Classifications

• • 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
  • C11D3/37—Polymers
  • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines

Definitions

• the present invention relates to the use of certain copolymers of ethylenically unsaturated compounds for the removal of unpleasant odors from textiles, hard surfaces and / or rinsing or washing machine interiors.
• An object of the invention is therefore the use of polymers obtainable by free-radical copolymerization of at least one compound of the formula (I), in which n is a number equal to or greater than 3, in particular a number in the range of 3 to 120, more preferably a number in the range of 5 to 50, and particularly preferred a number in the range of 7 to 46, wherein in one embodiment n is selected from the group comprising the numbers 7, 23 and 46, with at least one compound of the formula (II), in the A - represents an anion, in particular selected from halides such as fluoride, chloride, bromide, iodide, sulfate, hydrogen sulfate, alkyl sulfate such as methyl sulfate and mixtures thereof, to eliminate odors from textiles, hard surfaces and / or washing and / or dishwasher interior.
• halides such as fluoride, chloride, bromide, iodide, sulfate, hydrogen sulfate,
• the polymers essential to the invention can be obtained by basically known radical polymerization processes.
• a radical initiator such as a bi-azo compound, a persulfate, a peroxide or a hydroperoxide
• the monomer of the general formula (I) or the monomer of the general formula (II) can first be subjected to free-radical polymerization and then free-radically polymerized onto the monomer of the general formula (II) or the monomer of the general formula (I), such that Copolymers receives.
• Preferred polymers used according to the invention are obtainable by copolymerization of the compound according to general formula (I) and the compound according to general formula (II) in molar ratios in the range from 1:99 to 75:25, in particular in the range from 5:95 to 70: 30th
• the polymers used according to the invention preferably contain no moieties derived from monomers other than the compounds of the general formulas (I) and (II).
• part of the amount of compounds of general formula (II) preferably not more than 60 mol%, may be represented by the corresponding non-quaternized compound of formula (III), be replaced.
• the average molecular weight (weight average) of the polymers used according to the invention is preferably in the range from 10,000 g / mol to 100,000 g / mol, in particular from 20,000 g / mol to 70,000 g / mol.
• the use according to the invention removes undesirable odors from textiles, hard surfaces and / or rinsing and washing machine interiors. This creates a pleasant smell on textiles and hard surfaces and in the machines and creates the impression of freshness and hygiene in the consumer.
• the polymer essential to the invention is particularly effective for removing malodorous molecules from the substance groups of the sulfides, such as dimethyl sulfide and dimethyl sulfide, thiols such as methyl mercaptan, and acids such as butyric acid, isovaleric acid, caproic acid and unsaturated short-chain carboxylic acids.
• the use according to the invention in both embodiments is preferably realized by the use of a washing, laundry aftertreatment or cleaning agent containing a polymer essential to the invention, or by addition of the polymer to a washing, laundering or cleaning liquor which is an agent free of the corresponding polymer wherein the addition amount of polymer, based on the amount of free of the corresponding polymer free agent, preferably in the range of 0.0001 wt .-% to 20 wt .-%, in particular from 0.01 wt .-% to 10 wt .-% lies.
• the polymer essential to the invention is used together with detergents or cleaners which contain from 0.1% by weight to 50% by weight, in particular from 5% by weight to 40% by weight, of non-soap surfactant.
• the weight ratio of non-soap surfactant to polymer essential to the invention is in the range from 5: 1 to 5000: 1, in particular 8: 1 to 23: 1 and particularly preferably to 18: 1.
• non-soap surfactant is meant the total amount of surfactants present which are not soaps.
• the concentration of above-defined polymer in aqueous liquor is 0.001 g / l to 5 g / l, in particular 0.01 g / l to 2 g / l.
• the reaction is preferably carried out at temperatures in the range from 10 ° C. to 95 ° C., in particular in the range from 20 ° C. to 40 ° C.
• the use according to the invention is preferably carried out at pH values in the range from pH 5 to pH 12, in particular from pH 7 to pH 11.
• pH values below the alkaline range are particularly suitable when using acidic cleansing agents or "functional finishers" which usually have pH values in the range of pH 2 to pH 4 (measured on the undiluted liquid medium or in 10 percent by weight solution of solid agents in distilled water).
• Such agents preferably contain the polymer used in the invention; Alternatively, the polymer used according to the invention may also be used separately at the same time as or subsequent to the use of agents in which the said polymer is not contained.
• the polymer essential to the invention be obtained by spraying an aqueous formulation containing the polymer on textiles, hard surfaces and / or washing and Dishwasher interior is applied, for example by means of spray can (compressed gas can, compressed gas package, aerosol) or mechanically operated pump sprayer (pump spray), from which the polymer preparation exits, for example, to form a spray, a foam, a paste or a liquid jet.
• spray can compressed gas can, compressed gas package, aerosol
• pump sprayer pump spray
• Wäschenach accordinglys- or cleaning agents which are preferably liquid and hydrous, but also in particular powdered solids, in nachverêtter particle form, may be present as solutions or suspensions, all known and in such agents usual ingredients.
• the agents may in particular be builders, surfactants, water-miscible organic solvents, enzymes, sequestering agents, electrolytes, pH regulators, special effect polymers such as soil release polymers, dye transfer inhibitors, grayness inhibitors, wrinkle reducing and formaldehyde polymeric actives, and other adjuvants such as optical brighteners , Foam regulators, dyes and fragrances.
• the polymer essential to the invention is used together with fragrances, in particular comprising at least one fragrance aldehyde and / or at least one fragrance ketone.
• fragrance aldehydes are those fragrances which are chemically an aldehyde and which advantageously cause a particularly pleasant odor sensation in humans.
• Fragrance ketones are those fragrances which are chemically a ketone and which advantageously cause in humans a particularly pleasant sense of smell.
• the fragrance aldehyde is selected according to a preferred embodiment of the invention from adoxal (2,6,10-trimethyl-9-undecenal), anisaldehyde (4-methoxybenzaldehyde), cymal (3- (4-isopropyl-phenyl) -2-methylpropanal ), Ethylvanillin, florhydral (3- (3-isopropylphenyl) butanal), helional (3- (3,4-methylenedioxyphenyl) -2-methylpropanal), heliotropin, hydroxycitronellal, lauraldehyde, lyral (3- and 4- (4-hydroxy 4-methylpentyl) -3-cyclohexene-1-carboxaldehyde), methylnonylacetaldehyde, lilial (3- (4-tert-butylphenyl) -2-methylpropanal), phenylacetaldehyde, undecylenealdehyde, van
• the fragrance ketone is selected according to a preferred embodiment of the invention from methyl-beta-naphthyl ketone, muskedanone (1,2,3,5,6,7-hexahydro-1,1,2,3,3-pentamethyl-4H-indene 4-one), tartalide (6-acetyl-1,1,2,4,4,7-hexamethyltetralin), alpha-damascone, beta-damascone, delta-damascone, iso-damascone, damascenone, methyldihydrojasmonate, menthone, carvone , Camphor, koavon (3,4,5,6,6-pentamethylhept-3-en-2-one), fenchone, alpha-ionone, beta-ionone, gamma-methyl-ionone, fleuramon (2-heptylcyclopentanone) , Dihydrojasmon, cis-Jasmon, iso-
• fragrances which may additionally be used in the context of the use according to the invention are not subject to any particular restrictions, provided that they contribute to producing an attractive fragrance note.
• individual fragrance compounds of natural or synthetic origin for example of the ester type, ethers, aldehydes, ketones, alcohols and hydrocarbons can be used.
• Fragrance type compounds of the ester type include, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinylacetate (DMBCA), phenylethylacetate, benzylacetate, ethylmethylphenylglycinate, allylcyclohexylpropionate, styrallylpropionate, benzylsalicylate, cyclohexylsalicylate, floramate, melusate and jasmacyclate.
• DMBCA dimethylbenzylcarbinylacetate
• the ethers include, for example, benzyl ethyl ether and ambroxane, to the aldehydes, for example, the linear alkanals having 8 to 18 carbon atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde (3- (4-propan-2-ylphenyl) butanal), lilial and bourgeonal , to the ketones eg the ionones, ⁇ -isomethylionone and methylcedryl ketone, the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons mainly include terpenes such as limonene and pinene. Preferably, however, mixtures of different fragrances are used, which together produce an attractive fragrance.
• fragrance mixtures as obtainable from plant sources, e.g. Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil.
• plant sources e.g. Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil.
• suitable fragrance are Muskateller sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, lime blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil and orange blossom oil, neroli oil, orange peel oil and sandalwood oil.
• fragrances which can additionally be used in the context of the present invention are, for example, the essential oils such as angelica root oil, aniseed oil, arnica blossom oil, basil oil, bay oil, Champacablütenöl, Edeltannöl, Edeltannenzapfenapfen, Elemiöl, eucalyptus oil, fennel oil, spruce needle oil, galbanum oil, geranium oil, gingergrass oil, Guaiac wood oil, gurdy balm oil, helichrysum oil, ho oil, ginger oil, iris oil, cajeput oil, calamus oil, chamomile oil, camphor oil, kanga oil, cardamom oil, cassia oil, pine oil, copaia balsam oil, coriander oil, spearmint oil, caraway oil, cumin oil, lavender oil, lemongrass oil, lime oil, tangerine oil, lemon balm oil, Musk Grain Oil, Myrrh Oil, Clove Oil, Neroli Oil, Ni
• the content of optional fragrances in the composition is preferably 0.001% by weight to 10% by weight, advantageously 0.01% by weight to 5% by weight and in particular 0.1% by weight to 3% by weight. %, Wt .-% based on the total mean.
• fragrances preferably comprising fragrance aldehydes and / or fragrance ketones, in particular in combination with surfactants, allows a particularly good, according to the invention aimed at reducing bad smells.
• compositions containing the polymer according to the invention or used together with it may contain one or more surfactants, in particular anionic surfactants, nonionic surfactants and mixtures thereof, but also cationic and / or amphoteric surfactants may be present.
• surfactants in particular anionic surfactants, nonionic surfactants and mixtures thereof, but also cationic and / or amphoteric surfactants may be present.
• nonionic surfactants it is possible to use all nonionic surfactants known to the person skilled in the art.
• the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or linear and methyl branched May contain residues in the mixture, as they are usually present in Oxoalkoholresten.
• EO ethylene oxide
• alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 moles of EO per mole of alcohol are preferred.
• the preferred ethoxylated alcohols include, for example, C 12-14 alcohols with 3 EO or 4 EO, C 9-11 alcohols with 7 EO, C 13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C 12-14 -alcohol with 3 EO and C 12-18 -alcohol with 5 EO.
• the stated degrees of ethoxylation represent statistical averages, which may correspond to a particular product of an integer or a fractional number.
• Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
• nonionic surfactants it is also possible to use fatty alcohols with more than 12 EO. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
• other nonionic surfactants which can also be employed are alkylglycosides of the general formula R 5 O (G) x , in which R 5 is a primary straight-chain or methyl-branched, especially methyl-branched, 2-position aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms.
• R 5 is a primary straight-chain or methyl-branched, especially methyl-branched, 2-position aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms.
• Corresponds to atoms and G is the symbol which represents a glycose unit having 5 or 6 C atoms, preferably glucose.
• the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10;
• nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having from 1 to 4 carbon atoms in the alkyl chain.
• Nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can also be used.
• the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.
• polyhydroxy fatty acid amides of the formula R is an aliphatic acyl radical having 6 to 22 carbon atoms, R 1 is hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl radical having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups stands.
• the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
• the group of polyhydroxy fatty acid amides also includes compounds of the formula R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R 1 is a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R 2 is a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, with C 1-4 alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated Derivatives of this residue.
• [Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
• a reduced sugar for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
• the N-alkoxy- or N-aryloxy-substituted compounds can be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
• anionic surfactants for example, those of the sulfonate type and sulfates are used.
• Preferred surfactants of the sulfonate type are C 9-13 -alkylbenzenesulfonates, olefinsulfonates, that is to say mixtures of alkene and hydroxyalkanesulfonates and also disulfonates, as are obtained, for example, from C 12-18 -monoolefins having terminal or internal double bonds by sulfonation with gaseous Sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation obtained.
• alkanesulfonates which are obtained from C 12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
• esters of ⁇ -sulfo fatty acids esters of ⁇ -sulfo fatty acids (ester sulfonates), for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.
• sulfated fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and mixtures thereof, as obtained in the preparation by esterification of glycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol.
• Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
• alkyl sulfates of the general formula RO-SO 3 M in which R is a linear, branched or cyclic saturated hydrocarbon radical having from 12 to 18, in particular 12 to 14, carbon atoms and M is a countercation leading to charge neutralization of the sulfuric acid half-ester, in particular a sodium or potassium ion or an ammonium ion of the general formula R 1 R 2 R 3 R 4 N + , in which R 1 , R 2 , R 3 , and R 4 independently of one another represent hydrogen, an alkyl group having 1 to 4 C atoms or a hydroxyalkyl group having 2 to 3 C atoms.
• Preferred radicals R are derived from native C 12 -C 18 fatty alcohols, such as, for example, coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or the C 10 -C 20 oxo alcohols or secondary alcohols of these chain lengths.
• alkyl sulfates of said chain length which contain a synthetic, straight-chain alkyl radical produced on a petrochemical basis, which have an analogous degradation behavior as the adequate compounds based on oleochemical raw materials.
• C 12 -C 16 alkyl sulfates and C 12 -C 14 alkyl sulfates are particularly preferred.
• EO ethylene oxide
• Fatty alcohols with 1 to 4 EO are suitable.
• Suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols.
• alcohols preferably fatty alcohols and in particular ethoxylated fatty alcohols.
• Preferred sulfosuccinates contain C 8-18 fatty alcohol residues or mixtures of these.
• Particularly preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty alcohols, which by themselves are nonionic surfactants.
• Sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are again particularly preferred.
• alk (en) ylsuccinic acid having preferably 8 to 18 carbon atoms in the alkenyl chain or salts thereof.
• anionic surfactants are particularly soaps into consideration.
• Suitable are saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid and, in particular, soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids.
• the anionic surfactants may be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine.
• the anionic surfactants are preferably present in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
• Such surfactants are present in detergents in amounts of preferably from 5% by weight to 50% by weight, in particular from 8% by weight to 30% by weight.
• fabric softening compounds can be used in detergents and in particular in laundry after-treatment agents.
• the active ingredients of these formulations are quaternary Ammonium compounds with two hydrophobic radicals, such as the Disteraryldimethylammoniumchlorid, but which is increasingly replaced by its insufficient biodegradability by quaternary ammonium compounds containing ester groups in their hydrophobic residues as predetermined breaking points for biodegradation.
• esters with improved biodegradability are obtainable, for example, by esterifying mixtures of methyldiethanolamine and / or triethanolamine with fatty acids and then quaternizing the reaction products in a manner known per se with alkylating agents.
• Suitable as a finishing agent is dimethylolethyleneurea.
• 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 methylglycinediacetic acid, nitrilotriacetic acid and ethylenediaminetetraacetic acid and polyaspartic acid, polyphosphonic acids, in particular aminotris (methylenephosphonic acid), ethylenediaminetetrakis (methylenephosphonic acid) and 1-hydroxyethane-1,1-diene diphosphonic acid, polymeric hydroxy compounds such as dextrin and polymeric (poly) carboxylic acids, in particular by oxidation of polysaccharides or dextrins accessible polycarboxylates, and / or polymeric acrylic acids, methacrylic acids, maleic acids and copolymers thereof, which may also contain polymerized small amounts of polymerizable
• the 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 molecular weight of 50,000 g / mol to 100,000 g / mol.
• Suitable, although less preferred, compounds of this class are copolymers of acrylic or methacrylic acid with vinyl ethers, such as vinylmethyl ethers, vinyl esters, ethylene, propylene and styrene, in which the acid content is at least 50% by weight. It is also possible to use terpolymers which contain two unsaturated acids and / or salts thereof as monomers and also vinyl alcohol and / or an esterified vinyl alcohol or a carbohydrate as the third monomer as water-soluble organic builder substances.
• the first acidic monomer or its salt is derived from a monoethylenically unsaturated C 3 -C 8 -carboxylic acid and preferably from a C 3 -C 4 -monocarboxylic acid, in particular from (meth) -acrylic acid.
• the second acidic monomer or its salt may be a derivative of a C 4 -C 8 -dicarboxylic acid, with maleic acid being particularly preferred, and / or a derivative of an allylsulfonic acid which is substituted in the 2-position by an alkyl or aryl radical.
• Such polymers generally have a molecular weight between 1,000 g / mol and 200,000 g / mol.
• copolymers are those which are used 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 in the upper half of said ranges are preferably used in pasty or liquid, in particular water-containing agents.
• Suitable water-soluble inorganic builder materials are, in particular, polymeric alkali metal phosphates, which may be in the form of their alkaline neutral or acidic sodium or potassium salts. Examples of these are tetrasodium diphosphate, disodium dihydrogen diphosphate, pentasodium triphosphate, so-called sodium hexametaphosphate and the corresponding potassium salts or mixtures of sodium and potassium salts. Crystalline or amorphous alkali metal aluminosilicates, in amounts of up to 50% by weight, preferably not more than 40% by weight, and in liquid agents, in particular from 1% by weight to 5% by weight, are particularly suitable as water-insoluble, water-dispersible inorganic builder materials. used.
• detergent grade crystalline sodium aluminosilicates especially zeolite A, P and optionally X. 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 mg to 200 mg CaO per gram.
• Suitable substitutes or partial substitutes for the said aluminosilicate are crystalline alkali silicates which may be present alone or in a mixture with amorphous silicates.
• the alkali metal silicates useful as builders preferably have a molar ratio of alkali metal oxide to SiO 2 below 0.95, in particular from 1: 1.1 to 1:12, and may be present in amorphous or crystalline form.
• Preferred alkali metal silicates are the sodium silicates, in particular the amorphous sodium silicates, with a molar ratio of Na 2 O: SiO 2 of 1: 2 to 1: 2.8.
• the crystalline silicates which may be present alone or in admixture with amorphous silicates, are crystalline layer silicates with the general formula of Na 2 Si x O used 2x + 1 ⁇ y H 2 O in which x, known as the modulus, an integer of 1, 9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4.
• Preferred crystalline phyllosilicates are those in which x in the abovementioned general formula assumes the values 2 or 3.
• both ⁇ - and ⁇ -sodium disilicates Na 2 Si 2 O 5 .yH 2 O
• amorphous alkali silicates practical Anhydrous crystalline alkali silicates of the abovementioned general formula in which x is a number from 1.9 to 2.1 can be used.
• a crystalline sodium layer silicate with a modulus of 2 to 3 is used, as can be prepared from sand and soda. Crystalline sodium silicates with a modulus in the range 1.9 to 3.5 are used in a further preferred embodiment.
• a granular compound of alkali metal silicate and alkali metal carbonate is used, as it is commercially available, for example, under the name Nabion® 15.
• the weight ratio of aluminosilicate to silicate is preferably 1:10 to 10: 1.
• the weight ratio of amorphous alkali metal silicate to crystalline alkali metal silicate is preferably 1: 2 to 2: 1 and especially 1: 1 to 2: 1.
• Builder substances are preferably contained in detergents in amounts of up to 60% by weight, in particular from 5% by weight to 40% by weight.
• the water-soluble builder block contains at least 2 of the components b), c), d) and e) in amounts greater than 0 wt .-%.
• component a) 15% by weight to 25% by weight of alkali carbonate, which may be replaced at least proportionally by alkali metal bicarbonate, and up to 5% by weight, in particular 0.5% by weight, bis 2.5% by weight of citric acid and / or alkali citrate.
• component a) 5 wt .-% to 25 wt .-%, in particular 5 wt .-% to 15 wt .-% citric acid and / or alkali citrate and up to 5 wt .-%, in particular 1 wt .-% to 5 wt .-% alkali carbonate, which may be at least partially replaced by alkali metal bicarbonate included.
• the component a) alkali carbonate and alkali metal bicarbonate preferably in a weight ratio of 10: 1 to 1: 1.
• component b in a preferred embodiment, 1 wt .-% to 5 wt .-% alkali silicate with a modulus in the range of 1.8 to 2.5 are included.
• phosphonic acid and / or alkali metal phosphonate in a preferred embodiment, from 0.05% by weight to 1% by weight of phosphonic acid and / or alkali metal phosphonate is contained.
• Phosphonic acids are also understood as meaning optionally substituted alkylphosphonic acids, which may also have a plurality of phosphonic acid groups (so-called polyphosphonic acids).
• They are preferably selected from the hydroxy and / or aminoalkylphosphonic acids and / or their alkali salts, for example dimethylaminomethane diphosphonic acid, 3-aminopropane-1-hydroxy-1,1-diphosphonic acid, 1-amino-1-phenylmethane diphosphonic acid, 1-hydroxyethane 1,1-diphosphonic acid, amino-tris (methylenephosphonic acid), N, N, N ', N'-ethylenediamine tetrakis (methylenephosphonic acid) and acylated derivatives of phosphorous acid, which can also be used in any mixtures.
• dimethylaminomethane diphosphonic acid 3-aminopropane-1-hydroxy-1,1-diphosphonic acid
• 1-amino-1-phenylmethane diphosphonic acid 1-hydroxyethane 1,1-diphosphonic acid
• amino-tris methylenephosphonic acid
• alkali metal phosphate in particular trisodium polyphosphate, is contained.
• Alkali phosphate is the summary term for the alkali metal (especially sodium and potassium) salts of the various phosphoric acids, in which one can distinguish metaphosphoric acids (HPO 3 ) n and orthophosphoric H 3 PO 4 in addition to high molecular weight representatives.
• the phosphates combine several advantages: they act as alkali carriers, prevent lime deposits on machine parts or lime incrustations in fabrics and also contribute to the cleaning performance.
• Sodium dihydrogen phosphate, NaH 2 PO 4 exists as a dihydrate (density 1.91 gcm -3 , melting point 60 °) and as a monohydrate (density 2.04 gcm -3 ). Both salts are white, very soluble in water powders, which lose the water of crystallization on heating and at 200 ° C in pass the weakly acidic diphosphate (disodium hydrogen diphosphate, Na 2 H 2 P 2 O 7 ), at higher temperature into sodium trimetaphosphate (Na 3 P 3 O 9 ) and Madrell's salt.
• NaH 2 PO 4 is acidic; It arises when phosphoric acid is adjusted to a pH of 4.5 with sodium hydroxide solution and the mash is sprayed.
• Potassium dihydrogen phosphate (potassium phosphate primary or monobasic potassium, potassium biphosphate, KDP), KH 2 PO 4 , is a white salt of density 2.33 gcm -3 , has a melting point of 253 ° (decomposition to form (KPO 3 ) x , potassium polyphosphate) and is slightly soluble in water.
• Disodium hydrogen phosphate (secondary sodium phosphate), Na 2 HPO 4 is a colorless, very slightly water-soluble crystalline salt.
• Disodium hydrogen phosphate is prepared by neutralization of phosphoric acid with soda solution using phenolphthalein as an indicator.
• Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K 2 HPO 4 , is an amorphous, white salt that is readily soluble in water.
• Trisodium phosphate, tertiary sodium phosphate, Na 3 PO 4 are colorless crystals which have a density of 1.62 gcm -3 as dodecahydrate and a melting point of 73-76 ° C (decomposition), as decahydrate (corresponding to 19-20% P 2 O 5 ) have a melting point of 100 ° C and in anhydrous form (corresponding to 39-40% P 2 O 5 ) have a density of 2.536 gcm -3 .
• Trisodium phosphate is readily soluble in water under alkaline reaction and is prepared by evaporating a solution of exactly 1 mole of disodium phosphate and 1 mole of NaOH.
• Tripotassium phosphate (tertiary or tribasic potassium phosphate), K 3 PO 4 , is a white, deliquescent, granular powder of density 2.56 gcm -3 , has a melting point of 1340 ° and is readily soluble in water with an alkaline reaction. It arises, for example, when heating Thomasschlacke with coal and potassium sulfate. Despite the higher price, the more soluble, therefore highly effective, potassium phosphates are often preferred over corresponding sodium compounds.
• Tetrasodium diphosphate (sodium pyrophosphate), Na 4 P 2 O 7 , exists in anhydrous form (density 2.534 gcm -3 , melting point 988 °, also indicated 880 °) and as decahydrate (density 1.815-1.836 gcm -3 , melting point 94 ° with loss of water) , For substances are colorless, in water with alkaline reaction soluble crystals.
• Na 4 P 2 O 7 is formed on heating of disodium phosphate to> 200 ° or by reacting phosphoric acid with soda in a stoichiometric ratio and dewatering the solution by spraying.
• the decahydrate complexes heavy metal salts and hardness agents and therefore reduces the hardness of the water.
• Potassium diphosphate (potassium pyrophosphate), K 4 P 2 O 7 , exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33 gcm -3 , which is soluble in water, the pH being 1% Solution at 25 ° 10.4.
• Condensation of the NaH 2 PO 4 or the KH 2 PO 4 results in higher molecular weight sodium and potassium phosphates, in which one can distinguish cyclic representatives, the sodium or potassium metaphosphates and chain types, the sodium or potassium polyphosphates.
• a variety of names are in use: hot or cold phosphates,
• Pentakaliumtriphosphat, K 5 P 3 O 10 (potassium tripolyphosphate), for example, in the form of a 50 wt .-% solution (> 23% P 2 O 5 , 25% K 2 O) in the trade.
• sodium potassium tripolyphosphates which can also be used in the context of the present invention. These arise, for example, when hydrolyzed sodium trimetaphosphate with KOH: (NaPO 3 ) 3 + 2 KOH ⁇ Na 3 K 2 P 3 O 10 + H 2 O
• sodium tripolyphosphate, potassium tripolyphosphate or mixtures of these two applicable are just like sodium tripolyphosphate, potassium tripolyphosphate or mixtures of these two applicable; It is also possible to use mixtures of sodium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of potassium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of sodium tripolyphosphate and potassium tripolyphosphate and sodium potassium tripolyphosphate.
• the agent contains 1.5% to 5% by weight of polymeric polycarboxylate, in particular selected from the polymerization or copolymerization products of acrylic acid, methacrylic acid and / or maleic acid.
• polymeric polycarboxylate in particular selected from the polymerization or copolymerization products of acrylic acid, methacrylic acid and / or maleic acid.
• homopolymers of acrylic acid particularly preferred are those having an average molecular weight in the range from 5,000 D to 15,000 D (PA standard).
• Suitable enzymes which can be used in the compositions are those from the class of lipases, cutinases, amylases, pullulanases, mannanases, cellulases, hemicellulases, xylanases and peroxidases and mixtures thereof, for example amylases such as Termamyl®, Amylase-LT®, Maxamyl®, Duramyl ® and / or Purafect® OxAm, lipases such as Lipolase®, Lipomax®, Lumafast®, Lipozym® and / or Lipex®, cellulases such as Celluzyme® and / or Carezyme®.
• amylases such as Termamyl®, Amylase-LT®, Maxamyl®, Duramyl ® and / or Purafect® OxAm
• lipases such as Lipolase®, Lipomax®, Lumafast®, Lipozym® and / or Lipex®
• cellulases such
• fungi or bacteria such as Bacillus subtilis, Bacillus licheniformis, Streptomyces Griseus, Humicola lanuginosa, Humicola insolens, Pseudomonas pseudoalcaligenes or Pseudomonas cepacia derived enzymatic agents.
• the optionally used enzymes may be adsorbed to carriers and / or embedded in encapsulants to protect against premature inactivation. They are preferably present in detergents in amounts of up to 10% by weight, in particular from 0.2% by weight to 2% by weight.
• the composition contains 5% by weight to 50% by weight, in particular 8% to 30% by weight, of anionic and / or nonionic surfactant, up to 60% by weight, in particular 5% to 40% by weight.
• organic solvents which can be used in the washing, laundry aftertreatment and cleaning agents, especially 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 preferably present in the compositions in amounts not exceeding 30% by weight, in particular from 6% by weight to 20% by weight.
• Naturally derived polymers which can be used as thickening agents in aqueous liquid agents include agar-agar, carrageenan, tragacanth, gum arabic, alginates, pectins, polyoses, guar flour, locust bean gum, starch, dextrins, gelatin and casein.
• Cellulose derivatives such as carboxymethyl cellulose, hydroxyethyl and propyl cellulose, and polymeric polysaccharide thickeners such as xanthan;
• fully synthetic polymers such as vinyl polymers, polycarboxylic acids, polyethers, polyimines, polyamides and polyurethanes are also suitable as thickeners.
• 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 bases, in particular ammonium or alkali metal hydroxides.
• Such pH regulators are preferably contained in the compositions not more than 20% by weight, in particular from 1.2% by weight to 17% by weight.
• Soil Release polymers often as “soil release” agents or because of their ability to render the treated surface, for example, the fiber, dirt repellent, as “Soil repellents” are, for example, nonionic or cationic cellulose derivatives.
• the particularly polyester-active soil release polymers include copolyesters of dicarboxylic acids, for example adipic acid, phthalic acid or terephthalic acid, diols, for example ethylene glycol or propylene glycol, and polydiols, for example polyethylene glycol or polypropylene glycol.
• Preferred soil release polymers include those compounds which are formally accessible by esterification of two monomeric moieties, wherein the first monomer is a dicarboxylic acid HOOC-Ph-COOH and the second monomer is a diol HO- (CHR 11 -) a OH, also known as polymeric Diol H- (O- (CHR 11 -) a ) b OH may be present.
• Ph is an o-, m- or p-phenylene radical which can carry 1 to 4 substituents selected from alkyl radicals having 1 to 22 C atoms, sulfonic acid groups, carboxyl groups and mixtures thereof
• R 11 denotes hydrogen
• a is a number from 2 to 6
• b is a number from 1 to 300.
• the molar ratio of monomer diol units to polymer diol units is preferably 100: 1 to 1: 100, in particular 10: 1 to 1:10.
• the degree of polymerization b is preferably in the range of 4 to 200, especially 12 to 140.
• the molecular weight or the average molecular weight or the maximum molecular weight distribution of preferred soil release polyester is in the range of 250 to 100,000, especially 500 to 50,000
• the acid underlying the radical Ph is preferably selected from terephthalic acid, isophthalic acid, phthalic acid, trimellitic acid, mellitic acid, the isomers of sulfophthalic acid, sulfoisophthalic acid and sulfoterephthalic acid and mixtures thereof.
• acids having at least two carboxyl groups may be included in the soil release-capable polyester.
• alkylene and alkenylene dicarboxylic acids such as malonic acid, succinic acid, fumaric acid, maleic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid.
• the preferred diols HO- (CHR 11 -) a OH include those in which R 11 is hydrogen and a is a number from 2 to 6, and those in which a is 2 and R 11 is hydrogen and the alkyl radicals 1 to 10, in particular 1 to 3 C-atoms is selected.
• R 11 is hydrogen and a is a number from 2 to 6
• R 11 is hydrogen and the alkyl radicals 1 to 10, in particular 1 to 3 C-atoms is selected.
• those of the formula HO-CH 2 -CHR 11 -OH in which R 11 has the abovementioned meaning are particularly preferred.
• diol components are ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,2-decanediol, 1, 2-dodecanediol and neopentyl glycol.
• Particularly preferred among the polymeric diols is polyethylene glycol having an average molecular weight in the range of 1,000 to 6,000. If desired, these polyesters may also be used be end-capped, with end groups alkyl groups having 1 to 22 carbon atoms and esters of monocarboxylic acids in question.
• the ester groups bonded via end groups can be based on alkyl, alkenyl and aryl monocarboxylic acids having 5 to 32 carbon atoms, in particular 5 to 18 carbon atoms. These include valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, undecenoic acid, lauric acid, lauroleinic acid, tridecanoic acid, myristic acid, myristoleic acid, pentadecanoic acid, palmitic acid, stearic acid, petroselinic acid, petroselaidic acid, oleic acid, linoleic acid, linolaidic acid, linolenic acid, levostearic acid, arachidic acid , Gadoleic acid, arachidonic acid, behenic acid, erucic acid, brassidic acid, clupanodonic acid, lignoceric acid, cerotic acid,
• the hydroxymonocarboxylic acids may in turn be linked to one another via their hydroxyl group and their carboxyl group and thus be present several times in an end group.
• the number of hydroxymonocarboxylic acid units per end group is in the range from 1 to 50, in particular from 1 to 10.
• suitable for use in laundry detergents of textiles color transfer inhibitors include polyvinylpyrrolidones, polyvinylimidazoles, polymeric N-oxides such as poly (vinylpyridine-N-oxide) and copolymers of vinylpyrrolidone with vinylimidazole and optionally other monomers.
• the agents may contain anti-crease agents, since textile fabrics, in particular of rayon, wool, cotton and their mixtures, can tend to wrinkle, because the individual fibers are sensitive to bending, buckling, pressing and squeezing transverse to the fiber direction.
• anti-crease agents since textile fabrics, in particular of rayon, wool, cotton and their mixtures, can tend to wrinkle, because the individual fibers are sensitive to bending, buckling, pressing and squeezing transverse to the fiber direction.
• These include, for example, synthetic products based on fatty acids, fatty acid esters, fatty acid amides, alkylol esters, -alkylolamides or fatty alcohols, which are usually reacted with ethylene oxide, or products based on lecithin or modified phosphoric acid ester.
• Graying inhibitors have the task of keeping suspended from the hard surface and in particular from the textile fiber suspended dirt in the fleet.
• water-soluble Colloids usually organic nature suitable, for example, starch, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
• water-soluble polyamides containing acidic groups are suitable for this purpose.
• starch derivatives can be used, for example aldehyde starches.
• cellulose ethers such as carboxymethylcellulose (Na salt), methylcellulose, hydroxyalkylcellulose and mixed ethers, such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof, for example in amounts of from 0.1 to 5% by weight, based on the compositions.
• the agents may contain optical brighteners, among these in particular derivatives of diaminostilbenedisulfonic acid or their alkali metal salts.
• Suitable salts are, for example, salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulphonic acid or compounds of similar construction which, instead of the morpholino Group carry a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group.
• brighteners of the substituted diphenylstyrene type may be present, for example, the alkali salts of 4,4'-bis (2-sulfostyryl) -diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) -diphenyl, or 4 - (4-chlorostyryl) -4 '- (2-sulfostyryl).
• Mixtures of the aforementioned optical brightener can be used.
• foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of C 18 -C 24 fatty acids.
• Suitable non-surfactant foam inhibitors are, for example, organopolysiloxanes and mixtures thereof with microfine, optionally silanized silica and paraffins, waxes, microcrystalline waxes and mixtures thereof with silanated silicic acid or bis-fatty acid alkylenediamides. It is also advantageous to use mixtures of various foam inhibitors, for example those of silicones, paraffins or waxes.
• the foam inhibitors, in particular silicone- and / or paraffin-containing foam inhibitors are preferably bound to a granular, water-soluble or dispersible carrier substance. In particular, mixtures of paraffins and bistearylethylenediamide are preferred.
• peroxygen compounds come in particular organic peracids or pers acid salts of organic acids such as phthalimidopercaproic acid, perbenzoic acid or salts of diperdodecanedioic acid, hydrogen peroxide and under the washing conditions hydrogen peroxide-releasing inorganic salts such as perborate, percarbonate and / or persilicate, into consideration.
• organic peracids or pers acid salts of organic acids such as phthalimidopercaproic acid, perbenzoic acid or salts of diperdodecanedioic acid, hydrogen peroxide and under the washing conditions hydrogen peroxide-releasing inorganic salts such as perborate, percarbonate and / or persilicate, into consideration.
• Hydrogen peroxide can also be produced by means of an enzymatic system, ie an oxidase and its substrate.
• solid peroxygen compounds ie an oxidase and its substrate.
• solid peroxygen compounds can be used in the form of powders or granules, which can also be enveloped in a manner known in principle.
• peroxygen compounds are present in detergents in amounts of up to 50% by weight, especially from 5% to 30% by weight.
• bleach activators which form peroxycarboxylic acids or peroxoimidic acids under perhydrolysis conditions and / or customary bleach-activating transition metal complexes can be used.
• the optional, especially in amounts of 0.5 wt .-% to 6 wt .-%, present component of the bleach activators include the commonly used N- or O-acyl compounds, for example, polyacylated alkylenediamines, especially tetraacetylethylenediamine, acylated glycolurils, especially tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, urazoles, diketopiperazines, sulfuryl amides and cyanurates, in addition to carboxylic anhydrides, in particular phthalic anhydride, carboxylic acid esters, especially sodium isononanoyl-phenolsulfonat, and acylated sugar derivatives, in particular pentaacetyl
• the bleach activators may have been coated or granulated in known manner with encapsulating substances, granulated tetraacetylethylenediamine having mean particle sizes of from 0.01 mm to 0.8 mm, granulated 1.5% by means of carboxymethylcellulose. Diacetyl-2,4-dioxohexahydro-1,3,5-triazine, and / or formulated in particulate trialkylammonium acetonitrile is particularly preferred.
• Such bleach activators are preferably contained in detergents in amounts of up to 8% by weight, in particular from 2% by weight to 6% by weight, based in each case on the total agent.
• 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.
• Detergents 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 in particular in concentrated liquid form, are present as a portion in a completely or partially water-soluble coating. Portioning makes it easier for the consumer to dose.
• the funds can be packed, for example, in foil bags.
• Pouches made of water-soluble film make it unnecessary for the consumer to tear open the packaging. In this way, a convenient dosing of a single, sized for a wash portion by inserting the bag directly into the washing machine or by throwing the bag into a certain amount of water, for example in a bucket, a bowl or hand basin, possible.
• the film bag surrounding the washing portion dissolves without residue when it reaches a certain temperature.
• thermoforming process thermoforming process
• the water-soluble envelopes need not necessarily consist of a film material, but can also represent dimensionally stable containers that can be obtained for example by means of an injection molding process.
• a seal takes place.
• the filling material is injected into the forming capsule, wherein the injection pressure of the filling liquid presses the polymer bands in the Kugelschschalenkavticianen.
• a process for the preparation of water-soluble capsules in which first the filling and then the sealing takes place, is based on the so-called Bottle-Pack® process. In this case, a tubular preform is guided into a two-part cavity. The cavity is closed, with the lower tube section is sealed, then the tube is inflated to form the capsule shape in the cavity, filled and finally sealed.
• the shell material used for the preparation of the water-soluble portion is preferably a water-soluble polymeric thermoplastic, more preferably selected from the group (optionally partially acetalized) polyvinyl alcohol, polyvinyl alcohol copolymers, polyvinylpyrrolidone, polyethylene oxide, gelatin, cellulose and derivatives thereof, starch and derivatives thereof, blends and composites, inorganic salts and mixtures of said materials, preferably hydroxypropylmethylcellulose and / or polyvinyl alcohol blends.
• Polyvinyl alcohols are commercially available, for example under the trademark Mowiol® (Clariant).
• Polyvinyl alcohols which are particularly suitable for the purposes of the present invention are, for example, Mowiol® 3-83, Mowiol® 4-88, Mowiol® 5-88, Mowiol® 8-88 and Clariant L648.
• the water-soluble thermoplastic used to prepare the portion may additionally optionally comprise polymers selected from the group comprising acrylic acid-containing polymers, polyacrylamides, oxazoline polymers, polystyrene sulfonates, polyurethanes, polyesters, polyethers and / or mixtures of the above polymers.
• the water-soluble thermoplastic used comprises a polyvinyl alcohol whose degree of hydrolysis is 70 mol% to 100 mol%, preferably 80 mol% to 90 mol%, more preferably 81 mol% to 89 mol% and especially 82 mol % to 88 mol%. It is further preferred that the water-soluble thermoplastic used comprises a polyvinyl alcohol whose molecular weight is in the range from 10,000 g / mol to 100,000 g / mol, preferably from 11,000 g / mol to 90,000 g / mol, particularly preferably from 12,000 g / mol to 80 000 g / mol and in particular from 13 000 g / mol to 70 000 g / mol.
• thermoplastics are used in amounts of at least 50% by weight, preferably of at least 70% by weight, more preferably of at least 80% by weight and in particular of at least 90% by weight, based in each case on the weight the water-soluble polymeric thermoplastic.
• Standardized flat fabric pieces of 30 cm by 30 cm of polyamide / micropolyamide were washed at 30 ° C with a commercial sports detergent, the washing liquor nothing or 0.1 wt .-% or 0.5 wt .-% - in each case based on the Detergent - on a polymer essential to the invention, prepared according to Example 1 of the European patent application EP 3 196 283 , added.

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• 2017
  • 2017-08-30 EP EP17188534.6A patent/EP3450531A1/fr not_active Withdrawn

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