperoxid kann dabei auch mit Hilfe eines enzymatischen Systems, das heißt einer Oxidase und ihres Substrats, erzeugt werden. Sofern feste Persauerstoffverbindungen eingesetzt werden sollen, können diese in Form von Pulvern oder Granulaten verwendet werden, die auch in im Prinzip bekannter Weise umhüllt sein können. Besonders bevorzugt wird Alkalipercarbonat, Alkaliperborat-Monohydrat oder Wasserstoffperoxid in Form wässriger Lösungen, die 3 Gew.-% bis 10 Gew.-% Wasserstoffperoxid enthalten, eingesetzt. Falls ein Waschmittel Persauerstoffverbindungen enthält, sind diese in Mengen von vorzugsweise bis zu 25 Gew.-%, insbesondere von 1 Gew.-% bis 20 Gew.-% und besonders bevorzugt von 7 Gew.-% bis 20 Gew.-% vorhanden.Suitable bleaching agents are those based on chlorine, in particular alkali hypochlorite, dichloroisocyanuric acid, trichloroisocyanuric acid and salts thereof, but especially those based on peroxygen. Suitable peroxygen compounds are, in particular, organic peracids or persaltic salts of organic acids, such as phthalimidopercaproic acid, perbenzoic acid, monoperoxyphthalic acid, and diperdodecanedioic acid and salts thereof, such as magnesium monoperoxyphthalate, hydrogen peroxide and inorganic salts which release hydrogen peroxide under the conditions of use, such as perborate, percarbonate and / or persilicate, and hydrogen peroxide. Inclusion compounds, such as H 2 O 2 -urea adducts, into consideration. Hydrogen peroxide can also be produced by means of an enzymatic system, ie an oxidase and its substrate. If solid peroxygen compounds are to be used, they can be used in the form of powders or granules, which can also be enveloped in a manner known in principle. Particular preference is given to using alkali metal percarbonate, alkali metal perborate monohydrate or hydrogen peroxide in the form of aqueous solutions which contain from 3% by weight to 10% by weight of hydrogen peroxide. If a detergent contains peroxygen compounds, they are present in amounts of preferably up to 25% by weight, more preferably from 1% to 20% and most preferably from 7% to 20% by weight.

Als bleichaktivierende, unter Perhydrolysebedingungen Peroxocarbonsäure-liefernde Verbindung können insbesondere Verbindungen, die unter Perhydrolysebedingungen gegebenenfalls substituierte Perbenzoesäure und/oder aliphatische Peroxocarbonsäuren mit 1 bis 12 C-Atomen, insbesondere 2 bis 4 C-Atomen ergeben, allein oder in Mischungen, eingesetzt werden. Geeignet Bleichaktivatoren, die O- und/oder N-Acylgruppen insbesondere der genannten C-Atomzahl und/oder gegebenenfalls substituierte Benzoylgruppen tragen. Bevorzugt sind mehrfach acylierte Alkylendiamine, insbesondere Tetraacetylethylendiamin (TAED), acylierte Glykolurile, insbesondere Tetraacetylglykoluril (TAGU), acylierte Triazinderivate, insbesondere 1,5-Diacetyl-2,4-dioxohexahydro-1,3,5-triazin (DADHT), N-Acylimide, insbesondere N-Nonanoylsuccinimid (NOSI), acylierte Phenolsulfonate oder -carboxylate beziehungsweise die Sulfon- oder Carbonsäuren von diesen, insbesondere Nonanoyl- oder Isononanoyl- oder Lauroyloxybenzolsulfonat (NOBS beziehungsweise iso-NOBS beziehungsweise LOBS) oder Decanoyloxybenzoat (DOBA), deren formale Kohlensäureesterderivate wie 4-(2-Decanoyloxyethoxycarbonyloxy)-benzolsulfonat (DECOBS), acylierte mehrwertige Alkohole, insbesondere Triacetin, Ethylenglykoldiacetat und 2,5-Diacetoxy-2,5-dihydrofuran sowie acetyliertes Sorbitol und Mannitol und deren Mischungen (SORMAN), acylierte Zuckerderivate, insbesondere Pentaacetylglukose (PAG), Pentaacetylfruktose, Tetraacetylxylose und Octaacetyllactose, acetyliertes, gegebenenfalls N-alkyliertes Glucamin und Gluconolacton, und/oder N-acylierte Lactame, beispielsweise N-Benzoylcaprolactam.As bleach-activating peroxycarboxylic acid-yielding compound under perhydrolysis conditions, it is possible in particular to use compounds which give perbenzoic acid which is optionally substituted under perhydrolysis conditions and / or aliphatic peroxycarboxylic acids having 1 to 12 C atoms, in particular 2 to 4 C atoms, alone or in mixtures. Suitable bleach activators which carry O- and / or N-acyl groups, in particular of the stated C atom number and / or optionally substituted benzoyl groups. Preference is given to polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates or carboxylates or the sulfonic or carboxylic acids of these, in particular nonanoyl or isononanoyl or lauroylbenzenesulfonate (NOBS or iso-NOBS or LOBS) or decanoyloxybenzoate ( DOBA), whose formal carbonic acid ester derivatives such as 4- (2-decanoyloxyethoxycarbonyloxy) benzene sulfonate (DECOBS), acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran and acetylated sorbitol and mannitol and mixtures thereof (SORMAN ), acylated sugar derivatives, especially pentaacetylglucose (PAG), pentaacetyl fructose, tetraacetylxylose and octaacetyl lactose, acetylated, optionally N-alkylated glucamine and gluconolactone, and / or N-acylated lactams, for example N-benzoyl caprolactam.

Zusätzlich zu den Verbindungen, die unter Perhydrolysebedingungen Peroxocarbonsäuren bilden, können weitere bleichaktivierende Verbindungen, wie beispielsweise Nitrile, aus denen sich unter Perhydrolysebedingungen Perimidsäuren bilden, vorhanden sein. Dazu gehören insbesondere Aminoacetonitrilderivate mit quaterniertem Stickstoffatom gemäß der Formel

Figure imgb0002
in der R1 für -H, -CH3, einen C2-24-Alkyl-oder-Alkenylrest, einen substituierten C1-24-Alkyl-oder C2-24-Alkenylrest mit mindestens einem Substituenten aus der Gruppe -Cl, -Br, -OH, -NH2, -CN und -N(+)-CH2-CN, einen Alkyl- oder Alkenylarylrest mit einer C1-24-Alkylgruppe, oder für einen substituierten Alkyl- oder Alkenylarylrest mit mindestens einer, vorzugsweise zwei, gegebenenfalls substituierten C1-24-Alkylgruppe(n) und gegebenenfalls weiteren Substituenten am aromatischen Ring steht, R2 und R3 unabhängig voneinander ausgewählt sind aus -CH2-CN, -CH3, -CH2-CH3, -CH2-CH2-CH3, -CH(CH3)-CH3, -CH2-OH, -CH2-CH2-OH, -CH(OH)-CH3, -CH2-CH2-CH2-OH, -CH2-CH(OH)-CH3, -CH(OH)-CH2-CH3, -(CH2CH2-O)nH mit n = 1, 2, 3, 4, 5 oder 6, R4 und R5 unabhängig voneinander eine voranstehend für R1, R2 oder R3 angegebene Bedeutung haben, wobei mindestens 2 der genannten Reste, insbesondere R2 und R3, auch unter Einschluß des Stickstoffatoms und gegebenenfalls weiterer Heteroatome ringschließend miteinander verknüpft sein können und dann vorzugsweise einen Morpholino-Ring ausbilden, und X(-) ein ladungsausgleichendes Anion, vorzugsweise ausgewählt aus Benzolsulfonat, Toluolsulfonat, Cumolsulfonat, den C9-15-Alkylbenzolsulfonaten, den C1-20-Alkylsulfaten, den C8-22-Carbonsäuremethylester-sulfonaten, Sulfat, Hydrogensulfat und deren Gemischen, ist, können eingesetzt werden. Auch sauerstoffübertragende Sulfonimine und/oder Acylhydrazone können eingesetzt werden.In addition to the compounds that form peroxycarboxylic acids under perhydrolysis conditions, other bleach-activating compounds, such as nitriles, from which perimide acids form under perhydrolysis conditions may be present. These include in particular aminoacetonitrile derivatives with quaternized nitrogen atom according to the formula
Figure imgb0002
 in the R 1 is -H, -CH 3 , a C 2-24 -alkyl or alkenyl radical, a substituted C 1-24 -alkyl or C 2-24 -alkenyl radical having at least one substituent from the group -Cl, -Br, -OH, -NH 2 , -CN and -N (+) -CH 2 -CN, an alkyl or alkenylaryl radical having a C 1-24 -alkyl group, or a substituted alkyl- or alkenylaryl radical having at least one, preferably two, optionally substituted C 1-24 alkyl group (s) and optionally further substituents on the aromatic ring, R 2 and R 3 are independently selected from -CH 2 -CN, -CH 3 , -CH 2 -CH 3 , -CH 2 -CH 2 -CH 3 , -CH (CH 3 ) -CH 3 , -CH 2 -OH, -CH 2 -CH 2 -OH, -CH (OH) -CH 3 , -CH 2 -CH 2 -CH 2 -OH, -CH 2 -CH (OH) -CH 3 , -CH (OH) -CH 2 -CH 3 , - (CH 2 CH 2 -O) n H where n = 1, 2, 3, 4, 5 or 6, R 4 and R 5 independently of one another have the meaning given above for R 1 , R 2 or R 3 , where at least 2 of the radicals mentioned, in particular R 2 and R 3 , also including the St ickstoffatoms and optionally other heteroatoms ring-closing linked together and then preferably form a Morpholino ring, and X ( - ) a charge-balancing anion, preferably selected from benzenesulfonate, toluenesulfonate, Cumolsulfonat, the C 9-15 -alkylbenzenesulfonates, the C 1-20 Alkyl sulfates, the C 8-22 -carboxylic acid methyl ester sulfonates, sulfate, hydrogen sulfate and mixtures thereof, can be used. Oxygen-carrying sulfonimines and / or acylhydrazones can also be used.

Auch die Anwesenheit von bleichkatalysierenden Übergangsmetallkomplexen ist möglich. Diese werden vorzugsweise unter den Cobalt-, Eisen-, Kupfer-, Titan-, Vanadium-, Mangan- und Rutheniumkomplexen ausgewählt. Als Liganden in derartigen Übergangsmetallkomplexen kommen sowohl anorganische als auch organische Verbindungen in Frage, zu denen neben Carboxylaten insbesondere Verbindungen mit primären, sekundären und/oder tertiären Amin- und/oder Alkohol-Funktionen, wie Pyridin, Pyridazin, Pyrimidin, Pyrazin, Imidazol, Pyrazol, Triazol, 2,2'-Bispyridylamin, Tris-(2-pyridylmethyl)amin, 1,4,7-Triazacyclononan, 1,4,7-Trimethyl-1,4,7-triazacyclononan, 1,5,9-Trimethyl-1,5,9-triazacyclododecan, (Bis-((1-methylimidazol-2-yl)-methyl))-(2-pyridylmethyl)-amin, N,N'-(Bis-(1-methylimidazol-2-yl)-methyl)-ethylendiamin, N-Bis-(2-benzimidazolylmethyl)-aminoethanol, 2,6-Bis-(bis-(2-benzimidazolylmethyl)aminomethyl)-4-methylphenol, N,N,N',N'-Tetrakis-(2-benzimidazolylmethyl)-2-hydroxy-1,3-diaminopropan, 2,6-Bis-(bis-(2-pyridylmethyl)aminomethyl)-4-methylphenol, 1,3-Bis-(bis-(2-benzimidazolylmethyl)aminomethyl)-benzol, Sorbitol, Mannitol, Erythritol, Adonitol, Inositol, Lactose, und gegebenenfalls substituierte Salene, Porphine und Porphyrine gehören. Zu den anorganischen Neutralliganden gehören insbesondere Ammoniak und Wasser. Falls nicht sämtliche Koordinationsstellen des Übergangsmetallzentralatoms durch Neutralliganden besetzt sind, enthält der Komplex weitere, vorzugsweise anionische und unter diesen insbesondere ein- oder zweizähnige Liganden. Zu diesen gehören insbesondere die Halogenide wie Fluorid, Chlorid, Bromid und lodid, und die (NO2)--Gruppe, das heißt ein Nitro-Ligand oder ein Nitrito-Ligand. Die (NO2)--Gruppe kann an ein Übergangsmetall auch chelatbildend gebunden sein oder sie kann zwei Übergangsmetallatome asymmetrisch oder η1-O-verbrücken. Außer den genannten Liganden können die Übergangsmetallkomplexe noch weitere, in der Regel einfacher aufgebaute Liganden, insbesondere ein- oder mehrwertige Anionliganden, tragen. In Frage kommen beispielsweise Nitrat, Acetat, Trifluoracetat, Formiat, Carbonat, Citrat, Oxalat, Perchlorat sowie komplexe Anionen wie Hexafluorophosphat. Die Anionliganden sollen für den Ladungsausgleich zwischen Übergangsmetall-Zentralatom und dem Ligandensystem sorgen. Auch die Anwesenheit von Oxo-Liganden, Peroxo-Liganden und Imino-Liganden ist möglich. Insbesondere derartige Liganden können auch verbrückend wirken, so dass mehrkernige Komplexe entstehen. Im Falle verbrückter, zweikerniger Komplexe müssen nicht beide Metallatome im Komplex gleich sein. Auch der Einsatz zweikerniger Komplexe, in denen die beiden Übergangsmetallzentralatome unterschiedliche Oxidationszahlen aufweisen, ist möglich. Falls Anionliganden fehlen oder die Anwesenheit von Anionliganden nicht zum Ladungsausgleich im Komplex führt, sind in den gemäß der Erfindung zu verwendenden Übergangsmetallkomplex-Verbindungen anionische Gegenionen anwesend, die den kationischen Übergangsmetall-Komplex neutralisieren. Zu diesen anionischen Gegenionen gehören insbesondere Nitrat, Hydroxid, Hexafluorophosphat, Sulfat, Chlorat, Perchlorat, die Halogenide wie Chlorid oder die Anionen von Carbonsäuren wie Formiat, Acetat, Oxalat, Benzoat oder Citrat. Beispiele für einsetzbare Übergangsmetallkomplex-Verbindungen sind Mn(IV)2(µ-O)3(1,4,7-trimethyl-1,4,7-triazacyclononan)-di-hexafluorophosphat, [N,N'-Bis[(2-hydroxy-5-vinylphenyl)-methylen]-1,2-diaminocyclohexan]-mangan-(III)-chlorid, [N,N'-Bis[(2-hydroxy-5-nitrophenyl)-methylen]-1,2-diaminocyclohexan]-mangan-(III)-acetat, [N,N'-Bis[(2-hydroxyphenyl)-methylen]-1,2-phenylendiamin]-mangan-(III)-acetat, [N,N'-Bis[(2-hydroxyphenyl)-methylen]-1,2-diaminocyclohexan]-mangan-(III)-chlorid, [N,N'-Bis[(2-hydroxyphenyl)-methylen]-1,2-diaminoethan]-mangan-(III)-chlorid, [N,N'-Bis[(2-hydroxy-5-sulfonatophenyl)-methylen]-1,2-diaminoethan]-mangan-(III)-chlorid, Mangan-oxalatokomplexe, Nitropentammin-cobalt(III)-chlorid, Nitritopentammin-cobalt(III)-chlorid, Hexammincobalt(III)-chlorid, Chloropentammin-cobalt(III)-chlorid sowie der Peroxo-Komplex [(NH3)5Co-O-O-Co(NH3)5]Cl4.The presence of bleach-catalyzing transition metal complexes is also possible. These are preferably selected from the cobalt, iron, copper, titanium, vanadium, manganese and ruthenium complexes. Suitable ligands in such transition metal complexes are both inorganic and organic compounds, which in addition to carboxylates in particular compounds having primary, secondary and / or tertiary amine and / or alcohol functions, such as pyridine, pyridazine, pyrimidine, pyrazine, imidazole, pyrazole , Triazole, 2,2'-bispyridylamine, tris (2-pyridylmethyl) amine, 1,4,7-triazacyclononane, 1,4,7-trimethyl-1,4,7-triazacyclononane, 1,5,9-trimethyl -1,5,9-triazacyclododecane, (bis ((1-methylimidazol-2-yl) methyl)) - (2-pyridylmethyl) amine, N, N '- (bis (1-methylimidazole-2-yl) yl) -methyl) -ethylenediamine, N-bis (2-benzimidazolylmethyl) aminoethanol, 2,6-bis (bis (2-benzimidazolylmethyl) aminomethyl) -4-methylphenol, N, N, N ', N' Tetrakis (2-benzimidazolylmethyl) -2-hydroxy-1,3-diaminopropane, 2,6-bis (bis (2-pyridylmethyl) aminomethyl) -4-methylphenol, 1,3-bis (bis (bis) 2-benzimidazolylmethyl) aminomethyl) benzene, sorbitol, mannitol, erythritol, adonitol, inositol, lactose, and optionally substituted ones Salene, porphins and porphyrins belong. The inorganic neutral ligands include in particular ammonia and water. If not all coordination sites of the transition metal central atom are occupied by neutral ligands, the complex contains further, preferably anionic and among these in particular mono- or bidentate ligands. These include in particular the halides such as fluoride, chloride, bromide and iodide, and the (NO 2 ) - group, that is a nitro ligand or a nitrito ligand. The (NO 2 ) - group may also be chelated to a transition metal, or it may bridge two transition metal atoms asymmetrically or η 1 -O-bridge. In addition to the ligands mentioned, the transition metal complexes may carry further, generally simpler ligands, in particular mono- or polyvalent anion ligands. In question, for example, nitrate, acetate, trifluoroacetate, formate, carbonate, citrate, oxalate, perchlorate and complex anions such as hexafluorophosphate. The anion ligands should provide charge balance between the transition metal central atom and the ligand system. The presence of oxo ligands, peroxo ligands and imino ligands is also possible. In particular, such ligands can also act bridging, so that polynuclear complexes arise. In the case of bridged, dinuclear complexes, both metal atoms in the complex need not be the same. The use of binuclear complexes in which the two transition metal central atoms have different oxidation numbers is also possible. If anion ligands are missing or the presence of anionic ligands does not result in charge balance in the complex, anionic counterions which neutralize the cationic transition metal complex are present in the transition metal complex compounds to be used according to the invention. These anionic counterions include in particular nitrate, hydroxide, hexafluorophosphate, sulfate, chlorate, perchlorate, the halides such as chloride or the anions of carboxylic acids such as formate, acetate, oxalate, benzoate or citrate. Examples of transition metal complex compounds that can be used are Mn (IV) 2 (μ-O) 3 (1,4,7-trimethyl-1,4,7-triazacyclononane) -di-hexafluorophosphate, [N, N'-bis [(2 -hydroxy-5-vinylphenyl) methylene] -1,2-diaminocyclohexane] manganese (III) chloride, [N, N'-bis [(2-hydroxy-5-nitrophenyl) methylene] -1,2 diaminocyclohexane] manganese (III) acetate, [N, N'-bis [(2-hydroxyphenyl) methylene] -1,2-phenylenediamine] manganese (III) acetate, [N, N'-bis [(2-hydroxyphenyl) methylene] -1,2-diaminocyclohexane] manganese (III) chloride, [N, N'-bis [(2-hydroxyphenyl) methylene] -1 , 2-diaminoethane] manganese (III) chloride, [N, N'-bis [(2-hydroxy-5-sulfonatophenyl) methylene] -1,2-diaminoethane] -manganese (III) chloride, Manganese oxalato complexes, nitropentammine cobalt (III) chloride, nitrite pentammine cobalt (III) chloride, hexammine cobalt (III) chloride, chloropentammine cobalt (III) chloride, and the peroxo complex [(NH 3 ) 5 Co). OO-Co (NH 3 ) 5 ] Cl 4 .

Als in den Waschmitteln gegebenenfalls enthaltene Enzyme kommen insbesondere solche aus der Klasse der Proteasen, Lipasen, Cutinasen, Amylasen, Pullulanasen, Xylanasen, Hemicellulasen, Cellulasen, Peroxidasen sowie Oxidasen beziehungsweise deren Gemische in Frage, wobei der Einsatz von Protease, Amylase, Lipase und/oder Cellulase besonders bevorzugt ist. Der Anteil beträgt vorzugsweise 0,2 Gew.-% bis 1,5 Gew.-%, insbesondere 0,5 Gew.-% bis 1 Gew.-%. Die Enzyme können in üblicher Weise an Trägerstoffen adsorbiert und/oder in Hüllsubstanzen eingebettet sein oder als konzentrierte, möglichst wasserfreie Flüssigformulierungen eingearbeitet werden.Suitable enzymes in the detergents are, in particular, those from the class of the proteases, lipases, cutinases, amylases, pullulanases, xylanases, hemicellulases, cellulases, peroxidases and oxidases or mixtures thereof, the use of protease, amylase, lipase and / or or cellulase is particularly preferred. The proportion is preferably 0.2 wt .-% to 1.5 wt .-%, in particular 0.5 wt .-% to 1 wt .-%. The enzymes can be adsorbed in a customary manner on carriers and / or embedded in coating substances or incorporated as concentrated, as anhydrous liquid formulations.

Geeignete Vergrauungsinhibitoren beziehungsweise soil-release-Wirkstoffe sind anionische Celluloseether wie Carboxymethylcellulose und Methyl-Carboxymethylcellulose. Vorzugsweise werden die Alkalisalze, insbesondere die Natriumsalze eingesetzt. Zu den üblicherweise eingesetzten Soil-release-Wirkstoffen gehören Copolyester, die Dicarbonsäureeinheiten, Alkylenglykoleinheiten und Polyalkylenglykoleinheiten enthalten. Der Anteil an Vergrauungsinhibitoren und/oder soil-release-Wirkstoffen in den Mitteln liegt im allgemeinen nicht über 2 Gew.-% und beträgt vorzugsweise 0,5 Gew.-% bis 1,5 Gew.-%.Suitable graying inhibitors or soil release agents are anionic cellulose ethers such as carboxymethyl cellulose and methyl carboxymethyl cellulose. Preferably, the alkali metal salts, in particular the sodium salts are used. Commonly used soil release agents include copolyesters containing dicarboxylic acid units, alkylene glycol units and polyalkylene glycol units. The proportion of graying inhibitors and / or soil-release agents in the compositions is generally not more than 2 wt .-%, and is preferably 0.5 wt .-% to 1.5 wt .-%.

Als optische Aufheller für insbesondere Textilien aus Cellulosefasern (zum Beispiel Baumwolle) können in Waschmitteln beispielsweise Derivate der Diaminostilbendisulfonsäure beziehungsweise deren Alkalimetallsalze enthalten sein. Geeignet sind zum Beispiel Salze der 4,4'-Bis(2-anilino-4-morpholino-1,3,5-triazin-6-yl-amino)-stilben-2,2'-disulfonsäure oder gleichartig aufgebaute Verbindungen, die anstelle der Morpholinogruppe eine Diethanolaminogruppe, eine Methylaminogruppe oder eine 2-Methoxyethylaminogruppe tragen. Weiterhin können Aufheller vom Typ des substituierten 4,4'-Distyryl-diphenyl anwesend sein, zum Beispiel 4,4'-Bis-(4-chlor-3-sulfostyryl)-diphenyl. Auch Gemische von Aufhellern können verwendet werden. Für Polyamidfasern eignen sich besonders gut Aufheller vom Typ der 1,3-Diaryl-2-pyrazoline, beispielsweise 1-(p-Sulfoamoylphenyl)-3-(p-chlorphenyl)-2-pyrazolin sowie gleichartig aufgebaute Verbindungen. Der Gehalt des Mittels an optischen Aufhellern beziehungsweise Aufhellergemischen liegt im allgemeinen nicht über 1 Gew.-%, vorzugsweise 0,05 Gew.-% bis 0,5 Gew.-%. In einer bevorzugten Ausführungsform ist das Mittel frei von derartigen Wirkstoffen.As optical brighteners for particular textiles made of cellulose fibers (for example cotton), detergents may contain, for example, derivatives of diaminostilbenedisulfonic acid or their alkali metal salts. For example, salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazin-6-yl-amino) -stilbene-2,2'-disulphonic acid or similarly constructed compounds which are suitable instead of the morpholino group, carry a diethanolamino group, a methylamino group or a 2-methoxyethylamino group. Further, brighteners of the substituted 4,4'-distyryl-diphenyl type may be present, for example, 4,4'-bis (4-chloro-3-sulfostyryl) -diphenyl. Also, mixtures of brighteners can be used. For polyamide fibers, brighteners of the 1,3-diaryl-2-pyrazolines type, for example 1- (p-sulfamoylphenyl) -3- (p-chlorophenyl) -2-pyrazoline, and compounds of similar construction are particularly suitable. The content of the composition in optical brighteners or brightener mixtures is generally not more than 1 wt .-%, preferably 0.05 wt .-% to 0.5 wt .-%. In a preferred embodiment, the agent is free of such agents.

Zu den in Waschmitteln einsetzbaren üblichen Schaumregulatoren gehören beispielsweise Polysiloxan-Kieselsäure-Gemische, wobei die darin enthaltene feinteilige Kieselsäure vorzugsweise silaniert oder anderweitig hydrophobiert ist. Die Polysiloxane können sowohl aus linearen Verbindungen wie auch aus vernetzten Polysiloxan-Harzen sowie aus deren Gemischen bestehen. Weitere Entschäumer sind Paraffinkohlenwasserstoffe, insbesondere Mikroparaffine und Paraffinwachse, deren Schmelzpunkt oberhalb 40 °C liegt, gesättigte Fettsäuren beziehungsweise Seifen mit insbesondere 20 bis 22 C-Atomen, zum Beispiel Natriumbehenat, und Alkalisalze von Phosphorsäuremono- und/oder -dialkylestern, in denen die Alkylketten jeweils 12 bis 22 C-Atome aufweisen. Unter diesen wird bevorzugt Natriummonoalkylphosphat und/oder -dialkylphosphat mit C16- bis C18-Alkylgruppen eingesetzt. Der Anteil der Schaumregulatoren kann vorzugsweise 0,2 Gew.-% bis 2 Gew.-% betragen.The customary foam regulators which can be used in detergents include, for example, polysiloxane-silica mixtures, the finely divided silica contained therein preferably being silanated or otherwise rendered hydrophobic. The polysiloxanes can consist of both linear compounds as well as crosslinked polysiloxane resins and mixtures thereof. Further antifoams are paraffin hydrocarbons, in particular microparaffins and paraffin waxes whose melting point is above 40 ° C., saturated fatty acids or soaps having in particular 20 to 22 carbon atoms, for example sodium behenate, and alkali metal salts of phosphoric mono- and / or dialkyl esters in which the alkyl chains each having 12 to 22 carbon atoms. Among these, preference is given to using sodium monoalkyl phosphate and / or dialkyl phosphate having C 16 - to C 18 -alkyl groups. The proportion of foam regulators may preferably be from 0.2% by weight to 2% by weight.

Die Mittel können Wasser als Lösungsmittel enthalten. Zu den in den Mitteln, insbesondere wenn sie in flüssiger oder pastöser Form vorliegen, verwendbaren organischen Lösungsmitteln gehören Alkohole mit 1 bis 4 C-Atomen, insbesondere Methanol, Ethanol, Isopropanol und tert.-Butanol, Diole mit 2 bis 4 C-Atomen, insbesondere Ethylenglykol und Propylenglykol, sowie deren Gemische und die aus den genannten Verbindungsklassen ableitbaren Ether. Derartige wassermischbare Lösungsmittel sind in den Mitteln in Mengen von vorzugsweise nicht über 20 Gew.-%, insbesondere von 1 Gew.-% bis 15 Gew.-%, vorhanden.The agents may contain water as a solvent. Among the organic solvents which can be used in the compositions, in particular if they are in liquid or pasty form, are alcohols having 1 to 4 C atoms, in particular methanol, ethanol, isopropanol and tert-butanol, diols having 2 to 4 C atoms, in particular ethylene glycol and propylene glycol, and mixtures thereof and the derivable from said classes of compounds ethers. Such water-miscible solvents are present in the compositions in amounts of preferably not more than 20% by weight, in particular from 1% by weight to 15% by weight.

Zur Einstellung eines gewünschten, sich durch die Mischung der übrigen Komponenten nicht von selbst ergebenden pH-Werts können die Mittel system- und umweltverträgliche Säuren, insbesondere Citronensäure, Essigsäure, Weinsäure, Äpfelsäure, Milchsäure, Glykolsäure, Bernsteinsäure, Glutarsäure und/oder Adipinsäure, aber auch Mineralsäuren, insbesondere Schwefelsäure oder Alkalihydrogensulfate, oder Basen, insbesondere Ammonium- oder Alkalihydroxide, enthalten. Derartige pH-Regulatoren sind vorzugsweise nicht über 10 Gew.-%, insbesondere von 0,5 Gew.-% bis 6 Gew.-%, enthalten.To establish a desired, by the mixture of the other components not automatically resulting pH, the agents can system and environmentally acceptable acids, in particular citric acid, acetic acid, tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid and / or adipic acid, but Also, mineral acids, in particular sulfuric acid or alkali metal hydrogen sulfates, or bases, in particular ammonium or alkali metal hydroxides. Such pH regulators are preferably not more than 10 wt .-%, in particular from 0.5 wt .-% to 6 wt .-%, included.

Die Herstellung fester Mittel bietet keine Schwierigkeiten und kann in im Prinzip bekannter Weise, zum Beispiel durch Sprühtrocknen oder Granulation, erfolgen, wobei thermisch empfindliche Inhaltsstoffe gegebenenfalls später getrennt zugesetzt werden.The preparation of solid compositions presents no difficulties and can be carried out in a manner known in the art, for example by spray-drying or granulation, thermally-sensitive ingredients optionally being added separately later.

Mittel in Form wässriger oder sonstige übliche Lösungsmittel enthaltender Lösungen werden besonders vorteilhaft durch einfaches Mischen der Inhaltsstoffe, die in Substanz oder als Lösung in einen automatischen Mischer gegeben werden können, hergestellt.Compositions in the form of aqueous or other conventional solvent-containing solutions are particularly advantageously prepared by simply mixing the ingredients, which can be added in bulk or as a solution in an automatic mixer.

Die Mittel liegen vorzugsweise als pulverförmige, granulare oder tablettenförmige Präparate vor, die in an sich bekannter Weise, beispielsweise durch Mischen, Granulieren, Walzenkompaktieren und/oder durch Sprühtrocknung der thermisch belastbaren Komponenten und Zumischen der empfindlicheren Komponenten, zu denen insbesondere Enzyme, Bleichmittel und bleichaktivierende Wirkstoffe zu rechnen sind, hergestellt werden können. Zur Herstellung von Mitteln mit erhöhtem Schüttgewicht, insbesondere im Bereich von 650 g/l bis 950 g/l, ist ein einen Extrusionsschritt aufweisendes Verfahren bevorzugt.The agents are preferably in the form of powdered, granular or tablet-shaped preparations which are compacted in a manner known per se, for example by mixing, granulating, roll compacting and / or by spray-drying the thermally stable components and admixing the more sensitive components, to which in particular enzymes, bleaching agents and bleach-activating agents are to be expected. For the production of compositions having an increased bulk density, in particular in the range from 650 g / l to 950 g / l, a process comprising an extrusion step is preferred.

Zur Herstellung von Mitteln in Tablettenform geht man vorzugsweise derart vor, dass man alle Bestandteile in einem Mischer miteinander vermischt und das Gemisch mittels herkömmlicher Tablettenpressen, beispielsweise Exzenterpressen oder Rundläuferpressen, mit Preßdrucken im Bereich von 200 · 105 Pa bis 1 500 · 105 Pa verpresst. Man erhält so problemlos bruchfeste und dennoch unter Anwendungsbedingungen ausreichend schnell lösliche Tabletten mit Biegefestigkeit von normalerweise über 150 N. Vorzugsweise weist eine derart hergestellte Tablette ein Gewicht von 15 g bis 40 g, insbesondere von 20 g bis 30 g auf, bei einem Durchmesser von 35 mm bis 40 mm.For the preparation of compositions in tablet form, the procedure is preferably such that all components are mixed together in a mixer and the mixture by means of conventional tablet presses, such as eccentric or rotary presses, with pressing pressures in the range of 200 · 10 5 Pa to 1 500 · 10 5 Pa pressed. This gives unbreakable, yet sufficiently rapidly soluble tablets under application conditions with flexural strength of usually over 150 N. Preferably, a tablet thus produced has a weight of 15 g to 40 g, in particular from 20 g to 30 g, with a diameter of 35 mm to 40 mm.

Beispielexample

Das Cellulosederivat Polyquaternium-67 (quaternisierte Hydroxyethylcellulose mit kationischer Substitution durch Trimethylammonium und Dimethyldodecylammonium; Softcat® SX 400 H) wurde in 1 gew-%iger Lösung auf Läppchen aus Baumwolle zwangsappliziert, die Läppchen wurden getrocknet und anschließend mit den Prüfbakterium Pseudomonas aeruginosa beaufschlagt. Dazu wurden die Prüfbakterien zuvor über Nacht auf TSA Agarmedium kultiviert und anschließend mit Trypton-NaCl von den Agarplatten abgeschwemmt. Es erfolgten Verdünnungsschritte in Trypton-NaCl. Der letzte Verdünnungsschritt wurde in PBS-Puffer (1fach) durchgeführt. Nach Inkubation der Prüfkeimsuspension auf den Textilprüfläppchen wurden diese anschließend wiederholt mit Pufferlösung gespült, um nicht adhärierte Testkeime abzuwaschen. Die Anzahl der an die Textilprüfläppchen adhärierten Mikroorganismen wurde bestimmt, indem die Textilprüfläppchen in sterile Röhrchen mit PBS + 0,05% Tween 80 und Glasperlen transferiert wurden, um fest anhaftende Testkeime abzulösen. Anschließend wurden die Läppchen in sterile Petrischalen gelegt, mit Caso-Agar überschichtet und bis zu 48 h bei 37°C aerob inkubiert. Zusätzlich erfolgte eine Keimzahlbestimmung der Schüttellösung. Die Menge an adhäriertem Mikroorganismus im Vergleich zu der Menge (100 %), die unter den gleichen Bedingungen an einem unbehandelten Läppchen anhaftete, betrug nur 70 %. Die Mikroorganismen waren demnach an die behandelten Läppchen signifikant geringer als an die unbehandelten Läppchen gebunden worden.The cellulose derivative Polyquaternium-67 (quaternized hydroxyethylcellulose with cationic substitution by trimethylammonium and dimethyldodecylammonium, Softcat® SX 400 H) was forcibly applied in 1% strength solution to cotton lobes, the lobules were dried and then treated with the test bacterium Pseudomonas aeruginosa. For this purpose, the test bacteria were previously cultivated overnight on TSA agar medium and then washed away with the tryptone-NaCl from the agar plates. There were dilution steps in tryptone-NaCl. The final dilution step was carried out in PBS buffer (1-fold). After incubation of the test microbial suspension on the Textilprüflppchen these were then rinsed repeatedly with buffer solution to wash off non-adherent test germs. The number of microorganisms adhered to the textile scratches was determined by transferring the scrims to sterile tubes containing PBS + 0.05% Tween 80 and glass beads to strip off adherent test bacteria. Subsequently, the lobes were placed in sterile Petri dishes, covered with Caso agar and incubated aerobically for 48 h at 37 ° C. In addition, a germ count of the shaking solution was carried out. The amount of adhered microorganism compared to the amount (100%) adhered to an untreated lobe under the same conditions was only 70%. The microorganisms were therefore significantly lower in the treated lobes than bound to the untreated lobules.

Claims (10)

  1. The use of cellulose derivatives of general formula (I),

            ((R-O-)3RCell)y     (I)

    where RCell is the functional group of an anhydroglucose unit, the degree of polymerization y is a number from 1000 to 5000 and each of the functional groups R corresponds to general formula (II) or (III),

            -(CaH2a-O)m-(CbH2b-O)n-(CcH2c)o-R1     (II)

    Figure imgb0005
     where
    a and b, independently of one another, represent 2 or 3,
    c is a number from 1 to 10,
    m, n and p, independently of one another, represent a number from 0 to 10,
    o represents 0 or 1,
    R1 represents hydrogen, a C1-18 alkyl, alkyl aryl, aryl alkyl, or aryl functional group, or represents the group -NR2R3(R4)q Ys, where R1 represents hydrogen when o = 0,
    R2, R3 and R4, independently of one another, represent hydrogen, a C1-18 alkyl, alkyl aryl, aryl alkyl or aryl functional group,
    q represents 0 or 1,
    Y represents an anion, and
    s is a number greater than or equal to zero, such that the whole molecule of formula (I) has no charge,
    and in the cellulose derivative of general formula (I) at least one functional group R corresponds to general formula (II) or (III), where m, n, and o are greater than 0 and/or the group -R1 represents -NR2R3(R4)q,
    for preventing microbial colonization of textile surfaces.
  2. The use of cellulose derivatives of general formula (I),

            ((R-O-)3RCell)y     (I)

    where RCell is the functional group of an anhydroglucose unit, the degree of polymerization y is a number from 1000 to 5000 and each of the functional groups R corresponds to general formula (II) or (III),

            -(CaH2a-O)m-(CbH2b-O)n-(CcH2c)o-R1     (II)

    Figure imgb0006
     where
    a and b, independently of one another, represent 2 or 3,
    c is a number from 1 to 10,
    m, n and p, independently of one another, represent a number from 0 to 10,
    o represents 0 or 1,
    R1 represents hydrogen, a C1-18 alkyl, alkyl aryl, aryl alkyl or aryl radical group or represents the group -NR2R3(R4)q Ys, where R1 represents hydrogen when o = 0,
    R2, R3 and R4, independently of one another, represent hydrogen, a C1-18 alkyl, alkyl aryl, aryl alkyl or aryl functional group,
    q represents 0 or 1,
    Y represents an anion, and
    s is a number greater than or equal to zero, such that the whole molecule of formula (I) has no charge,
    and in the cellulose derivative of general formula (I) at least 1 functional group R corresponds to general formula (II) or (III), where m, n, and o are greater than 0 and/or the group -R1 represents -NR2R3(R4)q,
    for preventing or reducing the adhesion of microorganisms to textiles.
  3. The use according to claim 1 or 2, characterized in that the cellulose derivative is a component of a washing agent.
  4. The use according to one of claims 1 to 3, characterized in that the colonization is by means of bacteria, fungi and/or viruses.
  5. The use according to one of claims 1 to 4, characterized in that a washing agent containing the cellulose derivative is allowed to act on a textile as part of a washing process that is automatic or carried out by hand.
  6. The use according to one of claims 3 to 5, characterized in that the agent contains 0.01 wt.% to 2 wt.%, in particular 0.05 wt.% to 1.5 wt.% of the cellulose derivative.
  7. The use according to one of claims 1 to 6, characterized in that an aqueous liquor is used that contains 1 mg/l to 5000 mg/l, in particular 10 mg/l to 500 mg/l of the cellulose derivative.
  8. The use according to one of claims 1 to 7, characterized in that in at least one of the functional groups R, m, n, and o are greater than 0 and the group -R1 represents -NR2R3(R4)q.
  9. The use according to one of claims 1 to 8, characterized in that the cellulose derivative is selected from the group comprising trialkyl ammonium hydroxypropyl cellulose and trialkyl ammonium ethyl cellulose and mixtures thereof.
  10. The use according to one of claims 1 to 9, characterized in that in the cellulose derivative according to formula (I), on average 0.01 to 1, in particular 0.1 to 0.8, of functional groups R1, which carry the group -NR2R3(R4)q, are present per group RCell.
EP13791992.4A 2012-11-20 2013-11-14 Use of antiadhesive polymers for microbe-repulsive textile finishing Active EP2922941B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102012221197.7A DE102012221197A1 (en) 2012-11-20 2012-11-20 Anti-adhesive polymers for microbial-repulsive textile finishing
PCT/EP2013/073773 WO2014079757A1 (en) 2012-11-20 2013-11-14 Use of antiadhesive polymers for microbe-repulsive textile finishing

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EP2922941A1 EP2922941A1 (en) 2015-09-30
EP2922941B1 true EP2922941B1 (en) 2018-06-27

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DE (1) DE102012221197A1 (en)
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Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5171526A (en) * 1990-01-05 1992-12-15 Allergan, Inc. Ophthalmic compositions and methods for preserving and using same
DE10351321A1 (en) * 2003-02-10 2004-08-26 Henkel Kgaa Enhancing the cleaning performance of detergents through a combination of cellulose derivatives
DE102004018051A1 (en) * 2004-04-08 2005-11-10 Clariant Gmbh Detergents and cleaning agents containing dye fixing agents and soil release polymers
US20090111786A1 (en) 2004-12-03 2009-04-30 Glass Christopher K Compounds that Prevent Macrophage Apoptosis and Uses Thereof
WO2006071452A2 (en) 2004-12-28 2006-07-06 General Instrument Corporation System and method for pre-caching media content
DE102005003122A1 (en) 2005-01-21 2006-07-27 Henkel Kgaa Anti-adhesive polymers to prevent the adhesion of microorganisms to textiles and to prevent laundry odor
US20080249136A1 (en) * 2005-10-25 2008-10-09 Ioana Annis Antimicrobial Composition and Method
AU2011240856B2 (en) * 2010-04-12 2014-02-13 Basf Se Antimicrobial treatment of synthetic nonwoven textiles

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
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DE102012221197A1 (en) 2014-05-22
WO2014079757A1 (en) 2014-05-30
EP2922941A1 (en) 2015-09-30

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