EP1915438B1 - Colour protection washing product - Google Patents

Colour protection washing product Download PDF

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Publication number
EP1915438B1
EP1915438B1 EP06776638A EP06776638A EP1915438B1 EP 1915438 B1 EP1915438 B1 EP 1915438B1 EP 06776638 A EP06776638 A EP 06776638A EP 06776638 A EP06776638 A EP 06776638A EP 1915438 B1 EP1915438 B1 EP 1915438B1
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EP
European Patent Office
Prior art keywords
hal
triazine
equivalents
general formula
triazinyl
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EP06776638A
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German (de)
French (fr)
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EP1915438A1 (en
Inventor
Josef Penninger
Birgit GLÜSEN
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Priority to PL06776638T priority Critical patent/PL1915438T3/en
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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
    • C11D3/34—Organic compounds containing sulfur
    • C11D3/349—Organic compounds containing sulfur additionally containing nitrogen atoms, e.g. nitro, nitroso, amino, imino, nitrilo, nitrile groups containing compounds or their derivatives or thio urea
    • 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
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0021—Dye-stain or dye-transfer inhibiting compositions

Definitions

  • the present invention relates to the use of sulfonated triazine derivatives as dye transfer inhibiting agents in the washing of textiles and detergents containing such compounds.
  • detergents In addition to the ingredients indispensable for the washing process, such as surfactants and builders, detergents generally contain further constituents, which can be summarized by the term washing aids and which comprise such different active ingredient groups as foam regulators, graying inhibitors, bleaching agents, bleach activators and enzymes.
  • auxiliaries also include substances which are intended to prevent dyed textiles from causing a changed color impression after washing. This color impression change washed, i. cleaner, textiles can be based on the one hand on the fact that dye components are removed by the washing process from the textile ("fading"), on the other hand may be deposited by differently colored textiles dyes on the textile ("discoloration").
  • the discoloration aspect may also play a role in undyed laundry items when washed together with colored laundry items.
  • detergents In order to avoid these undesirable side effects of removing dirt from textiles by treatment with usually surfactant-containing aqueous systems, detergents, especially when they are provided as so-called color or colored laundry detergents for colored textiles, contain active ingredients which prevent the detachment of dyes from the textile or At least the deposition of detached, located in the wash liquor to avoid dyes on textiles.
  • Many of the commonly used polymers have such a high affinity for dyes that they draw them more from the dyed fiber, resulting in increased color losses.
  • Triazine derivatives of general formula I are obtainable by reacting 2,4,6-trihalo-1,3,5-triazines with 1 or 2 equivalents of aminoaryl compound, wherein the aryl group of the aminoaryl compound is a 1 to 3-fold sulfonate-substituted benzene or Napthalene unit is.
  • Suitable aminoaryl compounds are, for example, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 2-amino-1,3-benzenedisulfonic acid, 4-amino-1,3-benzenedisulfonic acid, 2-amino-1, 3,5-benzenetrisulfonic acid, 2-amino-1-naphthalenesulfonic acid, 3-amino-1-naphthalenesulfonic acid, 4-amino-1-naphthalenesulfonic acid, 2-amino-1,5-naphthalenedisulfonic acid, 7-amino-1,6-naphthalenedisulfonic acid, 2-amino-3,6,8-naphthalenetrisulfonic acid and 7-amino-1,3,6-naphthalenetrisulfonic acid, wherein their sulfonic acid groups are in salt form. It is also possible to use mixtures
  • Omega.-diaminoalkanes are particularly preferred, but if appropriate, oligo- or polyethyleneimines or -propylenimines may also be suitable; preferred oligo- or polyethyleneimines are those of the formula NH 2 -CH 2 CH 2 - (NH-CH 2 CH 2 -) n NH 2 , in which n is a number from 1 to 9, in particular 2 to 5, wherein also Mixtures of oligo- or polyethyleneimines of different degrees of oligo- or polymerization can be used so that n can take as an average value and non-integer values.
  • the diaminostilbene or diaminobiphenyl also additionally has at least 1, in particular 2 or sulfonic acid salt substituents, for example 4,4'-diamino-2,2'-biphenyldisulfonic acid disodium salt or 4,4'-diamino-2,2 ' -stilbendisulfonklare disodium salt.
  • substituents for example 4,4'-diamino-2,2'-biphenyldisulfonic acid disodium salt or 4,4'-diamino-2,2 ' -stilbendisulfonklad salt.
  • these are trans-configured stilbenes, but optionally also the cis-configured stilbenes and mixtures thereof can be used. It is also possible to use mixtures of diaminostilbenes with diamino-biphenylene.
  • An inventive composition preferably contains 0.05 wt .-% to 2 wt .-%, in particular 0.2 wt .-% to 1 wt .-%, dye transfer inhibiting compound of general formula II and / or III and optionally additionally triazine derivative of the general Formula I.
  • the "and / or" formulation is intended to make it clear that the joint use of compounds which correspond in each case to one of the abovementioned formulas is also possible.
  • the compounds of the general formula I, II or III contribute to both the above-mentioned aspects of color constancy, that is to say they reduce both discoloration and fading, although the effect of preventing staining, especially when washing white textiles, is most pronounced is.
  • Another object of the invention is therefore the use of a corresponding compound to avoid the change in the color impression of textiles in their Laundry in particular surfactant-containing aqueous solutions. By changing the color impression is by no means the difference between polluted and clean textile, but the difference between each clean textile before and after the washing process.
  • triazine derivatives of the general formulas II or III in which, however, in each case X represents a carbon chain interrupted by NH groups, to avoid the transfer of textile dyes of dyed textiles to undyed or differently colored textiles in their joint washing in in particular surfactant-containing aqueous solutions, or to avoid the change in the color impression of dyed textiles in their washing in particular surfactant-containing aqueous solutions, wherein the triazine derivative of general formula II is obtainable by reacting 2 equivalents of such compounds of formula I, the nor 1 or 2 halogens on the triazine radical, with 1 equivalent of oligo- or polyethyleneimine of the formula NH 2 -CH 2 CH 2 - (NH-CH 2 CH 2 -) n NH 2 , in which n is a number from 1 to 9, in particular 2 to 5, and wherein the triazine derivative of general formula III is obtainable by reaction ng of diaminostilbenes or diaminobiphenyl
  • an agent according to the invention may comprise a known dye transfer inhibitor, then preferably in amounts of from 0.1% by weight to 2% by weight, in particular 0.2% by weight 1 wt .-%, which in a preferred embodiment of the invention is a polymer of vinylpyrrolidone, vinylimidazole, vinylpyridine-N-oxide or a copolymer thereof.
  • Polyvinylpyrrolidone preferably has an average molecular weight in the range from 10 000 to 60 000, in particular in the range from 25 000 to 50 000, for use in compositions according to the invention.
  • those of vinylpyrrolidone and vinylimidazole in a molar ratio of 5: 1 to 1: 1 having an average molecular weight in the range of 5,000 to 50,000, especially 10,000 to 20,000 are preferred.
  • the detergents according to the invention which may be in the form of homogeneous solutions or suspensions, in particular in powdered solids, in densified particle form, can in principle contain, in addition to the active ingredient used according to the invention, all known ingredients customary in such agents.
  • the agents according to the invention may in particular be builders, surface-active surfactants, bleaches based on organic and / or inorganic peroxygen compounds, bleach activators, water-miscible organic solvents, enzymes, sequestering agents, electrolytes, pH regulators and other auxiliaries, such as optical brighteners, grayness inhibitors, foam regulators and colorants Contain fragrances.
  • compositions according to the invention may comprise one or more surfactants, in particular anionic surfactants, nonionic surfactants and mixtures thereof, but also cationic, zwitterionic and amphoteric surfactants.
  • 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. Furthermore, corresponding 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, as well as of alkylphenols having 5 to 12 C atoms in the alkyl radical.
  • 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 may contain linear and methyl-branched radicals in the mixture, as they are usually present in Oxoalkoholresten.
  • EO ethylene oxide
  • alcohol radical can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as they are usually present in Oxoalkoholresten.
  • the preferred ethoxylated alcohols include, for example, C 12 -C 14 -alcohols with 3 EO or 4 EO, C 9 -C 11 -alcohols with 7 EO, C 13 -C 15 -alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12 -C 18 -alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C 12 -C 14 -alcohol with 3 EO and C 12 -C 18 -alcohol with 7 EO.
  • the degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples include (tallow) fatty alcohols with 14 EO, 16 EO, 20 EO, 25 EO, 30 EO or 40 EO.
  • agents for use in mechanical processes usually extremely low-foam compounds are used. These include preferably C 12 -C 18 -alkylpolyethylenglykol-polypropylene glycol ethers with in each case at to 8 mol ethylene oxide and propylene oxide units in the molecule.
  • low-foam nonionic surfactants such as, for example, C 12 -C 18 -alkylpolyethylene glycol-polybutylene glycol ethers having up to 8 mol of ethylene oxide and butylene oxide units in the molecule and also end-capped alkylpolyalkylene glycol mixed ethers.
  • hydroxyl-containing alkoxylated alcohols as described in the European patent application EP 0 300 305 are described, so-called Hydroxymischether.
  • the nonionic surfactants also include alkyl glycosides of the general formula RO (G) x are used, in the R a primary straight-chain or methyl-branched, in particular in the 2-position methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is a glycose unit having 5 or 6 carbon atoms, preferably glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is an arbitrary number - which, as a variable to be determined analytically, may also assume fractional values - between 1 and 10; preferably x is 1.2 to 1.4.
  • polyhydroxy fatty acid amides of the formula (IV) in which R 1 CO is an aliphatic acyl radical having 6 to 22 carbon atoms, R 2 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:
  • the polyhydroxy fatty acid amides are preferably derived from reducing sugars having 5 or 6 carbon atoms, in particular from glucose.
  • the group of polyhydroxy fatty acid amides also includes compounds of the formula (V), in the R 3 is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R 4 is a linear, branched or cyclic alkylene radical or an arylene radical having 2 to 8 carbon atoms and R 5 is a linear, branched or cyclic alkyl radical or a Aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, wherein C 1 -C 4 alkyl or phenyl radicals are preferred, and [Z] is a linear polyhydroxyalkyl radical whose alkyl chain is substituted with at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this group.
  • [Z] is also here preferably by reductive amination of a sugar such as glucose, fructose, maltose, lactose, galactose, Mannose or xylose received.
  • a sugar such as glucose, fructose, maltose, lactose, galactose, Mannose or xylose received.
  • the N-alkoxy- or N-aryloxy-substituted compounds can then be used, for example, according to the teaching of the international patent application WO 95/07331 be transferred by reaction with fatty acid methyl esters in the presence of an alkoxide as a catalyst in the desired polyhydroxy fatty acid amides.
  • nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants, in particular together with alkoxylated fatty alcohols and / or alkyl glycosides, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably from 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl ester, as described for example in the Japanese patent application JP 58/217598 are described or preferably according to the in the international patent application WO 90/13533 be prepared described methods.
  • 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 may also be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.
  • Other suitable surfactants are so-called gemini surfactants. These are generally understood as meaning those compounds which have two hydrophilic groups per molecule. These groups are usually separated by a so-called "spacer".
  • This spacer is usually a carbon stalk chain that should be long enough for the hydrophilic groups to be spaced sufficiently apart for them to act independently of each other.
  • Such surfactants are generally characterized by an unusually low critical micelle concentration and the ability to greatly reduce the surface tension of the water.
  • gemini surfactants not only such "dimer”, but also corresponding to "trimeric” surfactants understood.
  • Suitable gemini surfactants are, for example, sulfated hydroxy mixed ethers according to the German patent application DE 43 21 022 or dimer alcohol bis and trimer alcohol tris sulfates and ether sulfates according to the German patent application DE 195 03 061 , End-capped dimeric and trimeric mixed ethers according to the German patent application DE 195 13 391 They are characterized by their bi- and multi-functionality. So own the mentioned End disabilityver fieen surfactants good wetting properties and are low in foam, so that they are particularly suitable for use in machine washing or cleaning processes.
  • Suitable anionic surfactants are in particular soaps and those which contain sulfate or sulfonate groups.
  • surfactants of the sulfonate type are preferably C 9 -C 13 alkylbenzenesulfonates, Olefinsulfonate, that is, mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as they are, for example, from C 12 -C 18 monoolefins with terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation obtained.
  • alkanesulfonates which are obtained from C 12 -C 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 obtained by ⁇ -sulfonation of the methyl esters of fatty acids of plant and / or animal origin with 8 to 20 C -Atomen in the fatty acid molecule and subsequent neutralization to water-soluble mono-salts are prepared, into consideration.
  • ⁇ -sulfonated esters of hydrogenated coconut, palm, palm kernel or tallow fatty acids although sulfonated products of unsaturated fatty acids, for example oleic acid, in small amounts, preferably in amounts not above about 2 to 3 wt. %, can be present.
  • ⁇ -sulfofatty acid alkyl esters are preferred which have an alkyl chain with not more than 4 C atoms in the ester group, for example, methyl ester, ethyl ester, propyl ester and butyl ester.
  • the methyl esters of ⁇ -sulfo fatty acids (MES), but also their saponified disalts are used.
  • Suitable anionic surfactants are sulfated fatty acid glycerol esters, which are mono-, di- and triesters and mixtures thereof, as in the preparation by esterification by a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol to be obtained.
  • alk (en) ylsulfate the alkali and in particular the sodium salts of sulfuric monoesters of C 12 -C 18 fatty alcohols for example, from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or C 10 -C 20 -oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred.
  • alk (en) ylsulfates of said chain length which contain a synthetic, petrochemical-based straight-chain alkyl radical, 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 15 -alkyl sulfates and C 14 -C 15 -alkyl sulfates are particularly preferred.
  • 2,3-alkyl sulfates which, for example, according to the US patents US 3,234,258 or US 5 075 041 which can be obtained as commercial products of the Shell Oil Company under the name DAN® are suitable anionic surfactants.
  • sulfuric acid monoesters of straight-chain or branched C 7 -C 21 -alcohols ethoxylated with from 1 to 6 mol of ethylene oxide such as 2-methyl-branched C 9 -C 11 -alcohols having on average 3.5 mol of ethylene oxide (EO) or C 12 - C 18 -fatty alcohols with 1 to 4 EO.
  • EO ethylene oxide
  • the preferred anionic surfactants also include the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters, and the 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 to C 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 alk (en) yl chain or salts thereof.
  • Suitable further anionic surfactants are fatty acid derivatives of amino acids, for example N-methyltaurine (Tauride) and / or N-methylglycine (sarcosides).
  • sarcosides or the sarcosinates and here especially sarcosinates of higher and optionally monounsaturated or polyunsaturated fatty acids such as oleyl sarcosinate.
  • anionic surfactants are particularly soaps into consideration.
  • Particularly suitable are saturated fatty acid soaps, such as the salts of Laürinklare, 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. Together with these soaps or as a substitute for soaps, it is also possible to use the known alkenylsuccinic acid salts.
  • 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.
  • Surfactants are present in detergents according to the invention in proportions of preferably from 5% by weight to 50% by weight, in particular from 8% by weight to 30% by weight.
  • An agent according to the invention 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 also polymeric (poly) -carboxylic acids, in particular the polycarboxylates of the European patent specification obtainable by oxidation of polysaccharides or dextrins EP 0 625 992 or the international patent application WO 92/18542 or the European patent specification EP
  • the molecular weight of the homopolymers of unsaturated carboxylic acids is generally between 3,000 and 200,000, that of the copolymers between 2,000 and 200,000, preferably 30,000 to 120,000, in each case based on the free acid.
  • a particularly preferred acrylic acid-maleic acid copolymer has a molecular weight of from 30,000 to 100,000.
  • Commercially available products are, for example, Sokalan® CP 5, CP 10 and PA 30 from BASF.
  • Suitable, albeit less preferred, compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinylmethyl ethers, vinyl esters, ethylene, propylene and styrene, in which the proportion of acid is at least 50 wt .-%.
  • 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 can be prepared in particular by methods described in the German patent DE 42 21 381 and the German patent application DE 43 00 772 are generally described, and generally have a molecular weight between 1,000 and 200,000. Further preferred copolymers are those described in the German patent applications DE 43 03 320 and DE 44 17 734 be described and as monomers preferably 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 paste-form or liquid, in particular water-containing, agents according to the invention.
  • Suitable water-soluble inorganic builder materials are, in particular, alkali metal silicates, alkali metal carbonates and alkali metal phosphates, which may be in the form of their alkaline, neutral or acidic sodium or potassium salts.
  • alkali metal silicates alkali metal carbonates and alkali metal phosphates, which may be in the form of their alkaline, neutral or acidic sodium or potassium salts.
  • examples of these are trisodium phosphate, tetrasodium diphosphate, disodium dihydrogen diphosphate, pentasodium triphosphate, so-called sodium hexametaphosphate, oligomeric trisodium phosphate with degrees of oligomerization of from 5 to 1000, in particular from 5 to 50, 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.
  • preferred are the detergent grade crystalline sodium aluminosilicates, particularly zeolite A, P and optionally X, alone or in mixtures, for example in the form of a cocrystal of zeolites A and X (Vegoborid® AX, a commercial product of Condea Augusta SpA) , 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 usually in the range of 100 to 200 mg CaO per gram.
  • Suitable substitutes or partial substitutes for the said aluminosilicate are crystalline alkali silicates which may be present alone or in a mixture with amorphous silicates.
  • the alkali metal silicates useful as builders in the compositions according to the invention 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.
  • crystalline silicates which may be present alone or in admixture with amorphous silicates, are crystalline layer silicates with the general formula Na 2 Si x O y are used 2x + 1 H 2 O, in which x, the so-called module, a number from 1.9 to 22, in particular 1.9 to 4 and y is a number from 0 to 33 and preferred values for x are 2, 3 or 4. Crystalline layered silicates which fall under this general formula are described, for example, in the European patent application EP 0 164 514 described.
  • Preferred crystalline phyllosilicates are those in which x in the abovementioned general formula assumes the values 2 or 3.
  • both .beta.- and ⁇ -sodium (Na 2 Si 2 O 5 y H 2 O) are preferred, with beta-sodium disilicate being obtainable, for example, by the method described in the international patent application WO 91/08171 is described.
  • ⁇ -Sodium silicates with a modulus between 1.9 and 3.2 can according to Japanese Patent Applications JP 04/238 809 or JP 04/260 610 getting produced.
  • Crystalline sodium silicates with a modulus ranging from 1.9 to 3.5, as prepared by the methods of European patents EP 0 164 552 and or EP 0 294 753 are available are used in a further preferred embodiment of the invention means.
  • Crystalline layer-form silicates of formula (I) given above are sold by Clariant GmbH under the trade name Na-SKS, eg Na-SKS-1 (Na 2 Si 22 O 45 .H 2 O, Kenyaite), Na-SKS-2 (Na 2 Si 14 O 29 ⁇ H 2 O, magadiite), Na-SKS-3 (Na 2 Si 8 O 17 -xH 2 O) or Na-SKS-4 (Na 2 Si 4 O 9 ⁇ H 2 O, makatite) , Of these, especially Na-SKS-5 ( ⁇ -Na 2 Si 2 O 5 ), Na-SKS-7 ( ⁇ -Na 2 Si 2 O 5 , Natrosilit), Na-SKS-9 (NaHSi 2 O 5 3H 2 O), Na
  • compositions according to the invention a granular compound of crystalline phyllosilicate and citrate, of crystalline phyllosilicate and of the abovementioned (co) polymeric polycarboxylic acid, as described, for example, in the German patent application DE 198 19 187 or from alkali metal silicate and alkali metal carbonate, as described for example in the international patent application WO 95/22592 or as it is commercially available, for example, under the name Nabion® 15.
  • Builder substances are preferably present in the compositions according to the invention in amounts of up to 75% by weight, in particular 5% by weight to 50.
  • suitable peroxygen compounds are 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 donating inorganic salts, which include perborate, percarbonate, persilicate and / or persulfate Caroat belong 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 donating inorganic salts, which include perborate, percarbonate, persilicate and / or persulfate Caroat belong into consideration.
  • 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.
  • an agent according to the invention contains peroxygen compounds, they are present in amounts of preferably up to 50% by weight, in particular from 5% by weight to 30% by weight.
  • bleach stabilizers such as phosphonates, borates or metaborates and metasilicates and magnesium salts such as magnesium sulfate may be useful.
  • bleach activators it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid.
  • Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups.
  • polyacylated alkylenediamines in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate, 2,5-diacetoxy- 2,5-dihydrofuran and from the German patent applications DE
  • Such bleach activators can, in particular in the presence of the abovementioned hydrogen peroxide-producing bleach, in the usual amount range, preferably in amounts of from 0.5 wt .-% to 10 wt .-%, in particular 1 wt .-% to 8 wt .-%, based on However, total agent, be included, missing when using percarboxylic acid as the sole bleach, preferably completely.
  • Suitable enzymes which can be used in the compositions are those from the class of amylases, proteases, lipases, cutinases, pullulanases, hemicellulases, cellulases, oxidases, laccases and peroxidases and mixtures thereof. Particularly suitable are from fungi or bacteria, such as Bacillus subtilis, Bacillus licheniformis, Bacillus lentus, Streptomyces griseus, Humicola lanuginosa, Humicola insolens, Pseudomonas pseudoalcaligenes, Pseudomonas cepacia or Coprinus cinereus derived enzymatic agents.
  • the enzymes can be as described, for example, in the European patent EP 0 564 476 or in the international patent application WO 94/23005 be adsorbed to carriers and / or embedded in encapsulating substances to protect against premature inactivation. They are preferably present in the detergents or cleaners according to the invention in amounts of up to 5% by weight, in particular from 0.2% by weight to 4% by weight. If the agent of the invention contains protease, it preferably has a proteolytic activity in the range of about 100 PE / g to about 10 000 PE / g, in particular 300 PE / g to 8000 PE / g.
  • organic solvents which can be used in addition to water include alcohols having 1 to 4 C atoms, in particular methanol, ethanol, isopropanol and tert-butanol, diols having 2 to 4 C -Atomen, in particular ethylene glycol and propylene glycol, and mixtures thereof and derived from the classes of compounds mentioned ether.
  • Such water-miscible solvents are preferably present in the compositions according to the invention in amounts of not more than 30% by weight, in particular from 6% by weight to 20% by weight.
  • the compositions according to the invention can contain system- and environmentally compatible 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 present in the compositions according to the invention in amounts of preferably not more than 20% by weight, in particular from 1.2% by weight to 17% by weight.
  • Graying inhibitors have the task of keeping suspended from the textile fiber dirt suspended in the fleet.
  • Water-soluble colloids of mostly organic nature are suitable for this purpose, for example starch, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or of 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 (sodium salt), methylcellulose, Hydroxyalkylcellulose and mixed ethers, such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof, for example in amounts of 0.1 to 5 wt .-%, based on the means used.
  • Detergents according to the invention may contain, for example, derivatives of diaminostilbenedisulfonic acid or their alkali metal salts as optical brighteners, although they are preferably free of optical brighteners for use as color detergents.
  • 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.
  • compositions according to the invention presents no difficulties and can be carried out in a known manner, for example by spray-drying or granulation, enzymes and possibly other thermally sensitive ingredients such as, for example, bleaching agents optionally being added separately later.
  • Agent with increased bulk density in particular in the range of 650 g / l to 950 g / l, is one from the European patent EP 0 486 592 known method comprising an extrusion step is preferred.
  • Another preferred preparation by means of a granulation process is in the European patent specification EP 0 642 576 described.
  • compositions according to the invention in tablet form, which may be monophasic or multiphase, monochromatic or multicolor and in particular consist of one or more layers, in particular two layers
  • the procedure is preferably such that all constituents - if appropriate one per layer - in one Mixer mixed together and the mixture by means of conventional tablet presses, such as eccentric or rotary presses, pressed with compressive forces in the range of about 50 to 100 kN, preferably at 60 to 70 kN.
  • a tablet produced in this way has a weight of 10 g to 50 g, in particular 15 g up to 40 g.
  • the spatial form of the tablets is arbitrary and can be round, oval or angular, with intermediate forms are also possible. Corners and edges are advantageously rounded. Round tablets preferably have a diameter of 30 mm to 40 mm.
  • the size of rectangular or cuboid-shaped tablets, which are introduced predominantly via the metering device, for example the dishwasher, is dependent on the geometry and the volume of this metering device.
  • Exemplary preferred embodiments have a base area of (20 to 30 mm) x (34 to 40 mm), in particular of 26x36 mm or 24x38 mm.
  • Liquid or pasty compositions according to the invention in the form of customary solvent-containing solutions are generally prepared by simply mixing the ingredients, which can be added in bulk or as a solution in an automatic mixer.
  • Cyanuric chloride (8.26 g, 0.044 mol) suspended in a mixture of ice and acetone (50 ml) was added at 0 ° C to a stirred aqueous solution of 4-aminonaphthalene-1-sulfonic acid (10.1 g, 0.044 mol ). The mixture was stirred at pH 4.5 to 5 (adjusted with sodium carbonate) and 0 to 5 ° C for 5 hours, then heated to 20 ° C within 1 hour. Seventy-five percent of ethylenediamine (1.78 g, 0.022 mol) was added and the mixture was stirred for 16 hours at 30 ° C and pH 8.5 (adjusted by NaOH). Phosphate buffer mixture (pH 6.5) and then acetone (1.5 L) were added. The precipitated colorless solid was separated (yield 10.9 g, 53.8% purity).
  • Cyanuric chloride (3.24 g, 0.018 mol) suspended in a mixture of ice and acetone (50 ml) was added at 0 ° C to a stirred aqueous solution of 2-aminonaphthalene-3,6,8-trisulfonic acid (66.5 percent, 10 g, 0.017 mol). The mixture was stirred at pH 5 to 5.5 (adjusted with sodium carbonate) and 0 to 5 ° C for 5 hours, then heated to 20 ° C within 1 hour. Seventy-five percent of ethylenediamine (0.70 g, 0.009 mol) was added and the mixture was stirred for 18 hours at 30 ° C and pH 8 to 8.5 (adjusted by NaOH). Phosphate buffer mixture (pH 6.5) and then acetone were added. The precipitated colorless solid was separated (yield 4.14 g, 51% purity).

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Abstract

Washing products comprising a dye transfer inhibitor selected from triazine derivatives of the general formulae T(NH—Ar(SO3Na)a)bHalc (I), X(NH-T(NH—Ar(SO3Na)a)eHalf)2 (II), X(NH-T(NH—Ar(SO3Na)d—NH-T(NH—Ar(SO3Na)a)Hal)Hal)7 (III) and combinations thereof, wherein T represents a 1,3,5-triazinyl; each Ar independently represents a naphthalene or benzene; X represents a divalent hydrocarbyl selected from linear or branched C1-20 hydrocarbon groups optionally including one or more —N(H)— carbon chain interruptions, stilbene and biphenyl groups which may optionally be mono- or poly-SO3Na-substituted; each Hal independently represents a halogen selected chlorine, bromine, and iodine; each of a and d independently represents 1, 2 or 3; b and c each represent 1 or 2 such that b+c=3; e represents 1 or 2 and f represents 0 or 1 such that e+f=2; and wherein the triazinyl substituents are located at the 2, 4 and 6 positions of the 1,3,5-triazinyl.

Description

Die vorliegende Erfindung betrifft die Verwendung sulfonierter Triazin-Derivate als farbübertragungsinhibierende Wirkstoffe beim Waschen von Textilien und Waschmittel, welche derartige Verbindungen enthalten.The present invention relates to the use of sulfonated triazine derivatives as dye transfer inhibiting agents in the washing of textiles and detergents containing such compounds.

Waschmittel enthalten neben den für den Waschprozess unverzichtbaren Inhaltsstoffen wie Tensiden und Buildermaterialien in der Regel weitere Bestandteile, die man unter dem Begriff Waschhilfsstoffe zusammenfassen kann und die so unterschiedliche Wirkstoffgruppen wie Schaumregulatoren, Vergrauungsinhibitoren, Bleichmittel, Bleichaktivatoren und Enzyme umfassen. Zu derartigen Hilfsstoffen gehören auch Substanzen, welche verhindern sollen, daß gefärbte Textilien nach der Wäsche einen veränderten Farbeindruck hervorrufen. Diese Farbeindrucksveränderung gewaschener, d.h. sauberer, Textilien kann zum einen darauf beruhen, daß Farbstoffanteile durch den Waschprozeß vom Textil entfernt werden ("Verblassen"), zum anderen können sich von andersfarbigen Textilien abgelöste Farbstoffe auf dem Textil niederschlagen ("Verfärben"). Der Verfärbungsaspekt kann auch bei ungefärbten Wäschesstücken eine Rolle spielen, wenn diese zusammen mit farbigen Wäschestücken gewaschen werden. Um diese unerwünschten Nebeneffekte des Entfernens von Schmutz von Textilien durch Behandeln mit üblicherweise tensidhaltigen wäßrigen Systemen zu vermeiden, enthalten Waschmittel, insbesondere wenn sie als sogenannte Color- oder Buntwaschmittel zum Waschen farbiger Textilien vorgesehen sind, Wirkstoffe, die das Ablösen von Farbstoffen vom Textil verhindern oder zumindest das Ablagern von abgelösten, in der Waschflotte befindlichen Farbstoffen auf Textilien vermeiden sollen. Viele der üblicherweise zum Einsatz kommenden Polymere haben eine derart hohe Affinität zu Farbstoffen, daß sie diese verstärkt von der gefärbten Faser ziehen, so daß es zu verstärkten Farbverlusten kommt.In addition to the ingredients indispensable for the washing process, such as surfactants and builders, detergents generally contain further constituents, which can be summarized by the term washing aids and which comprise such different active ingredient groups as foam regulators, graying inhibitors, bleaching agents, bleach activators and enzymes. Such auxiliaries also include substances which are intended to prevent dyed textiles from causing a changed color impression after washing. This color impression change washed, i. cleaner, textiles can be based on the one hand on the fact that dye components are removed by the washing process from the textile ("fading"), on the other hand may be deposited by differently colored textiles dyes on the textile ("discoloration"). The discoloration aspect may also play a role in undyed laundry items when washed together with colored laundry items. In order to avoid these undesirable side effects of removing dirt from textiles by treatment with usually surfactant-containing aqueous systems, detergents, especially when they are provided as so-called color or colored laundry detergents for colored textiles, contain active ingredients which prevent the detachment of dyes from the textile or At least the deposition of detached, located in the wash liquor to avoid dyes on textiles. Many of the commonly used polymers have such a high affinity for dyes that they draw them more from the dyed fiber, resulting in increased color losses.

Aus US 3 947 374 sind Waschmittel, enthaltend Chlor-di-(sulfonylphenylamino)-triazin und Perborat, bekannt. Diese werden zum Waschen weißer Textilien eingesetzt.Out US 3,947,374 detergents containing chloro-di- (sulfonylphenylamino) -triazine and perborate are known. These are used for washing white textiles.

Überraschenderweise wurde nun gefunden, daß bestimmte sulfonierte Triazin-Derivate zu unerwartetet hohen Farbübertragungsinhibierungen führen, wenn man sie in Waschmitteln einsetzt. Besonders ausgeprägt ist die Verhinderung des Anfärbens von weißen oder auch andersfarbigen Textilien durch aus Textilien herausgewaschene Farbstoffe. Denkbar ist, daß die unten noch näher definierten Triazin-Derivate beim Waschen auf die Textilien aufziehen und - möglicherweise durch ihren Sulfonsäuregruppen-Anteil - abstoßend auf in der Flotte befindliche Farbstoffmoleküle wirken.Surprisingly, it has now been found that certain sulfonated triazine derivatives lead to unexpectedly high color transfer inhibition when used in detergents. Particularly pronounced is the prevention of dyeing of white or other colored fabrics by washed out of textiles dyes. It is conceivable that the triazine derivatives, which are defined in more detail below, are applied to the textiles during washing and, possibly due to their sulphonic acid group content, have a repellent effect on dye molecules present in the liquor.

Gegenstand der Erfindung ist daher ein Verfahren zum Waschen von gefärbten Textilien in tensidhaltigen wäßrigen Lösungen, wobei man eine tensidhaltige wäßrige Lösung einsetzt, die ein Triazinderivat der allgemeinen Formeln I, II oder III

        T(NH-Ar(SO3Na)a)bHalc     (I)

        X(NH-T(NH-Ar(SO3Na)a)eHalf)2     (II)

        X(NH-T(NH-Ar(SO3Na)d-NH-T(NH-Ar(SO3Na)a)Hal)Hal)2     (III)

in denen

  • T für einen 1,3,5-Triazinylrest,
  • Ar für eine Naphtalin- oder Benzolgruppierung,
  • X für eine gegebenenfalls durch NH-Gruppen unterbrochene lineare oder verzweigte Kohlenstoffkette mit 1 bis 20, insbesondere 2 bis 12 C-Atomen oder eine gegebenenfalls ein- oder mehrfach -SO3Na-substituierte Stilben- oder Biphenyl-Gruppierung,
  • Hal für Chlor, Brom oder Jod,
  • a und d unabhängig voneinander für 1, 2 oder 3,
  • b für 1 und c für 2 oder b für 2 und c für 1 stehen,
  • e für 1 und f für 1 oder e für 2 und f für 0 stehen,
  • und die -NH- wie auch die -Hal- Substituenten sich in den Positionen 2, 4 und 6 des Triazinylrings befinden, enthält. In einem solchen Verfahren ist es möglich, zusammen mit dem gefärbten Textil auch weiße beziehungsweise ungefärbte Textilien zu waschen, ohne daß das weiße beziehungsweise ungefärbte Textil angefärbt wird.
Ein weiterer Gegenstand der Erfindung ist ein farbschützendes Waschmittel, enthaltend einen Farbübernagungsinhibitor in Form eines Triazinderivates der oben definierten allgemeinen Formeln II oder III, in denen allerdings jeweils X für eine durch NH-Gruppen unterbrochene Kohlenstoffkette steht, neben üblichen mit diesem Bestandteil verträglichen Inhaltsstoffen, wobei das Triazinderivat der allgemeinen Formel II erhältlich ist durch Umsetzung von 2 Equivalenten solcher Verbindungen gemäß Formel I, die noch 1 oder 2 Halogene am Triazinrest tragen, mit 1 Equivalent Oligo- bzw. Polyethylenimin der Formel NH2-CH2CH2-(NH-CH2CH2-)nNH2, in der n eine Zahl von 1 bis 9, insbesondere 2 bis 5, ist, und wobei das Triazinderivat der allgemeinen Formel III erhältlich ist durch Umsetzung von Diaminostilbenen oder Diaminobiphenylen mit 2 Equivalenten 2,4,6-Trihalogen-1,3,5-Triazin, anschließende Umsetzung mit 2 Equivalenten einer Diaminoarylverbindung, wiederum anschließende Umsetzung mit 2 Equivalenten 2,4,6-Trihalogen-1,3,5-Triazin und anschließende Umsetzung mit 2 Equivalenten Aminoarylverbindung.The invention therefore provides a process for washing dyed textiles in surfactant-containing aqueous solutions, wherein a surfactant-containing aqueous solution is used, which is a triazine derivative of the general formulas I, II or III

T (NH-Ar (SO 3 Na) a ) b Hal c (I)

X (NH-T (NH-Ar (SO 3 Na) a ) e Hal f ) 2 (II)

X (NH-T (NH-Ar (SO 3 Na) d -NH-T (NH-Ar (SO 3 Na) a ) Hal) Hal) 2 (III)

in which
  • T is a 1,3,5-triazinyl radical,
  • Ar for a naphthalene or benzene moiety,
  • X is an optionally interrupted by NH groups linear or branched carbon chain having 1 to 20, in particular 2 to 12 carbon atoms or an optionally mono- or polysubstituted -SO 3 Na-substituted stilbene or biphenyl grouping,
  • Hal for chlorine, bromine or iodine,
  • a and d are independently 1, 2 or 3,
  • b is 1 and c is 2 or b is 2 and c is 1,
  • e is 1 and f is 1 or e is 2 and f is 0,
  • and the -NH- as well as the -Hal substituents are located in positions 2, 4 and 6 of the triazinyl ring. In such a process, it is possible to wash white or undyed textiles together with the dyed textile without the white or undyed textile being dyed.
Another object of the invention is a color-protective detergent containing a Farbübernagungsinhibitor in the form of a triazine derivative of the above-defined general formulas II or III, in which, however, each X is interrupted by NH groups carbon chain, in addition to conventional ingredients compatible with this ingredient, wherein the triazine derivative of the general formula II is obtainable by reacting 2 equivalents of such compounds of the formula I which carry 1 or 2 halogens on the triazine radical, with 1 equivalent of oligo- or polyethylenimine of the formula NH 2 -CH 2 CH 2 - (NH-) CH 2 CH 2 -) n NH 2 , in which n is a number from 1 to 9, in particular 2 to 5, and wherein the triazine derivative of general formula III is obtainable by reaction of diaminostilbenzenes or diaminobiphenyls with 2 equivalents of 2,4, 6-trihalo-1,3,5-triazine, followed by reaction with 2 equivalents of a diaminoaryl compound, followed by Um with 2 equivalents of 2,4,6-trihalo-1,3,5-triazine and subsequent reaction with 2 equivalents of aminoaryl compound.

Triazinderivate der allgemeinen Formel I sind erhältlich durch Umsetzung von 2,4,6-Trihalogen-1,3,5-Triazinen mit 1 oder 2 Equivalenten Aminoarylverbindung, wobei es sich bei der Arylgruppe der Aminoarylverbindung um eine 1 bis 3 fach sulfonatsubstituierte Benzol- oder Napthalin-Einheit handelt. In Frage kommende Aminoarylverbindungen sind beispielsweise 2-Amino-benzolsulfonsäure, 3-Amino-benzolsulfonsäure, 4-Amino-benzolsulfonsäure, 2-Amino-1,3-benzoldisulfonsäure, 4-Amino-1,3-benzoldisulfonsäure, 2-Amino-1,3,5-benzoltrisulfonsäure, 2-Amino-1-naphthalinsulfonsäure, 3-Amino-1-naphthalinsulfonsäure, 4-Amino-1-naphthalinsulfonsäure, 2-Amino-1,5-naphthalindisulfonsäure, 7-Amino-1,6-naphthalindisulfonsäure, 2-Amino-3,6,8-naphthalintrisulfonsäure und 7-Amino-1,3,6-naphthalintrisulfonsäure, wobei deren Sulfonsäuregruppen in Salzform vorliegen. Auch Mischungen der genannten Aminoarylverbindungen können eingesetzt werden.Triazine derivatives of general formula I are obtainable by reacting 2,4,6-trihalo-1,3,5-triazines with 1 or 2 equivalents of aminoaryl compound, wherein the aryl group of the aminoaryl compound is a 1 to 3-fold sulfonate-substituted benzene or Napthalene unit is. Suitable aminoaryl compounds are, for example, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 2-amino-1,3-benzenedisulfonic acid, 4-amino-1,3-benzenedisulfonic acid, 2-amino-1, 3,5-benzenetrisulfonic acid, 2-amino-1-naphthalenesulfonic acid, 3-amino-1-naphthalenesulfonic acid, 4-amino-1-naphthalenesulfonic acid, 2-amino-1,5-naphthalenedisulfonic acid, 7-amino-1,6-naphthalenedisulfonic acid, 2-amino-3,6,8-naphthalenetrisulfonic acid and 7-amino-1,3,6-naphthalenetrisulfonic acid, wherein their sulfonic acid groups are in salt form. It is also possible to use mixtures of the aminoaryl compounds mentioned.

Durch Umsetzung von 2 Equivalenten solcher Verbindungen gemäß Formel I, die noch 1 oder 2 Halogene am Triazinrest tragen, mit 1 Equivalent C1-20-Diaminoalkan, Diaminostilben oder Diaminobiphenyl (H2N-X-NH2) gelangt man zu Verbindungen gemäß Formel II. Unter den Diaminoalkanen sind α,ω-Diaminoalkane besonders bevorzugt, doch können gegebenenfalls auch Oligo- bzw. Polyethylenimine oder -propylenimine in Frage kommen; bevorzugte Oligo- bzw. Polyethylenimine sind solche der Formel NH2-CH2CH2-(NH-CH2CH2-)nNH2, in denen n eine Zahl von 1 bis 9, insbesondere 2 bis 5, ist, wobei auch Mischungen aus Oligo- bzw. Polyethyleniminen verschiedener Oligo- bzw. Polymerisierungsgrade eingesetzt werden können, so daß n als Durchschnittswert auch nicht-ganzzahlige Werte annehmen kann. Bevorzugt ist, wenn das Diaminostilben oder das Diaminobiphenyl auch noch zusätzlich mindestens 1, insbesondere 2 oder Sulfonsäuresalzsubstituenten aufweist, wie beispielsweise 4,4'-Diamino-2,2'-biphenyldisulfonsäure-dinatriumsalz oder 4,4'-Diamino-2,2'-stilbendisulfonsäure-dinatriumsalz. Vorzugsweise handelt es sich um trans-konfigirierte Stilbene, wobei jedoch gegebenenfalls auch die cis-konfigurierten Stilbene und Mischungen aus diesen eingesetzt werden können. Auch Mischungen von Diaminostilbenen mit Diaminobiphenylen können eingesetzt werden.By reacting 2 equivalents of such compounds according to formula I, which carry 1 or 2 halogens on Triazinrest with 1 equivalent of C 1-20 -Diaminoalkan, diaminostilbene or Diaminobiphenyl (H 2 NX-NH 2 ) leads to compounds of formula II. Among the diaminoalkanes, .alpha.,. Omega.-diaminoalkanes are particularly preferred, but if appropriate, oligo- or polyethyleneimines or -propylenimines may also be suitable; preferred oligo- or polyethyleneimines are those of the formula NH 2 -CH 2 CH 2 - (NH-CH 2 CH 2 -) n NH 2 , in which n is a number from 1 to 9, in particular 2 to 5, wherein also Mixtures of oligo- or polyethyleneimines of different degrees of oligo- or polymerization can be used so that n can take as an average value and non-integer values. It is preferred if the diaminostilbene or diaminobiphenyl also additionally has at least 1, in particular 2 or sulfonic acid salt substituents, for example 4,4'-diamino-2,2'-biphenyldisulfonic acid disodium salt or 4,4'-diamino-2,2 ' -stilbendisulfonsäure disodium salt. Preferably, these are trans-configured stilbenes, but optionally also the cis-configured stilbenes and mixtures thereof can be used. It is also possible to use mixtures of diaminostilbenes with diamino-biphenylene.

Entsprechende Diaminoalkane, Diaminostilbene oder Diaminobiphenyle, umgesetzt mit 2 Equivalenten 2,4,6-Trihalogen-1,3,5-Triazin, das Reaktionsprodukt anschließend umgesetzt mit 2 Equivalenten einer Diaminoarylverbindung H2N-Ar(SO3Na)d-NH2, das daraus entstehende Reaktionsprodukt wiederum umgesetzt mit 2 Equivalenten 2,4,6-Trihalogen-1,3,5-Triazin und anschließend mit 2 Equivalenten Aminoarylverbindung, ergeben Verbindungen gemäß allgemeiner Formel III. Die Aminoarylverbindung ist dabei mit der bei der Herstellung der Verbindung gemäß Formel I diskutierten Aminoarylverbindung identisch. Die Diaminoarylverbindung wird aus den diesen im Grundgerüst völlig entsprechenden Verbindungen ausgewählt, die zusätzlich eine zweite Aminogruppe tragen.Corresponding diaminoalkanes, diaminostilbenes or diamino-biphenyls reacted with 2 equivalents of 2,4,6-trihalo-1,3,5-triazine, the reaction product subsequently reacted with 2 equivalents of a diaminoaryl compound H 2 N-Ar (SO 3 Na) d -NH 2 , the reaction product formed therefrom in turn reacted with 2 equivalents of 2,4,6-trihalo-1,3,5-triazine and then with 2 equivalents of aminoaryl compound, give compounds according to general formula III. The aminoaryl compound is identical to the aminoaryl compound discussed in the preparation of the compound according to formula I. The diaminoaryl compound is selected from the compounds corresponding to these in the skeleton, which additionally carry a second amino group.

Bei gleichzeitigem Einsatz verschiedener Aminoarylverbindungen beziehungsweise bei gleichzeitigem Einsatz verschiedener Diaminoarylverbindungen beziehungsweise bei gleichzeitigem Einsatz verschiedener Diaminoalkane und/oder gegebenenfalls verschieden substituierter Diaminostilbene und/oder Diaminobiphenyle erhält man in den beschriebenen Herstellungsverfahren zwanglos Verbindungen gemäß den Formel I, II oder III, in denen die jeweiligen Variablen a, b, c, d, e, f, X und Ar nicht jeweils immer gleich sind.In the simultaneous use of different aminoaryl compounds or simultaneous use of different diaminoaryl compounds or simultaneous use of different diaminoalkanes and / or optionally differently substituted diaminostilbene and / or Diaminobiphenyle obtained in the described preparation process casually compounds according to the formula I, II or III, in which the respective variables a, b, c, d, e, f, X and Ar are not always the same.

Ein erfindungsgemäßes Mittel enthält vorzugsweise 0,05 Gew.-% bis 2 Gew.-%, insbesondere 0,2 Gew.-% bis 1 Gew.-%, farbübertragungsinhibierende Verbindung der allgemeinen Formel II und/oder III und gegebenenfalls zusätzlich Triazinderivat der allgemeinen Formel I. Durch die "und/oder"-Formulierung soll deutlich gemacht werden, daß auch der gemeinsame Einsatz von Verbindungen, welche jeweils einer der genannten Formeln entsprechen, möglich ist.An inventive composition preferably contains 0.05 wt .-% to 2 wt .-%, in particular 0.2 wt .-% to 1 wt .-%, dye transfer inhibiting compound of general formula II and / or III and optionally additionally triazine derivative of the general Formula I. The "and / or" formulation is intended to make it clear that the joint use of compounds which correspond in each case to one of the abovementioned formulas is also possible.

Die Verbindungen der allgemeinen Formel I, II oder III leisten bei beiden zuvor angesprochenen Aspekten der Farbkonstanz einen Beitrag, das heißt sie vermindern sowohl das Verfärben wie auch die Verblassung, wenn auch der Effekt der Verhinderung des Anfärbens, insbesondere beim Waschen weißer Textilien, am ausgeprägtesten ist. Ein weiterer Gegenstand der Erfindung ist daher die Verwendung einer entsprechenden Verbindung zur Vermeidung der Veränderung des Farbeindrucks von Textilien bei deren Wäsche in insbesondere tensidhaltigen wäßrigen Lösungen. Unter der Veränderung des Farbeindrucks ist dabei keineswegs der Unterschied zwischen verschmutztem und
sauberem Textil zu verstehen, sondern der Unterschied zwischen jeweils sauberem Textil vor und nach dem Waschvorgang.The compounds of the general formula I, II or III contribute to both the above-mentioned aspects of color constancy, that is to say they reduce both discoloration and fading, although the effect of preventing staining, especially when washing white textiles, is most pronounced is. Another object of the invention is therefore the use of a corresponding compound to avoid the change in the color impression of textiles in their Laundry in particular surfactant-containing aqueous solutions. By changing the color impression is by no means the difference between polluted and
clean textile, but the difference between each clean textile before and after the washing process.

Weitere Gegenstände der Erfindung sind die Verwendung von Triazinderivaten der allgemeinen Formeln II oder III, in denen allerdings jeweils X für eine durch NH-Gruppen unterbrochene Kohlenstoffkette steht, zur Vermeidung der Übertragung von Textilfarbstoffen von gefärbten Textilien auf ungefärbte oder andersfarbige Textilien bei deren gemeinsamer Wäsche in insbesondere tensidhaltigen wäßrigen Lösungen, oder zur Vermeidung der Veränderung des Farbeindrucks von gefärbten Textilien bei deren Wäsche in insbesondere tensidhaltigen wäßrigen Lösungen, wobei das Triazinderivat der allgemeinen Formel II erhältlich ist durch Umsetzung von 2 Equivalenten solcher Verbindungen gemäß Formel I, die noch 1 oder 2 Halogene am Triazinrest tragen, mit 1 Equivalent Oligo- bzw. Polyethylenimin der Formel NH2-CH2CH2-(NH-CH2CH2-)nNH2, in der n eine Zahl von 1 bis 9, insbesondere 2 bis 5, ist, und wobei das Triazinderivat der allgemeinen Formel III erhältlich ist durch Umsetzung von Diaminostilbenen oder Diaminobiphenylen mit 2 Equivalenten 2,4,6-Trihalogen-1,3,5-Triazin, anschließende Umsetzung mit 2 Equivalenten einer Diaminoarylverbindung, wiederum anschließende Umsetzung mit 2 Equivalenten 2,4,6-Trihalogen-1,3,5-Triazin und anschließende Umsetzung mit 2 Equivalenten Aminoarylverbindung.Further objects of the invention are the use of triazine derivatives of the general formulas II or III, in which, however, in each case X represents a carbon chain interrupted by NH groups, to avoid the transfer of textile dyes of dyed textiles to undyed or differently colored textiles in their joint washing in in particular surfactant-containing aqueous solutions, or to avoid the change in the color impression of dyed textiles in their washing in particular surfactant-containing aqueous solutions, wherein the triazine derivative of general formula II is obtainable by reacting 2 equivalents of such compounds of formula I, the nor 1 or 2 halogens on the triazine radical, with 1 equivalent of oligo- or polyethyleneimine of the formula NH 2 -CH 2 CH 2 - (NH-CH 2 CH 2 -) n NH 2 , in which n is a number from 1 to 9, in particular 2 to 5, and wherein the triazine derivative of general formula III is obtainable by reaction ng of diaminostilbenes or diaminobiphenyls with 2 equivalents of 2,4,6-trihalo-1,3,5-triazine, followed by reaction with 2 equivalents of a diaminoaryl compound, followed by reaction with 2 equivalents of 2,4,6-trihalogen-1,3, 5-triazine and subsequent reaction with 2 equivalents of aminoaryl compound.

Ein erfindungsgemäßes Mittel kann neben der Verbindung gemäß Formel II oder III und gegebenenfalls der Formel I einen bekannten Farbübertragungsinhibitor, diesen dann vorzugsweise in Mengen von 0,1 Gew.-% bis 2 Gew.-%, insbesondere 0,2 Gew.-% bis 1 Gew.-%, enthalten, der in einer bevorzugten Ausgestaltung der Erfindung ein Polymer aus Vinylpyrrolidon, Vinylimidazol, Vinylpyridin-N-Oxid oder ein Copolymer aus diesen ist. Brauchbar sind sowohl die beispielsweise aus der europäischen Patentanmeldung EP 0 262 897 bekannten Polyvinylpyrrolidone mit Molgewichten von 15 000 bis 50 000 wie auch die aus der internationalen Patentanmeldung WO 95/06098 bekannten Polyvinylpyrrolidone mit Molgewichten über 1 000 000, insbesondere von 1 500 000 bis 4 000 000, die aus den deutschen Patentanmeldungen DE 28 14 287 oder DE 38 03 630 oder den internationalen Patentanmeldungen WO 94/10281 , WO 94/26796 , WO 95/03388 und WO 95/03382 bekannten N-Vinylimidazol/N-Vinylpyrrolidon-Copolymere, die aus der deutschen Patentanmeldung DE 28 14 329 bekannten Polyvinyloxazolidone, die aus der europäischen Patentanmeldung EP 610 846 bekannten Copolymere auf Basis von Vinylmonomeren und Carbonsäureamiden, die aus der internationalen Patentanmeldung WO 95/09194 bekannten pyrrolidongruppenhaltigen Polyester und Polyamide, die aus der internationalen Patentanmeldung WO 94/29422 bekannten gepfropften Polyamidoamine und Polyethylenimine, die aus der deutschen Patentanmeldung DE 43 28 254 bekannten Polymere mit Amidgruppen aus sekundären Aminen, die aus der internationalen Patentanmeldung WO 94/02579 oder der europäischen Patentanmeldung EP 0 135 217 bekannten Polyamin-N-Oxid-Polymere, die aus der europäischen Patentanmeldung EP 0 584 738 bekannten Polyvinylalkohole und die aus der europäischen Patentanmeldung EP 0 584 709 bekannten Copolymere auf Basis von Acrylamidoalkenylsulfonsäuren. Eingesetzt werden können aber auch enzymatischeIn addition to the compound of the formula II or III and, if appropriate, of the formula I, an agent according to the invention may comprise a known dye transfer inhibitor, then preferably in amounts of from 0.1% by weight to 2% by weight, in particular 0.2% by weight 1 wt .-%, which in a preferred embodiment of the invention is a polymer of vinylpyrrolidone, vinylimidazole, vinylpyridine-N-oxide or a copolymer thereof. Useful are both the example of the European patent application EP 0 262 897 known Polyvinylpyrrolidone with molecular weights of 15,000 to 50,000 as well as those of the international patent application WO 95/06098 known polyvinylpyrrolidones having molecular weights above 1 000 000, in particular from 1 500 000 to 4 000 000, which are known from the German patent applications DE 28 14 287 or DE 38 03 630 or the international patent applications WO 94/10281 . WO 94/26796 . WO 95/03388 and WO 95/03382 known N-vinylimidazole / N-vinylpyrrolidone copolymers, which are known from the German patent application DE 28 14 329 Polyvinyloxazolidone known from the European patent application EP 610 846 known copolymers based on vinyl monomers and carboxylic acid amides, which are known from international patent application WO 95/09194 known pyrrolidone group-containing polyesters and polyamides which are known from the international patent application WO 94/29422 known grafted polyamidoamines and polyethyleneimines, from the German patent application DE 43 28 254 known polymers with amide groups from secondary amines, which are known from the international patent application WO 94/02579 or the European patent application EP 0 135 217 known polyamine N-oxide polymers, from the European patent application EP 0 584 738 known polyvinyl alcohols and those of the European patent application EP 0 584 709 known copolymers based on acrylamidoalkenylsulfonic acids. But can also be used enzymatic

Systeme, umfassend eine Peroxidase und Wasserstoffperoxid beziehungsweise eine in Wasser Wasserstoffperoxid-liefernde Substanz, wie sie zum Beispiel aus den internationalen Patentanmeldungen WO 92/18687 und WO 91/05839 bekannt sind. Der Zusatz einer Mediatorverbindung für die Peroxidase, zum Beispiel eines aus der internationalen Patentanmeldung WO 96/10079 bekannten Acetosyringons, eines aus der internationalen Patentanmeldung WO 96/12845 bekannten Phenolderivats oder eines aus der internationalen Patentanmeldung WO 96/12846 bekannten Phenotiazins oder Phenoxazins, ist in diesem Fall bevorzugt, wobei auch zusätzlich obengenannte polymere Farbübertragungsinhibitorwirkstoffe eingesetzt werden können. Polyvinylpyrrolidon weist zum Einsatz in erfindungsgemäßen Mitteln vorzugsweise eine durchschnittliche Molmasse im Bereich von 10 000 bis 60 000, insbesondere im Bereich von 25 000 bis 50 000 auf. Unter den Copolymeren sind solche aus Vinylpyrrolidon und Vinylimidazol im Molverhältnis 5:1 bis 1:1 mit einer durchschnittlichen Molmasse im Bereich von 5 000 bis 50 000, insbesondere 10 000 bis 20 000 bevorzugt.Systems comprising a peroxidase and hydrogen peroxide or a water-hydrogen peroxide-yielding substance, as disclosed, for example, in International Patent Applications WO 92/18687 and WO 91/05839 are known. The addition of a mediator compound for the peroxidase, for example one from the international patent application WO 96/10079 known acetosyringone, one from the international patent application WO 96/12845 known phenol derivative or one from the international patent application WO 96/12846 known phenotiazine or phenoxazine, is preferred in this case, whereby also above-mentioned polymeric Farbübertragungsinhibitorwirkstoffe can be used. Polyvinylpyrrolidone preferably has an average molecular weight in the range from 10 000 to 60 000, in particular in the range from 25 000 to 50 000, for use in compositions according to the invention. Among the copolymers, those of vinylpyrrolidone and vinylimidazole in a molar ratio of 5: 1 to 1: 1 having an average molecular weight in the range of 5,000 to 50,000, especially 10,000 to 20,000 are preferred.

Die erfindungsgemäßen Waschmittel, die als insbesondere pulverförmige Feststoffe, in nachverdichteter Teilchenform, als homogene Lösungen oder Suspensionen vorliegen können, können außer dem erfingdungsgemäß eingesetzten Wirkstoff im Prinzip alle bekannten und in derartigen Mitteln üblichen Inhaltsstoffe enthalten. Die erfindungsgemäßen Mittel können insbesondere Buildersubstanzen, oberflächenaktive Tenside, Bleichmittel auf Basis organischer und/oder anorganischer Persauerstoffverbindungen, Bleichaktivatoren, wassermischbare organische Lösungsmittel, Enzyme, Sequestrierungsmittel, Elektrolyte, pH-Regulatoren und weitere Hilfsstoffe, wie optische Aufheller, Vergrauungsinhibitoren, Schaumregulatoren sowie Farb- und Duftstoffe enthalten.The detergents according to the invention, which may be in the form of homogeneous solutions or suspensions, in particular in powdered solids, in densified particle form, can in principle contain, in addition to the active ingredient used according to the invention, all known ingredients customary in such agents. The agents according to the invention may in particular be builders, surface-active surfactants, bleaches based on organic and / or inorganic peroxygen compounds, bleach activators, water-miscible organic solvents, enzymes, sequestering agents, electrolytes, pH regulators and other auxiliaries, such as optical brighteners, grayness inhibitors, foam regulators and colorants Contain fragrances.

Die erfindungsgemäßen Mittel können ein Tensid oder mehrere Tenside enthalten, wobei insbesondere anionische Tenside, nichtionische Tenside und deren Gemische, aber auch kationische, zwitterionische und amphotere Tenside in Frage kommen.The compositions according to the invention may comprise one or more surfactants, in particular anionic surfactants, nonionic surfactants and mixtures thereof, but also cationic, zwitterionic and amphoteric surfactants.

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.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. Furthermore, corresponding 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, as well as of alkylphenols having 5 to 12 C atoms in the alkyl radical.

Als nichtionische Tenside werden vorzugsweise alkoxylierte, vorteilhafterweise ethoxylierte, insbesondere primäre Alkohole mit vorzugsweise 8 bis 18 C-Atomen und durchschnittlich 1 bis 12 Mol Ethylenoxid (EO) pro Mol Alkohol eingesetzt, in denen der Alkoholrest linear oder bevorzugt in 2-Stellung methylverzweigt sein kann beziehungsweise lineare und methylverzweigte Reste im Gemisch enthalten kann, so wie sie üblicherweise in Oxoalkoholresten vorliegen. Insbesondere sind jedoch Alkoholethoxylate mit linearen Resten aus Alkoholen nativen Ursprungs mit 12 bis 18 C-Atomen, z.B. aus Kokos-; Palm-, Talgfett- oder Oleylalkohol, und durchschnittlich 2 bis 8 EO pro Mol Alkohol bevorzugt. Zu den bevorzugten ethoxylierten Alkoholen gehören beispielsweise C12-C14-Alkohole mit 3 EO oder 4 EO, C9-C11-Alkohole mit 7 EO, C13-C15-Alkohole mit 3 EO, 5 EO, 7 EO oder 8 EO, C12-C18-Alkohole mit 3 EO, 5 EO oder 7 EO und Mischungen aus diesen, wie Mischungen aus C12-C14-Alkohol mit 3 EO und C12-C18-Alkohol mit 7 EO. Die angegebenen Ethoxylierungsgrade stellen statistische Mittelwerte dar, die für ein spezielles Produkt eine ganze oder eine gebrochene Zahl sein können. Bevorzugte Alkoholethoxylate weisen eine eingeengte Homologenverteilung auf (narrow range ethoxylates, NRE). Zusätzlich zu diesen nichtionischen Tensiden können auch Fettalkohole mit mehr als 12 EO eingesetzt werden. Beispiele hierfür sind (Talg-) Fettalkohole mit 14 EO, 16 EO, 20 EO, 25 EO, 30 EO oder 40 EO. Insbesondere in Mitteln für den Einsatz in maschinellen Verfahren werden üblicherweise extrem schaumarme Verbindungen eingesetzt. Hierzu zählen vorzugsweise C12-C18-Alkylpolyethylenglykol-polypropylenglykolether mit jeweils bei zu 8 Mol Ethylenoxid- und Propylenoxideinheiten im Molekül. Man kann aber auch andere bekannt schaumarme nichtionische Tenside verwenden, wie zum Beispiel C12-C18-Alkylpolyethylenglykol-polybutylenglykolether mit jeweils bis zu 8 Mol Ethylenoxid- und Butylenoxideinheiten im Molekül sowie endgruppenverschlossene Alkylpolyalkylenglykolmischether. Besonders bevorzugt sind auch die hydroxylgruppenhaltigen alkoxylierten Alkohole, wie sie in der europäischen Patentanmeldung EP 0 300 305 beschrieben sind, sogenannte Hydroxymischether. Zu den nichtionischen Tensiden zählen auch Alkylglykoside der allgemeinen Formel RO(G)x eingesetzt werden, in der R einen primären geradkettigen oder methylverzweigten, insbesondere in 2-Stellung methylverzweigten aliphatischen Rest mit 8 bis 22, vorzugsweise 12 bis 18 C-Atomen bedeutet und G für eine Glykoseeinheit mit 5 oder 6 C-Atomen, vorzugsweise für Glucose, steht. Der Oligomerisierungsgrad x, der die Verteilung von Monoglykosiden und Oligoglykosiden angibt, ist eine beliebige Zahl - die als analytisch zu bestimmende Größe auch gebrochene Werte annehmen kann - zwischen 1 und 10; vorzugsweise liegt x bei 1,2 bis 1,4. Ebenfalls geeignet sind Polyhydroxyfettsäureamide der Formel (IV), in der R1CO für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen, R2 für Wasserstoff, einen Alkyl- oder Hydroxyalkylrest mit 1 bis 4 Kohlenstoffatomen und [Z] für einen linearen oder verzweigten Polyhydroxyalkylrest mit 3 bis 10 Kohlenstoffatomen und 3 bis 10 Hydroxylgruppen steht:

Figure imgb0001
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 may contain linear and methyl-branched radicals in the mixture, as they are usually present in Oxoalkoholresten. In particular, however, are alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example from coconut; Palm, tallow or oleyl alcohol, and on average from 2 to 8 EO per mole of alcohol. The preferred ethoxylated alcohols include, for example, C 12 -C 14 -alcohols with 3 EO or 4 EO, C 9 -C 11 -alcohols with 7 EO, C 13 -C 15 -alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12 -C 18 -alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C 12 -C 14 -alcohol with 3 EO and C 12 -C 18 -alcohol with 7 EO. The degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include (tallow) fatty alcohols with 14 EO, 16 EO, 20 EO, 25 EO, 30 EO or 40 EO. In particular, agents for use in mechanical processes usually extremely low-foam compounds are used. These include preferably C 12 -C 18 -alkylpolyethylenglykol-polypropylene glycol ethers with in each case at to 8 mol ethylene oxide and propylene oxide units in the molecule. However, it is also possible to use other known low-foam nonionic surfactants, such as, for example, C 12 -C 18 -alkylpolyethylene glycol-polybutylene glycol ethers having up to 8 mol of ethylene oxide and butylene oxide units in the molecule and also end-capped alkylpolyalkylene glycol mixed ethers. Also particularly preferred are the hydroxyl-containing alkoxylated alcohols, as described in the European patent application EP 0 300 305 are described, so-called Hydroxymischether. The nonionic surfactants also include alkyl glycosides of the general formula RO (G) x are used, in the R a primary straight-chain or methyl-branched, in particular in the 2-position methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is a glycose unit having 5 or 6 carbon atoms, preferably glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is an arbitrary number - which, as a variable to be determined analytically, may also assume fractional values - between 1 and 10; preferably x is 1.2 to 1.4. Also suitable are polyhydroxy fatty acid amides of the formula (IV) in which R 1 CO is an aliphatic acyl radical having 6 to 22 carbon atoms, R 2 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:
Figure imgb0001

Vorzugsweise leiten sich die Polyhydroxyfettsäureamide von reduzierenden Zuckern mit 5 oder 6 Kohlenstoffatomen, insbesondere von der Glucose ab. Zur Gruppe der Polyhydroxyfettsäureamide gehören auch Verbindungen der Formel (V),

Figure imgb0002
in der R3 für einen linearen oder verzweigten Alkyl- oder Alkenylrest mit 7 bis 12 Kohlenstoffatomen, R4 für einen linearen, verzweigten oder cyclischen Alkylenrest oder einen Arylenrest mit 2 bis 8 Kohlenstoffatomen und R5 für einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest oder einen Oxy-Alkylrest mit 1 bis 8 Kohlenstoffatomen steht, wobei C1-C4-Alkyl- oder Phenylreste bevorzugt sind, und [Z] für einen linearen Polyhydroxyalkylrest, dessen Alkylkette mit mindestens zwei Hydroxylgruppen substituiert ist, oder alkoxylierte, vorzugsweise ethoxylierte oder propoxylierte Derivate dieses Restes steht. [Z] wird auch hier vorzugsweise durch reduktive Aminierung eines Zuckers wie Glucose, Fructose, Maltose, Lactose, Galactose, Mannose oder Xylose erhalten. Die N-Alkoxy- oder N-Aryloxy-substituierten Verbindungen können dann beispielsweise nach der Lehre der internationalen Patentanmeldung WO 95/07331 durch Umsetzung mit Fettsäuremethylestern in Gegenwart eines Alkoxids als Katalysator in die gewünschten Polyhydroxyfettsäureamide überfährt werden. Eine weitere Klasse bevorzugt eingesetzter nichtionischer Tenside, die entweder als alleiniges nichtionisches Tensid oder in Kombination mit anderen nichtionischen Tensiden, insbesondere zusammen mit alkoxylierten Fettalkoholen und/oder Alkylglykosiden, eingesetzt werden, sind alkoxylierte, vorzugsweise ethoxylierte oder ethoxylierte und propoxylierte Fettsäurealkylester, vorzugsweise mit 1 bis 4 Kohlenstoffatomen in der Alkylkette, insbesondere Fettsäuremethylester, wie sie beispielsweise in der japanischen Patentanmeldung JP 58/217598 beschrieben sind oder die vorzugsweise nach dem in der internationalen Patentanmeldung WO 90/13533 beschriebenen Verfahren hergestellt werden. Auch nichtionische Tenside vom Typ der Aminoxide, beispielsweise N-Kokosalkyl-N,N-dimethylaminoxid und N-Talgalkyl-N,N-dihydroxyethylaminoxid, und der Fettsäurealkanolamide können geeignet sein. Die Menge dieser nichtionischen Tenside beträgt vorzugsweise nicht mehr als die der ethoxylierten Fettalkohole, insbesondere nicht mehr als die Hälfte davon. Als weitere Tenside kommen sogenannte Gemini-Tenside in Betracht. Hierunter werden im allgemeinen solche Verbindungen verstanden, die zwei hydrophile Gruppen pro Molekül besitzen. Diese Gruppen sind in der Regel durch einen sogenannten "Spacer" voneinander getrennt. Dieser Spacer ist in der Regel eine Kohlenstorfkette, die lang genug sein sollte, daß die hydrophilen Gruppen einen ausreichenden Abstand haben, damit sie unabhängig voneinander agieren können. Derartige Tenside zeichnen sich im allgemeinen durch eine ungewöhnlich geringe kritische Micellkonzentration und die Fähigkeit, die Oberflächenspannung des Wassers stark zu reduzieren, aus. In Ausnahmefällen werden unter dem Ausdruck Gemini-Tenside nicht nur derartig "dimere", sondern auch entsprechend "trimere" Tenside verstanden. Geeignete Gemini-Tenside sind beispielsweise sulfatierte Hydroxymischether gemäß der deutschen Patentanmeldung DE 43 21 022 oder Dimeralkohol-bis- und Trimeralkohol-tris-sulfate und -ethersulfate gemäß der deutschen Patentanmeldung DE 195 03 061 . Endgruppenverschlossene dimere und trimere Mischether gemäß der deutschen Patentanmeldung DE 195 13 391 zeichnen sich insbesondere durch ihre Bi- und Multifunktionalität aus. So besitzen die genannten endgruppenverschlossenen Tenside gute Netzeigenschaften und sind dabei schaumarm, so daß sie sich insbesondere für den Einsatz in maschinellen Wasch- oder Reinigungsverfahren eignen. Eingesetzt werden können aber auch Gemini-Polyhydroxyfettsäureamide oder Poly-Polyhydroxyfettsäureamide, wie sie in den internationalen Patentanmeldungen WO 95/19953 , WO 95/19954 und WO 95/19955 beschrieben werden.The polyhydroxy fatty acid amides are preferably derived from reducing sugars having 5 or 6 carbon atoms, in particular from glucose. The group of polyhydroxy fatty acid amides also includes compounds of the formula (V),
Figure imgb0002
 in the R 3 is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R 4 is a linear, branched or cyclic alkylene radical or an arylene radical having 2 to 8 carbon atoms and R 5 is a linear, branched or cyclic alkyl radical or a Aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, wherein C 1 -C 4 alkyl or phenyl radicals are preferred, and [Z] is a linear polyhydroxyalkyl radical whose alkyl chain is substituted with at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this group. [Z] is also here preferably by reductive amination of a sugar such as glucose, fructose, maltose, lactose, galactose, Mannose or xylose received. The N-alkoxy- or N-aryloxy-substituted compounds can then be used, for example, according to the teaching of the international patent application WO 95/07331 be transferred by reaction with fatty acid methyl esters in the presence of an alkoxide as a catalyst in the desired polyhydroxy fatty acid amides. Another class of preferred nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants, in particular together with alkoxylated fatty alcohols and / or alkyl glycosides, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably from 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl ester, as described for example in the Japanese patent application JP 58/217598 are described or preferably according to the in the international patent application WO 90/13533 be prepared described methods. 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 may also be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof. Other suitable surfactants are so-called gemini surfactants. These are generally understood as meaning those compounds which have two hydrophilic groups per molecule. These groups are usually separated by a so-called "spacer". This spacer is usually a carbon stalk chain that should be long enough for the hydrophilic groups to be spaced sufficiently apart for them to act independently of each other. Such surfactants are generally characterized by an unusually low critical micelle concentration and the ability to greatly reduce the surface tension of the water. In exceptional cases, the term gemini surfactants not only such "dimer", but also corresponding to "trimeric" surfactants understood. Suitable gemini surfactants are, for example, sulfated hydroxy mixed ethers according to the German patent application DE 43 21 022 or dimer alcohol bis and trimer alcohol tris sulfates and ether sulfates according to the German patent application DE 195 03 061 , End-capped dimeric and trimeric mixed ethers according to the German patent application DE 195 13 391 They are characterized by their bi- and multi-functionality. So own the mentioned Endgruppenverschlossenen surfactants good wetting properties and are low in foam, so that they are particularly suitable for use in machine washing or cleaning processes. However, it is also possible to use gemini-polyhydroxy fatty acid amides or poly-polyhydroxy fatty acid amides, as described in international patent applications WO 95/19953 . WO 95/19954 and WO 95/19955 to be discribed.

Geeignete anionische Tenside sind insbesondere Seifen und solche, die Sulfat- oder Sulfonat-Gruppen enthalten. Als Tenside vom Sulfonat-Typ kommen vorzugsweise C9-C13-Alkylbenzolsulfonate, Olefinsulfonate, das heißt Gemische aus Alken- und Hydroxyalkansulfonaten sowie Disulfonaten, wie man sie beispielsweise aus C12-C18-Monoolefinen mit end- oder innenständiger Doppelbindung durch Sulfonieren mit gasförmigem Schwefeltrioxid und anschließende alkalische oder saure Hydrolyse der Sulfonierungsprodukte erhält, in Betracht. Geeignet sind auch Alkansulfonate, die aus C12-C18-Alkanen beispielsweise durch Sulfochlorierung oder Sulfoxidation mit anschließender Hydrolyse beziehungsweise Neutralisation gewonnen werden. Geeignet sind auch die Ester von α-Sulfofettsäuren (Estersulfonate), zum Beispiel die α-sulfonierten Methylester der hydrierten Kokos-, Palmkern- oder Talgfettsäuren, die durch α-Sulfonierung der Methylester von Fettsäuren pflanzlichen und/oder tierischen Ursprungs mit 8 bis 20 C-Atomen im Fettsäuremolekül und nachfolgende Neutralisation zu wasserlöslichen Mono-Salzen hergestellt werden, in Betracht. Vorzugsweise handelt es sich hierbei um die α-sulfonierten Ester der hydrierten Kokos-, Palm-, Palmkern- oder Talgfettsäuren, wobei auch Sulfonierungsprodukte von ungesättigten Fettsäuren, beispielsweise Ölsäure, in geringen Mengen, vorzugsweise in Mengen nicht oberhalb etwa 2 bis 3 Gew.-%, vorhanden sein können. Insbesondere sind α-Sulfofettsäurealkylester bevorzugt, die eine Alkylkette mit nicht mehr als 4 C-Atomen in der Estergruppe aufweisen, beispielsweise Methylester, Ethylester, Propylester und Butylester. Mit besonderem Vorteil werden die Methylester der α-Sulfofettsäuren (MES), aber auch deren verseifte Disalze eingesetzt. Weitere geeignete Aniontenside sind sulfierte Fettsäureglycerinester, welche Mono-, Di- und Triester sowie deren Gemische darstellen, wie sie bei der Herstellung durch Veresterung durch ein Monoglycerin mit 1 bis 3 Mol Fettsäure oder bei der Umesterung von Triglyceriden mit 0,3 bis 2 Mol Glycerin erhalten werden. Als Alk(en)ylsulfate werden die Alkali- und insbesondere die Natriumsalze der Schwefelsäurehalbester der C12-C18-Fettalkohole beispielsweise aus Kokosfettalkohol, Talgfettalkohol, Lauryl-, Myristyl-, Cetyl- oder Stearylalkohol oder der C10-C20-Oxoalkohole und diejenigen Halbester sekundärer Alkohole dieser Kettenlänge bevorzugt. Weiterhin bevorzugt sind Alk(en)ylsulfate der genannten Kettenlänge, ,welche einen synthetischen, auf petrochemischer Basis hergestellten geradkettigen Alkylrest enthalten, die ein analoges Abbauverhalten besitzen wie die adäquaten Verbindungen auf der Basis von fettchemischen Rohstoffen. Aus waschtechnischem Interesse sind C12-C16-Alkylsulfate und C12-C15-Alkylsulfate sowie C14-C15-Alkylsulfate insbesondere bevorzugt. Auch 2,3-Alkylsulfate, welche beispielsweise gemäß den US-amerikanischen Patentschriften US 3 234 258 oder US 5 075 041 hergestellt werden und als Handelsprodukte der Shell Oil Company unter dem Namen DAN® erhalten werden können, sind geeignete Aniontenside. Geeignet sind auch die Schwefelsäuremonoester der mit 1 bis 6 Mol Ethylenoxid ethoxylierten geradkettigen oder verzweigten C7-C21-Alkohole, wie 2-Methylverzweigte C9-C11-Alkohole mit im Durchschnitt 3,5 Mol Ethylenoxid (EO) oder C12-C18-Fettalkohole mit 1 bis 4 EO. Zu den bevorzugten Aniontensiden gehören auch die Salze der Alkylsulfobernsteinsäure, die auch als Sulfosuccinate oder als Sulfobernsteinsäureester bezeichnet werden, und die Monoester und/oder Diester der Sulfobernsteinsäure mit Alkoholen, vorzugsweise Fettalkoholen und insbesondere ethoxylierten Fettalkoholen darstellen. Bevorzugte Sulfosuccinate enthalten C8- bis C18-Fettalkoholreste oder Mischungen aus diesen. Insbesondere bevorzugte Sulfosuccinate enthalten einen Fettalkoholrest, der sich von ethoxylierten Fettalkoholen ableitet, die für sich betrachtet nichtionische Tenside darstellen. Dabei sind wiederum Sulfosuccinate, deren Fettalkohol-Reste sich von ethoxylierten Fettalkoholen mit eingeengter Homologenverteilung ableiten, besonders bevorzugt. Ebenso ist es auch möglich, Alk(en)ylbernsteinsäure mit vorzugsweise 8 bis 18 Kohlenstoffatomen in der Alk(en)ylkette oder deren Salze einzusetzen. Als weitere anionische Tenside kommen Fettsäure-Derivate von Aminosäuren, beispielsweise von N-Methyltaurin (Tauride) und/oder von N-Methylglycin (Sarkoside) in Betracht. Insbesondere bevorzugt sind dabei die Sarkoside beziehungsweise die Sarkosinate und hier vor allem Sarkosinate von höheren und gegebenenfalls einfach oder mehrfach ungesättigten Fettsäuren wie Oleylsarkosinat. Als weitere anionische Tenside kommen insbesondere Seifen in Betracht. Geeignet sind insbesondere gesättigte Fettsäureseifen, wie die Salze der Laürinsäure, Myristinsäure, Palmitinsäure, Stearinsäure, hydrierten Erucasäure und Behensäure sowie insbesondere aus natürlichen Fettsäuren, zum Beispiel Kokos-, Palmkern- oder Talgfettsäuren, abgeleitete Seifengemische. Zusammen mit diesen Seifen oder als Ersatzmittel für Seifen können auch die bekannten Alkenylbernsteinsäuresalze eingesetzt werden.Suitable anionic surfactants are in particular soaps and those which contain sulfate or sulfonate groups. As surfactants of the sulfonate type are preferably C 9 -C 13 alkylbenzenesulfonates, Olefinsulfonate, that is, mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as they are, for example, from C 12 -C 18 monoolefins with terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation obtained. Also suitable are alkanesulfonates which are obtained from C 12 -C 18 -alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. Also suitable are the esters of α-sulfo fatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids obtained by α-sulfonation of the methyl esters of fatty acids of plant and / or animal origin with 8 to 20 C -Atomen in the fatty acid molecule and subsequent neutralization to water-soluble mono-salts are prepared, into consideration. These are preferably the α-sulfonated esters of hydrogenated coconut, palm, palm kernel or tallow fatty acids, although sulfonated products of unsaturated fatty acids, for example oleic acid, in small amounts, preferably in amounts not above about 2 to 3 wt. %, can be present. In particular, α-sulfofatty acid alkyl esters are preferred which have an alkyl chain with not more than 4 C atoms in the ester group, for example, methyl ester, ethyl ester, propyl ester and butyl ester. With particular advantage, the methyl esters of α-sulfo fatty acids (MES), but also their saponified disalts are used. Other suitable anionic surfactants are sulfated fatty acid glycerol esters, which are mono-, di- and triesters and mixtures thereof, as in the preparation by esterification by a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol to be obtained. As alk (en) ylsulfate the alkali and in particular the sodium salts of sulfuric monoesters of C 12 -C 18 fatty alcohols, for example, from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or C 10 -C 20 -oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) ylsulfates of said chain length, which contain a synthetic, petrochemical-based straight-chain alkyl radical, which have an analogous degradation behavior as the adequate compounds based on oleochemical raw materials. Of washing-technical interest, C 12 -C 16 -alkyl sulfates and C 12 -C 15 -alkyl sulfates and C 14 -C 15 -alkyl sulfates are particularly preferred. Also 2,3-alkyl sulfates, which, for example, according to the US patents US 3,234,258 or US 5 075 041 which can be obtained as commercial products of the Shell Oil Company under the name DAN® are suitable anionic surfactants. Also suitable are the sulfuric acid monoesters of straight-chain or branched C 7 -C 21 -alcohols ethoxylated with from 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C 9 -C 11 -alcohols having on average 3.5 mol of ethylene oxide (EO) or C 12 - C 18 -fatty alcohols with 1 to 4 EO. The preferred anionic surfactants also include the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters, and the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contain C 8 to C 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. Likewise, it is also possible to use alk (en) ylsuccinic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof. Suitable further anionic surfactants are fatty acid derivatives of amino acids, for example N-methyltaurine (Tauride) and / or N-methylglycine (sarcosides). Particularly preferred are the sarcosides or the sarcosinates and here especially sarcosinates of higher and optionally monounsaturated or polyunsaturated fatty acids such as oleyl sarcosinate. As further anionic surfactants are particularly soaps into consideration. Particularly suitable are saturated fatty acid soaps, such as the salts of Laürinsäure, 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. Together with these soaps or as a substitute for soaps, it is also possible to use the known alkenylsuccinic acid salts.

Die anionischen Tenside, einschließlich der Seifen, können in Form ihrer Natrium-, Kalium- oder Ammoniumsalze sowie als lösliche Salze organischer Basen, wie Mono-, Di- oder Triethanolamin, vorliegen. Vorzugsweise liegen die anionischen Tenside in Form ihrer Natrium- oder Kaliumsalze, insbesondere in Form der Natriumsalze vor.The anionic surfactants, including soaps, 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.

Tenside sind in erfindungsgemäßen Waschmitteln in Mengenanteilen von vorzugsweise 5 Gew.-% bis 50 Gew.-%, insbesondere von 8 Gew.-% bis 30 Gew.-%, enthalten.Surfactants are present in detergents according to the invention in proportions of preferably from 5% by weight to 50% by weight, in particular from 8% by weight to 30% by weight.

Ein erfindungsgemäßes Mittel 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 Methylglycindiessigsäure, Nitrilotriessigsäure und Ethylendiamintetraessigsäure sowie Polyasparaginsäure, Polyphosphonsäuren, insbesondere Aminotris(methylenphos-phonsäure), Ethylendiamintetrakis(methylenphosphonsäure) und 1-Hydroxyethan-1,1-diphosphonsäure, polymere Hydroxyverbindungen wie Dextrin sowie polymere (Poly-)carbonsäuren, insbesondere die durch Oxidation von Polysacchariden beziehungsweise Dextrinen zugänglichen Polycarboxylate der europäischen Patentschrift EP 0 625 992 beziehungsweise der internationalen Patentanmeldung WO 92/18542 oder der europäischen Patentschrift EP 0 232 202 , polymere Acrylsäuren, Methacrylsäuren, Maleinsäuren und Mischpolymere aus diesen, die auch geringe Anteile polymerisierbarer Substanzen ohne Carbonsäurefunktionalität einpolymerisiert enthalten können. Die relative . Molekülmasse der Homopolymeren ungesättiger Carbonsäuren liegt im allgemeinen zwischen 3 000 und 200 000, die der Copolymeren zwischen 2 000 und 200 000, vorzugsweise 30 000 bis 120 000, jeweils bezogen auf freie Säure. Ein besonders bevorzugtes Acrylsäure-Maleinsäure-Copolymer weist eine relative Molekülmasse von 30 000 bis 100 000 auf. Handelsübliche Produkte sind zum Beispiel Sokalan® CP 5, CP 10 und PA 30 der Firma BASF. 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 einem veresterten Vinylalkohol 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, wobei Maleinsäure besonders bevorzugt ist, und/oder ein Derivat einer Allylsulfonsäure, die in 2-Stellung mit einem Akyl- oder Arylrest substituiert ist, sein. Derartige Polymere lassen sich insbesondere nach Verfahren herstellen, die in der deutschen Patentschrift DE 42 21 381 und der deutschen Patentanmeldung DE 43 00 772 beschrieben sind, und weisen im allgemeinen eine relative Molekülmasse zwischen 1 000 und 200 000 auf. Weitere bevorzugte Copolymere sind solche, die in den deutschen Patentanmeldungen DE 43 03 320 und DE 44 17 734 beschrieben werden und als Monomere vorzugsweise 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.An agent according to the invention 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 also polymeric (poly) -carboxylic acids, in particular the polycarboxylates of the European patent specification obtainable by oxidation of polysaccharides or dextrins EP 0 625 992 or the international patent application WO 92/18542 or the European patent specification EP 0 232 202 , polymeric acrylic acids, methacrylic acids, maleic acids and copolymers thereof, which may also contain small amounts of polymerizable substances copolymerized without carboxylic acid functionality. The relative. The molecular weight of the homopolymers of unsaturated carboxylic acids is generally between 3,000 and 200,000, that of the copolymers between 2,000 and 200,000, preferably 30,000 to 120,000, in each case based on the free acid. A particularly preferred acrylic acid-maleic acid copolymer has a molecular weight of from 30,000 to 100,000. Commercially available products are, for example, Sokalan® CP 5, CP 10 and PA 30 from BASF. Suitable, albeit less preferred, compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinylmethyl ethers, vinyl esters, ethylene, propylene and styrene, in which the proportion of acid is at least 50 wt .-%. 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 can be prepared in particular by methods described in the German patent DE 42 21 381 and the German patent application DE 43 00 772 are generally described, and generally have a molecular weight between 1,000 and 200,000. Further preferred copolymers are those described in the German patent applications DE 43 03 320 and DE 44 17 734 be described and as monomers preferably 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, erfindungsgemäßen 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 paste-form or liquid, in particular water-containing, agents according to the invention.

Als wasserlösliche anorganische Buildermaterialien kommen insbesondere Alkalisilikate, Alkalicarbonate und Alkaliphosphate, die in Form ihrer alkalischen, neutralen oder sauren Natrium- oder Kaliumsalze vorliegen können, in Betracht. Beispiele hierfür sind Trinatriumphosphat, Tetranatriumdiphosphat, Dinatriumdihydrogendiphosphat, Pentanatriumtriphosphat, sogenanntes Natriumhexametaphosphat, oligomeres Trinatriumphosphat mit Oligomerisierungsgraden von 5 bis 1000, insbesondere 5 bis 50, sowie die entsprechenden Kaliumsalze beziehungsweise Gemische aus Natrium- und Kaliumsalzen. Als wasserunlösliche, wasserdispergierbare anorganische Buildermaterialien werden insbesondere kristalline oder amorphe Alkalialumosilikate, in Mengen von bis zu 50 Gew.-%, vorzugsweise nicht über 40 Gew.-% und in flüssigen Mitteln insbesondere von 1 Gew.-% bis 5 Gew.-%, eingesetzt. Unter diesen sind die kristallinen Natriumalumosilikate in Waschmittelqualität, insbesondere Zeolith A, P und gegebenenfalls X, allein oder in Mischungen, beispielsweise in Form eines Co-Kristallisats aus den Zeolithen A und X (Vegoborid® AX, ein Handelsprodukt der Condea Augusta S.p.A.), 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, das nach den Angaben der deutschen Patentschrift DE 24 12 837 bestimmt werden kann, liegt in der Regel im Bereich von 100 bis 200 mg CaO pro Gramm.Suitable water-soluble inorganic builder materials are, in particular, alkali metal silicates, alkali metal carbonates and alkali metal phosphates, which may be in the form of their alkaline, neutral or acidic sodium or potassium salts. Examples of these are trisodium phosphate, tetrasodium diphosphate, disodium dihydrogen diphosphate, pentasodium triphosphate, so-called sodium hexametaphosphate, oligomeric trisodium phosphate with degrees of oligomerization of from 5 to 1000, in particular from 5 to 50, 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. Among these, preferred are the detergent grade crystalline sodium aluminosilicates, particularly zeolite A, P and optionally X, alone or in mixtures, for example in the form of a cocrystal of zeolites A and X (Vegoborid® AX, a commercial product of Condea Augusta SpA) , 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, according to the information of the German Patent DE 24 12 837 can be determined, is usually in the range of 100 to 200 mg CaO per gram.

Geeignete Substitute beziehungsweise Teilsubstitute für das genannte Alumosilikat sind kristalline Alkalisilikate, die allein oder im Gemisch mit amorphen Silikaten vorliegen können. Die in den erfindungsgemäßen Mitteln als Gerüststoffe 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. Solche mit einem molaren Verhältnis Na2O:SiO2 von 1:1,9 bis 1:2,8 können nach dem Verfahren der europäischen Patentanmeldung EP 0 425 427 hergestellt werden. 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 22, insbesondere 1,9 bis 4 und y eine Zahl von 0 bis 33 ist und bevorzugte Werte für x 2, 3 oder 4 sind. Kristalline Schichtsilikate, die unter diese allgemeine Formel fallen, werden beispielsweise in der europäischen Patentanmeldung EP 0 164 514 beschrieben. Bevorzugte kristalline Schichtsilikate sind solche, bei denen x in der genannten allgemeinen Formel die Werte 2 oder 3 annimmt. Insbesondere sind sowohl ß- als auch δ-Natriumdisilikate (Na2Si2O5 y H2O) bevorzugt, wobei ß-Natriumdisilikat beispielsweise nach dem Verfahren erhalten werden kann, das in der internationalen Patentanmeldung WO 91/08171 beschrieben ist. δ-Natriumsilikate mit einem Modul zwischen 1,9 und 3,2 können gemäß den japanischen Patentanmeldungen JP 04/238 809 oder JP 04/260 610 hergestellt werden. 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, herstellbar wie in den europäischen Patentanmeldungen EP 0 548 599 , EP 0 502 325 und EP 0 452 428 beschrieben, können in erfindungsgemäßen Mitteln eingesetzt werden. In einer weiteren bevorzugten Ausführungsform erfindungsgemäßer Mittel wird ein kristallines Natriumschichtsilikat mit einem Modul von 2 bis 3 eingesetzt, wie es nach dem Verfahren der europäischen Patentanmeldung EP 0 436 835 aus Sand und Soda hergestellt werden kann. Kristalline Natriumsilikate mit einem Modul im Bereich von 1,9 bis 3,5, wie sie nach den Verfahren der europäischen Patentschriften EP 0 164 552 und/oder EP 0 294 753 erhältlich sind, werden in einer weiteren bevorzugten Ausführungsform erfindungsgemäßer Mittel eingesetzt. Kristalline schichtförmige Silikate der oben angegebenen Formel (I) werden von der Fa. Clariant GmbH unter dem Handelsnamen Na-SKS vertrieben, z.B. Na-SKS-1 (Na2Si22O45xH2O, Kenyait), Na-SKS-2 (Na2Si14O29xH2O, Magadiit), Na-SKS-3 (Na2Si8O17-xH2O) oder Na-SKS-4 (Na2Si4O9xH2O, Makatit). Von diesen eignen sich vor allem Na-SKS-5 (α-Na2Si2O5), Na-SKS-7 (ß-Na2Si2O5, Natrosilit), Na-SKS-9 (NaHSi2O53H2O), Na-SKS-10 (NaHSi2O5-3H2O, Kanemit), Na-SKS-11 (t-Na2Si2O5) und Na-SKS-13 (Na)HSi2O5), insbesondere aber Na-SKS-6 (S-Na2Si2O5). Einen Überblick über kristalline Schichtsilikate geben zum Beispiel die im " Hoechst High Chem Magazin 14/1993" auf den Seiten 33 - 38 und in " Seifen-Öle-Fette-Wachse, 116 Jahrgang, Nr. 20/-1990" auf den Seiten 805 - 808 veröffentlichten Artikel. In einer bevorzugten Ausgestaltung erfindungsgemäßer Mittel setzt man ein granulares Compound aus kristallinem Schichtsilikat und Citrat, aus kristallinem Schichtsilikat und oben genannter (co-)polymerer Polycarbonsäure, wie es zum Beispiel in der deutschen Patentanmeldung DE 198 19 187 beschrieben ist, oder aus Alkalisilikat und Alkalicarbonat ein, wie es zum Beispiel in der internationalen Patentanmeldung WO 95/22592 beschrieben ist oder wie es beispielsweise unter dem Namen Nabion® 15 im Handel erhältlich ist.Suitable substitutes or partial substitutes for the said aluminosilicate are crystalline alkali silicates which may be present alone or in a mixture with amorphous silicates. The alkali metal silicates useful as builders in the compositions according to the invention 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. Those with a molar ratio Na 2 O: SiO 2 of 1: 1.9 to 1: 2.8 can be prepared by the process of European patent application EP 0 425 427 getting produced. The crystalline silicates which may be present alone or in admixture with amorphous silicates, are crystalline layer silicates with the general formula Na 2 Si x O y are used 2x + 1 H 2 O, in which x, the so-called module, a number from 1.9 to 22, in particular 1.9 to 4 and y is a number from 0 to 33 and preferred values for x are 2, 3 or 4. Crystalline layered silicates which fall under this general formula are described, for example, in the European patent application EP 0 164 514 described. Preferred crystalline phyllosilicates are those in which x in the abovementioned general formula assumes the values 2 or 3. In particular, both .beta.- and δ-sodium (Na 2 Si 2 O 5 y H 2 O) are preferred, with beta-sodium disilicate being obtainable, for example, by the method described in the international patent application WO 91/08171 is described. δ-Sodium silicates with a modulus between 1.9 and 3.2 can according to Japanese Patent Applications JP 04/238 809 or JP 04/260 610 getting produced. Also prepared from amorphous alkali metal silicates, practically anhydrous crystalline alkali metal silicates of the above general formula in which x is a number from 1.9 to 2.1, preparable as in the European patent applications EP 0 548 599 . EP 0 502 325 and EP 0 452 428 can be used in agents according to the invention. In a further preferred embodiment of the composition according to the invention, a crystalline sodium layer silicate with a modulus of 2 to 3 is used, as it is by the process of European patent application EP 0 436 835 made from sand and soda. Crystalline sodium silicates with a modulus ranging from 1.9 to 3.5, as prepared by the methods of European patents EP 0 164 552 and or EP 0 294 753 are available are used in a further preferred embodiment of the invention means. Crystalline layer-form silicates of formula (I) given above are sold by Clariant GmbH under the trade name Na-SKS, eg Na-SKS-1 (Na 2 Si 22 O 45 .H 2 O, Kenyaite), Na-SKS-2 (Na 2 Si 14 O 29 × H 2 O, magadiite), Na-SKS-3 (Na 2 Si 8 O 17 -xH 2 O) or Na-SKS-4 (Na 2 Si 4 O 9 × H 2 O, makatite) , Of these, especially Na-SKS-5 (α-Na 2 Si 2 O 5 ), Na-SKS-7 (β-Na 2 Si 2 O 5 , Natrosilit), Na-SKS-9 (NaHSi 2 O 5 3H 2 O), Na-SKS-10 (NaHSi 2 O 5 -3H 2 O, kanemite), Na-SKS-11 (t-Na 2 Si 2 O 5 ), and Na-SKS-13 (Na) HSi 2 O 5 ), but especially Na-SKS-6 (S-Na 2 Si 2 O 5 ). For example, an overview of crystalline phyllosilicates can be found in the " Hoechst High Chem Magazine 14/1993 "on pages 33 - 38 and in " Soap-oil-grease waxes, 116 vintage, No. 20 / -1990 "on pages 805 - 808 published article. In a preferred embodiment of compositions according to the invention, a granular compound of crystalline phyllosilicate and citrate, of crystalline phyllosilicate and of the abovementioned (co) polymeric polycarboxylic acid, as described, for example, in the German patent application DE 198 19 187 or from alkali metal silicate and alkali metal carbonate, as described for example in the international patent application WO 95/22592 or as it is commercially available, for example, under the name Nabion® 15.

Buildersubstanzen sind in den erfindungsgemäßen Mitteln vorzugsweise in Mengen bis zu 75 Gew.-%, insbesondere 5 Gew.-% bis 50 enthalten.Builder substances are preferably present in the compositions according to the invention in amounts of up to 75% by weight, in particular 5% by weight to 50.

Als für den Einsatz in erfindungsgemäßen Mitteln geeignete Persauerstoffverbindungen kommen insbesondere organische Persäuren beziehungsweise persaure Salze organischer Säuren, wie Phthalimidopercapronsäure, Perbenzoesäure oder Salze der Diperdodecandisäure, Wasserstoffperoxid und unter den Waschbedingungen Wasserstoffperoxid abgebende anorganische Salze, zu denen Perborat, Percarbonat, Persilikat und/oder Persulfat wie Caroat gehören, in Betracht. 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. Falls ein erfindungsgemäßes Mittel Persauerstoffverbindungen enthält, sind diese in Mengen von vorzugsweise bis zu 50 Gew.-%, insbesondere von 5 Gew.-% bis 30 Gew.-%, vorhanden. Der Zusatz geringer Mengen bekannter Bleichmittelstabilisatoren wie beispielsweise von Phosphonaten, Boraten beziehungsweise Metaboraten und Metasilikaten sowie Magnesiumsalzen wie Magnesiumsulfat kann zweckdienlich sein.As for the use in agents according to the invention suitable peroxygen compounds are 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 donating inorganic salts, which include perborate, percarbonate, persilicate and / or persulfate Caroat belong into consideration. 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. If an agent according to the invention contains peroxygen compounds, they are present in amounts of preferably up to 50% by weight, in particular from 5% by weight to 30% by weight. The addition of small amounts of known bleach stabilizers such as phosphonates, borates or metaborates and metasilicates and magnesium salts such as magnesium sulfate may be useful.

Als Bleichaktivatoren können Verbindungen, die unter Perhydrolysebedingungen aliphatische Peroxocarbonsäuren mit vorzugsweise 1 bis 10 C-Atomen, insbesondere 2 bis 4 C-Atomen, und/oder gegebenenfalls substituierte Perbenzoesäure ergeben, eingesetzt werden. Geeignet sind Substanzen, die O- und/oder N-Acylgruppen der genannten C-Atomzahl und/oder gegebenenfalls substituierte Benzoylgruppen tragen. Bevorzugt sind mehrfach acylierte Alkylendiamine, insbesondere Tetraacetylethylendiamin (TAED), acylierte Triazinderivate, insbesondere 1,5-Diacetyl-2,4-dioxohexahydro-1,3,5-triazin (DADHT), acylierte Glykolurile, insbesondere Tetraacetylglykoluril (TAGU), N-Acylimide, insbesondere N-Nonanoylsuccinimid (NOSI), acylierte Phenolsulfonate, insbesondere n-Nonanoyl- oder Isononanoyloxybenzolsulfonat (n- bzw. iso-NOBS), Carbonsäureanhydride, insbesondere Phthalsäureanhydrid, acylierte mehrwertige Alkohole, insbesondere Triacetin, Ethylenglykoldiacetat, 2,5-Diacetoxy-2,5-dihydrofuran und die aus den deutschen Patentanmeldungen DE 196 16 693 und DE 196 16 767 bekannten Enolester sowie acetyliertes Sorbitol und Mannitol beziehungsweise deren in der europäischen Patentanmeldung EP 0 525 239 beschriebene Mischungen (SORMAN), acylierte Zuckerderivate, insbesondere Pentaacetylglukose (PAG), Pentaacetylfruktose, Tetraacetylxylose und Octaacetyllactose sowie acetyliertes, gegebenenfalls N-alkyliertes Glucamin und Gluconolacton, und/oder N-acylierte Lactame, beispielsweise N-Benzoylcaprolactam, die aus den internationalen Patentanmeldungen WO 94/27970 , WO 94/28102 , WO 94/28103 , WO 95/00626 , WO 95/14759 und WO 95/17498 bekannt sind. Die aus der deutschen Patentanmeldung DE 196 16 769 bekannten hydrophil substituierten Acylacetale und die in der deutschen Patentanmeldung DE 196 16 770 sowie der internationalen Patentanmeldung WO 95/14075 beschriebenen Acyllactame werden ebenfalls bevorzugt eingesetzt. Auch die aus der deutschen Patentanmeldung DE 44 43 177 bekannten Kombinationen konventioneller Bleichaktivatoren können eingesetzt werden. Derartige Bleichaktivatoren können, insbesondere bei Anwesenheit obengenannter Wasserstoffperoxid-liefernder Bleichmittel, im üblichen Mengenbereich, vorzugsweise in Mengen von 0,5 Gew.-% bis 10 Gew.-%, insbesondere 1 Gew.-% bis 8 Gew.-%, bezogen auf gesamtes Mittel, enthalten sein, fehlen bei Einsatz von Percarbonsäure als alleinigem Bleichmittel jedoch vorzugsweise ganz.As bleach activators, it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups. Preference is given to polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate, 2,5-diacetoxy- 2,5-dihydrofuran and from the German patent applications DE 196 16 693 and DE 196 16 767 known enol esters and acetylated sorbitol and mannitol or their in the European patent application EP 0 525 239 mixtures described (SORMAN), acylated sugar derivatives, in particular pentaacetylglucose (PAG), pentaacetyl fructose, Tetraacetylxylose and Octaacetyllactose and acetylated, optionally N-alkylated glucamine and gluconolactone, and / or N-acylated lactams, for example N-benzoyl-caprolactam, which are known from international patent applications WO 94/27970 . WO 94/28102 . WO 94/28103 . WO 95/00626 . WO 95/14759 and WO 95/17498 are known. The from the German patent application DE 196 16 769 known hydrophilic substituted acyl acetals and in the German patent application DE 196 16 770 as well as the international patent application WO 95/14075 Acyllactame described are also preferably used. Also from the German patent application DE 44 43 177 known combinations of conventional bleach activators can be used. Such bleach activators can, in particular in the presence of the abovementioned hydrogen peroxide-producing bleach, in the usual amount range, preferably in amounts of from 0.5 wt .-% to 10 wt .-%, in particular 1 wt .-% to 8 wt .-%, based on However, total agent, be included, missing when using percarboxylic acid as the sole bleach, preferably completely.

Zusätzlich zu den konventionellen Bleichaktivatoren oder an deren Stelle können auch die aus den europäischen Patentschriften EP 0 446 982 und EP 0 453 003 bekannten Sulfonimine und/oder bleichverstärkende Übergangsmetallsalze beziehungsweise Übergangsmetallkomplexe als sogenannte Bleichkatalysatoren enthalten sein.In addition to or instead of the conventional bleach activators, it is also possible to use those from European patents EP 0 446 982 and EP 0 453 003 be known sulphonic imines and / or bleach-enhancing transition metal salts or transition metal complexes as so-called bleach catalysts.

Als in den Mitteln verwendbare Enzyme kommen solche aus der Klasse der Amylasen, Proteasen, Lipasen, Cutinasen, Pullulanasen, Hemicellulasen, Cellulasen, Oxidasen, Laccasen und Peroxidasen sowie deren Gemische in Frage. Besonders geeignet sind aus Pilzen oder Bakterien, wie Bacillus subtilis, Bacillus licheniformis, Bacillus lentus, Streptomyces griseus, Humicola lanuginosa, Humicola insolens, Pseudomonas pseudoalcaligenes, Pseudomonas cepacia oder Coprinus cinereus gewonnene enzymatische Wirkstoffe. Die Enzyme können, wie zum Beispiel in der europäischen Patentschrift EP 0 564 476 oder in der internationalen Patentanmeldung WO 94/23005 beschrieben, an Trägerstoffen adsorbiert und/oder in Hüllsubstanzen eingebettet sein, um sie gegen vorzeitige Inaktivierung zu schützen. Sie sind in den erfindungsgemäßen Wasch- oder Reinigungsmitteln vorzugsweise in Mengen bis zu 5 Gew.-%, insbesondere von 0,2 Gew.-% bis 4 Gew.-%, enthalten. Falls das erfindungsgemäße Mittel Protease enthält, weist es vorzugsweise eine proteolytische Aktivität im Bereich von etwa 100 PE/g bis etwa 10 000 PE/g, insbesondere 300 PE/g bis 8000 PE/g auf. Falls mehrere Enzyme in dem erfindungsgemäßen Mittel eingesetzt werden sollen, kann dies durch Einarbeitung der zwei oder mehreren separaten beziehungsweise in bekannter Weise separat konfektionierten Enzyme oder durch zwei oder mehrere gemeinsam in einem Granulat konfektionierte Enzyme, wie zum Beispiel aus den internationalen Patentanmeldungen WO 96/00772 oder WO 96/00773 bekannt, durchgeführt werden.Suitable enzymes which can be used in the compositions are those from the class of amylases, proteases, lipases, cutinases, pullulanases, hemicellulases, cellulases, oxidases, laccases and peroxidases and mixtures thereof. Particularly suitable are from fungi or bacteria, such as Bacillus subtilis, Bacillus licheniformis, Bacillus lentus, Streptomyces griseus, Humicola lanuginosa, Humicola insolens, Pseudomonas pseudoalcaligenes, Pseudomonas cepacia or Coprinus cinereus derived enzymatic agents. The enzymes can be as described, for example, in the European patent EP 0 564 476 or in the international patent application WO 94/23005 be adsorbed to carriers and / or embedded in encapsulating substances to protect against premature inactivation. They are preferably present in the detergents or cleaners according to the invention in amounts of up to 5% by weight, in particular from 0.2% by weight to 4% by weight. If the agent of the invention contains protease, it preferably has a proteolytic activity in the range of about 100 PE / g to about 10 000 PE / g, in particular 300 PE / g to 8000 PE / g. If several enzymes are to be used in the agent according to the invention, this can be achieved by incorporation of the two or more separate or separately synthesized enzymes or by two or more enzymes synthesized together in a granulate, for example from international patent applications WO 96/00772 or WO 96/00773 known to be performed.

Zu den in den erfindungsgemäßen Mitteln, insbesondere wenn sie in flüssiger oder pastöser Form vorliegen, neben Wasser 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 erfindungsgemäßen Mitteln vorzugsweise in Mengen nicht über 30 Gew.-%, insbesondere von 6 Gew.-% bis 20 Gew.-%, vorhanden.Among the solvents according to the invention, in particular when they are in liquid or pasty form, organic solvents which can be used in addition to water include alcohols having 1 to 4 C atoms, in particular methanol, ethanol, isopropanol and tert-butanol, diols having 2 to 4 C -Atomen, in particular ethylene glycol and propylene glycol, and mixtures thereof and derived from the classes of compounds mentioned ether. Such water-miscible solvents are preferably present in the compositions according to the invention in amounts of not more than 30% by weight, in particular from 6% by weight to 20% by weight.

Zur Einstellung eines gewünschten, sich durch die Mischung der übrigen Komponenten nicht von selbst ergebenden pH-Werts können die erfindungsgemäßen Mittel system- und umweltverträgliche Säuren, insbesondere Citronensäure, Essigsäure, Weinsäure, Äpfelsäure, Milchsäure, Glykolsäure, Bernsteinsäure, Glutarsäure und/oder Adipinsäure, aber auch Mineralsäuren, insbesondere Schwefelsäure, oder Basen, insbesondere Ammonium- oder Alkalihydroxide, enthalten. Derartige pH-Regulatoren sind in den erfindungsgemäßen Mitteln in Mengen von vorzugsweise nicht über 20 Gew.-%, insbesondere von 1,2 Gew.-% bis 17 Gew.-%, enthalten.In order to establish a desired pH, which does not result from the mixture of the other components, the compositions according to the invention can contain system- and environmentally compatible 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 present in the compositions according to the invention in amounts of preferably not more than 20% by weight, in particular from 1.2% by weight to 17% by weight.

Vergrauungsinhibitoren haben die Aufgabe, den von der Textilfaser abgelösten Schmutz in der Flotte suspendiert zu halten. Hierzu sind wasserlösliche Kolloide meist organischer Natur geeignet, beispielsweise Stärke, Leim, Gelatine, Salze von Ethercarbonsäuren oder Ethersulfonsäuren der Stärke oder der Cellulose oder Salze von sauren Schwefelsäureestern der Cellulose oder der Stärke. Auch wasserlösliche, saure Gruppen enthaltende Polyamide sind für diesen Zweck geeignet. Weiterhin lassen sich andere als die obengenannten Stärkederivate verwenden, zum Beispiel Aldehydstärken. Bevorzugt werden Celluloseether, wie Carboxymethylcellulose (Na-Salz), Methylcellulose, Hydroxyalkylcellulose und Mischether, wie Methylhydroxyethylcellulose, Methylhydroxypropylcellulose, Methylcarboxymethylcellulose und deren Gemische, beispielsweise in Mengen von 0,1 bis 5 Gew.-%, bezogen auf die Mittel, eingesetzt.Graying inhibitors have the task of keeping suspended from the textile fiber dirt suspended in the fleet. Water-soluble colloids of mostly organic nature are suitable for this purpose, for example starch, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or of cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Also, water-soluble polyamides containing acidic groups are suitable for this purpose. Furthermore, other than the above-mentioned starch derivatives can be used, for example aldehyde starches. Preference is given to cellulose ethers, such as carboxymethylcellulose (sodium salt), methylcellulose, Hydroxyalkylcellulose and mixed ethers, such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof, for example in amounts of 0.1 to 5 wt .-%, based on the means used.

Erfindungsgemäße Textilwaschmittel können als optische Aufheller beispielsweise Derivate der Diaminostilbendisulfonsäure beziehungsweise deren Alkalimetallsalze enthalten, obgleich sie für den Einsatz als Colorwaschmittel vorzugsweise frei von optischen Aufhellern sind. Geeignet sind zum Beispiel Salze der 4,4'-Bis(2-anilino-4-morpholino-1,3,5-triazinyl-6-amino)stilben-2,2'-disulfonsäure oder gleichartig aufgebaute Verbindungen, die anstelle der Morpholino-Gruppe eine Diethanolaminogruppe, eine Methylaminogruppe, eine Anilinogruppe oder eine 2-Methoxyethylaminogruppe tragen. Weiterhin können Aufheller vom Typ der substituierten Diphenylstyryle anwesend sein, zum Beispiel die Alkalisalze des 4,4'-Bis(2-sulfostyryl)-diphenyls, 4,4'-Bis(4-chlor-3-sulfostyryl)-diphenyls, oder 4-(4-Chlorstyryl)-4'-(2-sulfostyryl)-diphenyls. Auch Gemische der vorgenannten optischen Aufheller können verwendet werden.Detergents according to the invention may contain, for example, derivatives of diaminostilbenedisulfonic acid or their alkali metal salts as optical brighteners, although they are preferably free of optical brighteners for use as color detergents. 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. Further, 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.

Insbesondere beim Einsatz in maschinellen Verfahren kann es von Vorteil sein, den Mitteln übliche Schauminhibitoren zuzusetzen. Als Schauminhibitoren eignen sich beispielsweise Seifen natürlicher oder synthetischer Herkunft, die einen hohen Anteil an C18-C24-Fettsäuren aufweisen. Geeignete nichttensidartige Schauminhibitoren sind beispielsweise Organopolysiloxane und deren Gemische mit mikrofeiner, gegebenenfalls silanierter Kieselsäure sowie Paraffine, Wachse, Mikrokristallinwachse und deren Gemische mit silanierter Kieselsäure oder Bisfettsäurealkylendiamiden. Mit Vorteilen werden auch Gemische aus verschiedenen Schauminhibitoren verwendet, zum Beispiel solche aus Silikonen, Paraffinen oder Wachsen. Vorzugsweise sind die Schauminhibitoren, insbesondere Silikon- und/oder Paraffin-haltige Schauminhibitoren, an eine granulare, in Wasser lösliche beziehungsweise dispergierbare Trägersubstanz gebunden. Insbesondere sind dabei Mischungen aus Paraffinen und Bistearylethylendiamid bevorzugt.In particular, when used in mechanical processes, it may be advantageous to add conventional foam inhibitors to the compositions. As 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.

Die Herstellung erfindungsgemäßer fester Mittel bietet keine Schwierigkeiten und kann auf bekannte Weise, zum Beispiel durch Sprühtrocknen oder Granulation, erfolgen, wobei Enzyme und eventuelle weitere thermisch empfindliche Inhaltsstoffe wie zum Beispiel Bleichmittel gegebenenfalls später separat zugesetzt werden. Zur Herstellung erfindungsgemäßer Mittel mit erhöhtem Schüttgewicht, insbesondere im Bereich von 650 g/l bis 950 g/l, ist ein aus der europäischen Patentschrift EP 0 486 592 bekanntes, einen Extrusionschritt aufweisendes Verfahren bevorzugt. Eine weitere bevorzugte Herstellung mit Hilfe eines Granulationsverfahrens ist in der europäischen Patentschrift EP 0 642 576 beschrieben.The preparation of solid compositions according to the invention presents no difficulties and can be carried out in a known manner, for example by spray-drying or granulation, enzymes and possibly other thermally sensitive ingredients such as, for example, bleaching agents optionally being added separately later. For the production according to the invention Agent with increased bulk density, in particular in the range of 650 g / l to 950 g / l, is one from the European patent EP 0 486 592 known method comprising an extrusion step is preferred. Another preferred preparation by means of a granulation process is in the European patent specification EP 0 642 576 described.

Zur Herstellung von erfindungsgemäßen Mitteln in Tablettenform, die einphasig oder mehrphasig, einfarbig oder mehrfarbig und insbesondere aus einer Schicht oder aus mehreren, insbesondere aus zwei Schichten bestehen können, geht man vorzugsweise derart vor, daß man alle Bestandteile - gegebenenfalls je einer Schicht - in einem Mischer miteinander vermischt und das Gemisch mittels herkömmlicher Tablettenpressen, beispielsweise Exzenterpressen oder Rundläuferpressen, mit Preßkräften im Bereich von etwa 50 bis 100 kN, vorzugsweise bei 60 bis 70 kN verpreßt. Insbesondere bei mehrschichtigen Tabletten kann es von Vorteil sein, wenn mindestens eine Schicht vorverpreßt wird. Dies wird vorzugsweise bei Preßkräften zwischen 5 und 20 kN, insbesondere bei 10 bis 15 kN durchgeführt. Man erhält so problemlos bruchfeste und dennoch unter Anwendungsbedingungen ausreichend schnell lösliche Tabletten mit Bruch- und Biegefestigkeiten von normalerweise 100 bis 200 N, bevorzugt jedoch über 150 N. Vorzugsweise weist eine derart hergestellte Tablette ein Gewicht von 10 g bis 50 g, insbesondere von 15 g bis 40 g auf. Die Raumform der Tabletten ist beliebig und kann rund, oval oder eckig sein, wobei auch Zwischenformen möglich sind. Ecken und Kanten sind vorteilhafterweise abgerundet. Runde Tabletten weisen vorzugsweise einen Durchmesser von 30 mm bis 40 mm auf. Insbesondere die Größe von eckig oder quaderförmig gestalteten Tabletten, welche überwiegend über die Dosiervorrichtung beispielsweise der Geschirrspülmaschine eingebracht werden, ist abhängig von der Geometrie und dem Volumen dieser Dosiervorrichtung. Beispielhaft bevorzugte Ausführungsformen weisen eine Grundfläche von (20 bis 30 mm) x (34 bis 40 mm), insbesondere von 26x36 mm oder von 24x38 mm auf.For the preparation of compositions according to the invention in tablet form, which may be monophasic or multiphase, monochromatic or multicolor and in particular consist of one or more layers, in particular two layers, the procedure is preferably such that all constituents - if appropriate one per layer - in one Mixer mixed together and the mixture by means of conventional tablet presses, such as eccentric or rotary presses, pressed with compressive forces in the range of about 50 to 100 kN, preferably at 60 to 70 kN. Particularly in the case of multilayer tablets, it may be advantageous if at least one layer is pre-compressed. This is preferably carried out at pressing forces between 5 and 20 kN, in particular at 10 to 15 kN. This gives fracture-resistant, yet sufficiently rapidly soluble tablets under application conditions with fracture and flexural strengths of normally 100 to 200 N, but preferably above 150 N. Preferably, a tablet produced in this way has a weight of 10 g to 50 g, in particular 15 g up to 40 g. The spatial form of the tablets is arbitrary and can be round, oval or angular, with intermediate forms are also possible. Corners and edges are advantageously rounded. Round tablets preferably have a diameter of 30 mm to 40 mm. In particular, the size of rectangular or cuboid-shaped tablets, which are introduced predominantly via the metering device, for example the dishwasher, is dependent on the geometry and the volume of this metering device. Exemplary preferred embodiments have a base area of (20 to 30 mm) x (34 to 40 mm), in particular of 26x36 mm or 24x38 mm.

Flüssige beziehungsweise pastöse erfindungsgemäße Mittel in Form von übliche Lösungsmittel enthaltenden Lösungen werden in der Regel durch einfaches Mischen der Inhaltsstoffe, die in Substanz oder als Lösung in einen automatischen Mischer gegeben werden können, hergestellt.Liquid or pasty compositions according to the invention in the form of customary solvent-containing solutions are generally prepared by simply mixing the ingredients, which can be added in bulk or as a solution in an automatic mixer.

BeispieleExamples Beispiel 1: Herstellung von N,N'-Bis-[2-chlor-4(sulfonaphth-1-yl-amino)-triazin-6-yl]-1,2-diaminoethanExample 1: Preparation of N, N'-bis [2-chloro-4 (sulfonaphth-1-yl-amino) -triazin-6-yl] -1,2-diaminoethane

Cyanurchlorid (8,26 g, 0,044 mol), suspendiert in einer Mischung aus Eis und Aceton (50 ml), wurde bei 0 °C zu einer gerührten wäßrigen Lösung von 4-Aminonaphthalin-1-sulfonsäure (10,1 g, 0,044 mol) gegeben. Die Mischung wurde bei pH 4,5 bis 5 (mit Natriumcarbonat eingestellt) und 0 bis 5 °C 5 Stunden gerührt, danach innerhalb von 1 Stunde auf 20 °C erwärmt. 75 prozentiges Ethylendiamin (1,78 g, 0,022 mol) wurde zugegeben und die Mischung wurde 16 Stunden bei 30 °C und pH 8,5 (eingestellt durch NaOH) gerührt. Phosphatpuffermischung (pH 6,5) und danach Aceton (1,5 1) wurden zugegeben. Der ausfallende farblose Feststoff wurde abgetrennt (Ausbeute 10,9 g, 53,8 % Reinheit).Cyanuric chloride (8.26 g, 0.044 mol) suspended in a mixture of ice and acetone (50 ml) was added at 0 ° C to a stirred aqueous solution of 4-aminonaphthalene-1-sulfonic acid (10.1 g, 0.044 mol ). The mixture was stirred at pH 4.5 to 5 (adjusted with sodium carbonate) and 0 to 5 ° C for 5 hours, then heated to 20 ° C within 1 hour. Seventy-five percent of ethylenediamine (1.78 g, 0.022 mol) was added and the mixture was stirred for 16 hours at 30 ° C and pH 8.5 (adjusted by NaOH). Phosphate buffer mixture (pH 6.5) and then acetone (1.5 L) were added. The precipitated colorless solid was separated (yield 10.9 g, 53.8% purity).

Beispiel 2: Herstellung von N,N'-Bis-[2-chlor-4-(1,5-disulfonaphth-2-yl-amino)-triazin-6-yl]-1,2-diaminoethanExample 2: Preparation of N, N'-bis [2-chloro-4- (1,5-disulfonaphth-2-yl-amino) -triazin-6-yl] -1,2-diaminoethane

2-Aminonaphthalin-1,5-disulfonsäure (77 prozentig, 20 g, 0,051 mol) wurde mit 1 Molequivalent Cyanurchlorid und 0,5 Molequivalenten Ethylendiamin unter den in Beispiel 1 beschrieben Bedingungen umgesetzt. Aceton wurde unter Rühren zugesetzt und das ausfallende Produkt wurde abgetrennt (Ausbeute 23 g, 64 % Reinheit).2-Aminonaphthalene-1,5-disulfonic acid (77 percent, 20 g, 0.051 mol) was reacted with 1 molar equivalent of cyanuric chloride and 0.5 molar equivalents of ethylenediamine under the conditions described in Example 1. Acetone was added with stirring and the precipitated product was separated (yield 23 g, 64% purity).

Beispiel 3: Herstellung von N.N'-Bis-[2-chlor-4-(3,6,8-trisulfonaphth-2-yl-amino)-triazin-6-yl]-1,2-diaminoethan Example 3: Preparation of N, N'-bis [2-chloro-4- (3,6,8-trisulfonaphth-2-yl-amino) -triazin- 6-yl] -1,2-diaminoethane

Cyanurchlorid (3,24 g, 0,018 mol), suspendiert in einer Mischung aus Eis und Aceton (50 ml), wurde bei 0 °C zu einer gerührten wäßrigen Lösung von 2-Aminonaphthalin-3,6,8-trisulfonsäure (66,5 prozentig, 10 g, 0,017 mol) gegeben. Die Mischung wurde bei pH 5 bis 5,5 (mit Natriumcarbonat eingestellt) und 0 bis 5°C 5 Stunden gerührt, danach innerhalb von 1 Stunde auf 20 °C erwärmt. 75 prozentiges Ethylendiamin (0,70 g, 0,009 mol) wurde zugegeben und die Mischung wurde 18 Stunden bei 30 °C und pH 8 bis 8,5 (eingestellt durch NaOH) gerührt. Phosphatpuffermischung (pH 6,5) und danach Aceton wurden zugegeben. Der ausfallende farblose Feststoff wurde abgetrennt (Ausbeute 4,14 g, 51 % Reinheit).Cyanuric chloride (3.24 g, 0.018 mol) suspended in a mixture of ice and acetone (50 ml) was added at 0 ° C to a stirred aqueous solution of 2-aminonaphthalene-3,6,8-trisulfonic acid (66.5 percent, 10 g, 0.017 mol). The mixture was stirred at pH 5 to 5.5 (adjusted with sodium carbonate) and 0 to 5 ° C for 5 hours, then heated to 20 ° C within 1 hour. Seventy-five percent of ethylenediamine (0.70 g, 0.009 mol) was added and the mixture was stirred for 18 hours at 30 ° C and pH 8 to 8.5 (adjusted by NaOH). Phosphate buffer mixture (pH 6.5) and then acetone were added. The precipitated colorless solid was separated (yield 4.14 g, 51% purity).

Beispiel 4: Herstellung von 4,4'-Bis-(2,4-dichlortriazin-6-ylamino)-stilben-2,2'-disulfonsäureExample 4: Preparation of 4,4'-bis (2,4-dichlorotriazine-6-ylamino) stilbene-2,2'-disulfonic acid

Cyanurchlorid (20,2 g, 0,109 mol), suspendiert in einer Mischung aus Eis und Aceton (80 ml), wurde bei 0 °C zu einer gerührten Lösung von 4,4'-Diaminostilben-2,2',-disulfonsäure (20 g, 0,054 mol) in 200 ml Wasser gegeben. Die Mischung wurde bei pH 5 bis 5,5 (mit Natriumcarbonat eingestellt) und 0 bis 5 °C 6 Stunden gerührt, danach auf 20 °C erwärmt und noch 2 Stunden bei dieser Temperatur gerührt. Die so angefallene Lösung wurde im Rahmen der Beispiele 5 bis 7 direkt weiter umgesetzt.Cyanuric chloride (20.2 g, 0.109 mol) suspended in a mixture of ice and acetone (80 ml) was added at 0 ° C to a stirred solution of 4,4'-diaminostilbene-2,2'-disulfonic acid (20 g, 0.054 mol) in 200 ml of water. The mixture was stirred at pH 5 to 5.5 (adjusted with sodium carbonate) and 0 to 5 ° C for 6 hours, then heated to 20 ° C and stirred for a further 2 hours at this temperature. The solution thus obtained was directly further reacted in the context of Examples 5 to 7.

Beispiel 5: Herstellung von 4,4'-Bis-[2-chlor-4-(4-sulfonaphth-1-yl-amino-)triazin-6-ylamino]-stilben-2,2'-disulfonsäureExample 5: Preparation of 4,4'-bis [2-chloro-4- (4-sulfonaphth-1-ylamino) triazin-6-ylamino] stilbene-2,2'-disulfonic acid

Zu der gemäß Beispiel 4 frisch hergestellten Lösung von 4,4'-Bis-(2,4-dichlortriazin-6-ylamino)-stilben-2,2'-disulfonsäure (0,006 mol) wurde eine wäßrige Lösung von 1-Aminonaphthalin-4-sulfonsäure (0,012 mol) gegeben. Die Mischung wurde bei pH 5,5 und 20 °C 24 Stunden gerührt.To the freshly prepared according to Example 4 solution of 4,4'-bis (2,4-dichlorotriazine-6-ylamino) -stilbene-2,2'-disulfonic acid (0.006 mol) was an aqueous solution of 1-aminonaphthalene-4th sulfonic acid (0.012 mol). The mixture was stirred at pH 5.5 and 20 ° C for 24 hours.

Beispiel 6: Herstellung von 4,4'-Bis-[2-chlor-4-(1,5-disulfonaphth-2-yl-amino-)triazin-6-ylamino]-stilben-2,2'-disulfonsäureExample 6: Preparation of 4,4'-bis [2-chloro-4- (1,5-disulfonaphth-2-ylamino) triazin-6-ylamino] stilbene-2,2'-disulfonic acid

Analog Beispiel 5 wurde 4,4'-Bis-(2,4-dichlortriazin-6-ylamino)-stilben-2,2'-disulfonsäure mit 2-Aminonaphthalin-1,5-disulfonsäure umgesetzt.4,4'-Bis (2,4-dichlorotriazine-6-ylamino) -stilbene-2,2'-disulphonic acid was reacted with 2-aminonaphthalene-1,5-disulphonic acid analogously to Example 5.

Beispiel 7: Herstellung von 4,4'-Bis-[2-chlor-4-(3,6,8-trisulfonaphth-2-yl-amino-)triazin-6-ylamino]-stilben-2,2'-disulfonsäureExample 7: Preparation of 4,4'-bis [2-chloro-4- (3,6,8-trisulfonaphth-2-ylamino) triazin-6-ylamino] stilbene-2,2'-disulfonic acid

Analog Beispiel 5 wurde 4,4'-Bis-(2,4-dichlortriazin-6-ylamino)-stilben-2,2'-disulfonsäure mit 2-Aminonaphthalin-3,6,8-trisulfonsäure umgesetzt.4,4'-Bis- (2,4-dichlorotriazine-6-ylamino) stilbene-2,2'-disulfonic acid was reacted with 2-aminonaphthalene-3,6,8-trisulfonic acid analogously to Example 5.

Beispiel 8: FarbübertragungsinhibierungExample 8: Color transfer inhibition

Durchführung: Die gemäß der voranstehenden Beispiele 1 bis 3 und 5 bis 7 hergestellten sulfonierten Triazin - Derivate wurden jeweils auf weiße Baumwolltextilien mit Hilfe einer wässrigen Lösung durch Tauchen zwangsappliziert und das weiße Textil dann in Gegenwart eines gefärbten Textils (Cibacron® Navy LS-G) bei 60 °C mit einem Pulverwaschmittel gewaschen. Die Anfärbung des weißen Textils wurde von einem erfahrenen Panel visuell begutachtet und auf einer Skala von 1 (= stark angefärbt) bis 5 (=keine erkennbare Anfärbung) benotet. Procedure: The sulfonated triazine derivatives prepared in accordance with the above Examples 1 to 3 and 5 to 7 were force-applied onto white cotton textiles by dipping with the aid of an aqueous solution and the white textile was then applied in the presence of a dyed textile (Cibacron® Navy LS-G). washed at 60 ° C with a powder detergent. The staining of the white textile was visually assessed by an experienced panel and graded on a scale from 1 (= strongly stained) to 5 (= no discernible staining).

Ergebnis: Die weißen Textilien wurden nicht angefärbt (Noten 4 bis 5), die ausgewaschene Farbe verblieb vollständig in der Flotte. Result: The white textiles were not stained (grades 4 to 5), the washed-out color remained completely in the liquor.

Claims (10)

  1. A method for washing dyed textiles in surfactant-containing aqueous solutions, characterized in that a surfactant-containing aqueous solution is applied, which contains a triazine derivative of general formulae I, II, III

            T(NH-Ar(SO3Na)a)bHalc     (I)

            X(NH-T(NH-Ar(SO3Na)a)eHalf)2     (II)

            X(NH-T(NH-Ar(SO3Na)d-NH-T(NH-Ar(SO3Na)a)Hal)Hal)2     (III)

    wherein
    T represents a 1,3,5-triazinyl radical,
    Ar represents a naphthalene or benzene group,
    X represents a linear or branched carbon chain optionally interrupted by NH groups, with 1 to 20, in particular 2 to 12 C atoms, or a stilbene or biphenyl group, optionally mono-or polysubstituted with -SO3Na,
    Hal represents chlorine, bromine or iodine,
    a and d, independently of each other, represent 1, 2 or 3,
    b represents 1 and c represents 2 or b represents 2 and c represents 1,
    e represents 1 and f represents 1 or e represents 2 and f represents 0,
    and the -NH- as well as the -Hal- substituents are found in the positions 2, 4 and 6 of the triazinyl ring.
  2. A washing agent, containing a dye transfer inhibitor in the form of a triazine derivative of general formula II,

            X(NH-T(NH-Ar(SO3Na)a)eHalf)2     (II)

    wherein
    T represents a 1,3,5-triazinyl radical,
    Ar represents a naphthalene or benzene group,
    X represents a carbon chain interrupted by NH groups
    Hal represents chlorine, bromine or iodine,
    a represents 1, 2 or 3,
    e represents 1 and f represents 1 or e represents 2 and f represents 0,
    and the -NH- as well as the -Hal- substituents are found in the positions 2, 4 and 6 of the triazinyl ring, in addition to common ingredients compatible with this constituent, characterized in that the triazine derivative of general formula II may be obtained by reacting 2 equivalents of such compounds according to formula I, which further bear 1 or 2 halogens on the triazine radical, with 1 equivalent of an oligo- or poly-ethyleneimine of formula NH2-CH2CH2-(NH-CH2CH2-)nNH2, wherein n is a number from 1 to 9, in particular 2 to 5.
  3. The agent according to claim 2, characterized in that the diaminostilbene or the diaminobiphenyl also additionally has at least 1, in particular 2 sulphonic acid salt substituents.
  4. A washing agent, containing a dye transfer inhibitor as a triazine derivative of general formula III,

            X(NH-T(NH-Ar(SO3Na)d-NH-T(NH-Ar(SO3Na)a)Hal)Hal)2     (III)

    wherein
    T represents a 1,3,5-triazinyl radical,
    Ar represents a naphthalene or benzene group,
    X represents a linear or branched carbon chain optionally interrupted by NH groups, with 1 to 20, in particular 2 to 12 C atoms, or a stilbene or biphenyl group, optionally mono-or polysubstituted with -SO3Na,
    Hal represents chlorine, bromine or iodine,
    a and d, independently of each other, represent 1, 2 or 3,
    and the -NH- as well as the -Hal- substituents are found in the positions 2, 4 and 6 of the triazinyl ring, in addition to common ingredients compatible with this constituent, characterized in that the triazine derivative of general formula III may be obtained by reacting diaminostilbenes or diaminobiphenyls with 2 equivalents of 2,4,6-trihalo-1,3,5-triazine, followed by reaction with 2 equivalents of a diaminoaryl compound, again followed by reaction with 2 equivalents of 2,4,6-trihalo-1,3,5-triazine and subsequent reaction with 2 equivalents of an aminoaryl compound.
  5. The agent according to any of claims 2 to 4, characterized in that it contains 0.1 % by weight to 2% by weight, in particular, 0.2% by weight to 1 percent by weight, of a triazine derivative inhibiting dye transfer, of general formula II and/or III and further optionally a triazine derivative of general formula I.
  6. The agent according to any of claims 2 to 5, characterized in that it further contains a polymer of vinylpyrrolidone, vinylimidazole, vinylpyridine N-oxide or a copolymer thereof.
  7. The use of triazine derivatives of general formula II,

            X(NH-T(NH-Ar(SO3Na)a)eHalf)2     (II)

    wherein
    T represents a 1,3,5-triazinyl radical,
    Ar represents a naphthalene or benzene group,
    X represents a carbon chain interrupted by NH groups Hal represents chlorine, bromine or iodine,
    a represents 1, 2 or 3,
    e represents 1 and f represents 1 or e represents 2 and f represents 0,
    and the -NH- as well as the -Hal- substituents are found in the positions 2, 4 and 6 of the triazinyl ring, in order to avoid transfer of textile dyes from dyed textiles to undyed textiles or of other colors upon laundering them together in particular surfactant-containing aqueous solutions, characterized in that the triazine derivative of general formula II may be obtained by reaction of 2 equivalents of such compounds according to formula I, which further bear one or two halogens on the triazine radical, with one equivalent of oligo- or poly-ethylene-imine of formula NH2-CH2CH2-(NH-CH2CH2-)nNH2, wherein n is a number from 1 to 9, in particular 2 to 5.
  8. The use of triazine derivatives of general formula III,

            X(NH-T(NH-Ar(SO3Na)d-NH-T(NH-Ar(SO3Na)a)Hal)Hal)2     (III)

    wherein
    T represents a 1,3,5-triazinyl radical,
    Ar represents a naphthalene or benzene group,
    X represents a linear or branched carbon chain optionally interrupted by NH groups, with 1 to 20, in particular 2 to 12 C atoms, or a stilbene or biphenyl group, optionally mono-or polysubstituted with -SO3Na,
    Hal represents chlorine, bromine or iodine,
    a and d, independently of each other, represent 1, 2 or 3,
    and the -NH- as well as the -Hal- substituents are found in the positions 2, 4 and 6 of the triazinyl ring, in order to avoid transfer of textile dyes from dyed textiles to undyed textiles or of other colors upon laundering them together in particular surfactant-containing aqueous solutions, characterized in that the triazine derivative of general formula III may be obtained by reacting diaminostilbenes or diaminobiphenyls with 2 equivalents of 2,4,6-trihalo-1,3,5-triazine, followed by reaction with 2 equivalents of a diaminoaryl compound, again followed by reaction with 2 equivalents of 2,4,6-trihalo-1,3,5-triazine and subsequent reaction with 2 equivalents of an aminoaryl compound.
  9. The use of triazine derivatives of general formula II,

            X(NH-T(NH-Ar(SO3Na)a)eHalf)2     (II)

    wherein
    T represents a 1,3,5-triazinyl radical,
    Ar represents a naphthalene or benzene group,
    X represents a carbon chain interrupted by NH groups Hal represents chlorine, bromine or iodine,
    a represents 1, 2 or 3,
    e represents 1 and f represents 1 or e represents 2 and f represents 0,
    and the -NH- as well as the -Hal- substituents are found in the positions 2, 4 and 6 of the triazinyl ring, in order to avoid modification of the color print of dyed textiles upon laundering them in particular surfactant-containing aqueous solutions, characterized in that the triazine derivative of general formula II may be obtained by reaction of 2 equivalents of such compounds according to formula I, which further bear one or two halogens on the triazine radical, with one equivalent of oligo- or poly-ethylene- imine of formula NH2-CH2CH2-(NH-CH2CH2-)nNH2, wherein n is a number from 1 to 9, in particular 2 to 5.
  10. The use of triazine derivatives of general formula III,

            X(NH-T(NH-Ar(SO3Na)d-NH-T(NH-Ar(SO3Na)a)Hal)Hal)2     (III)

    wherein
    T represents a 1,3,5-triazinyl radical,
    Ar represents a naphthalene or benzene group,
    X represents a linear or branched carbon chain optionally interrupted by NH groups, with 1 to 20, in particular 2 to 12 C atoms, or a stilbene or biphenyl group, optionally mono-or polysubstituted with -SO3Na,
    Hal represents chlorine, bromine or iodine,
    a and d, independently of each other, represent 1, 2 or 3,
    and the -NH- as well as the -Hal- substituents are found in the positions 2, 4 and 6 of the triazinyl ring, in order to avoid modification of the color print of dyed textiles upon laundering them in particular surfactant-containing aqueous solutions, characterized in that the triazine derivative of general formula III may be obtained by reacting diaminostilbenes or diaminobiphenyls with 2 equivalents of 2,4,6-trihalo-1,3,5-triazine, followed by reaction with 2 equivalents of a diaminoaryl compound, again followed by reaction with 2 equivalents of 2,4,6-trihalo-1,3,5-triazine and subsequent reaction with 2 equivalents of an aminoaryl compound.
EP06776638A 2005-08-19 2006-08-05 Colour protection washing product Not-in-force EP1915438B1 (en)

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DE102006012018B3 (en) * 2006-03-14 2007-11-15 Henkel Kgaa Color protecting detergent
DE102007012975A1 (en) * 2007-03-14 2008-09-18 Henkel Ag & Co. Kgaa Color protecting detergent
DE102009001813A1 (en) * 2009-03-24 2010-09-30 Henkel Ag & Co. Kgaa Graying-inhibiting detergent
JP5712921B2 (en) * 2009-05-07 2015-05-07 日産化学工業株式会社 Triazine ring-containing polymer and film-forming composition containing the same
DE102011008526A1 (en) 2011-01-13 2012-07-19 Henkel Ag & Co. Kgaa Color protecting detergents
WO2013123981A1 (en) * 2012-02-21 2013-08-29 Henkel Ag & Co. Kgaa Color protection detergent
US9702074B2 (en) 2013-03-15 2017-07-11 Whirlpool Corporation Methods and compositions for treating laundry items
US10072373B2 (en) 2013-03-15 2018-09-11 Whirlpool Corporation Methods and compositions for treating laundry items
DE102013226008A1 (en) 2013-12-16 2015-06-18 Henkel Ag & Co. Kgaa Color protecting detergents
DE102013021276A1 (en) 2013-12-17 2015-06-18 Clariant International Ltd. Color protecting detergents
DE102022200093A1 (en) 2022-01-06 2023-07-06 Henkel Ag & Co. Kgaa Color protecting detergents
DE102022200097A1 (en) 2022-01-06 2023-07-06 Henkel Ag & Co. Kgaa Color protecting detergents
DE102022200095A1 (en) 2022-01-06 2023-07-06 Henkel Ag & Co. Kgaa Color protecting detergents
DE102022200094A1 (en) 2022-01-06 2023-07-06 Henkel Ag & Co. Kgaa Color protecting detergents
DE102022200881A1 (en) 2022-01-26 2023-07-27 Henkel Ag & Co. Kgaa Color protecting detergents
CN115385905B (en) * 2022-08-29 2024-02-06 南通大学 PH color-changing reactive dye capable of dyeing cotton fabric and preparation method thereof

Family Cites Families (86)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE951339C (en) 1954-03-27 1956-10-25 Stroemmens Vaerksted As Propeller with interchangeable blades
US3234258A (en) 1963-06-20 1966-02-08 Procter & Gamble Sulfation of alpha olefins
US3617702A (en) * 1969-06-10 1971-11-02 Du Pont Apparatus and method for perforating sheet material
AU434105B2 (en) * 1969-10-28 1973-03-23 Ciba-Geigy Ag Asymmetrically substituted bistriazinylamino stilbene compounds
DE1962899B2 (en) 1969-12-16 1978-08-24 Bayer Ag, 5090 Leverkusen Process for the antimicrobial treatment of cellulose-containing! Textile material
US3947374A (en) 1973-03-21 1976-03-30 American Cyanamid Company Substituted halotriazines as peroxygen bleach activators
AT330930B (en) 1973-04-13 1976-07-26 Henkel & Cie Gmbh PROCESS FOR THE PRODUCTION OF SOLID, SPILLABLE DETERGENTS OR CLEANING AGENTS WITH A CONTENT OF CALCIUM BINDING SUBSTANCES
CA1037815A (en) 1973-06-20 1978-09-05 Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) Process for the production of solid, pourable washing or cleaning agents with a content of a calcium binding silicate
DE2814329A1 (en) 1978-04-03 1979-10-11 Henkel Kgaa Washing agents contg. N-vinyl-oxazolidone polymers - inhibiting transfer of dyes from coloured textiles onto white textiles
DE2814287A1 (en) 1978-04-03 1979-10-11 Henkel Kgaa Detergent compsn. contg. N-vinyl! imidazole polymer - as discoloration-inhibiting additive
JPS58217598A (en) 1982-06-10 1983-12-17 日本油脂株式会社 Detergent composition
US4548744A (en) 1983-07-22 1985-10-22 Connor Daniel S Ethoxylated amine oxides having clay soil removal/anti-redeposition properties useful in detergent compositions
DE3413571A1 (en) 1984-04-11 1985-10-24 Hoechst Ag, 6230 Frankfurt USE OF CRYSTALLINE LAYERED SODIUM SILICATES FOR WATER SOFTENING AND METHOD FOR WATER SOFTENING
DE3417649A1 (en) 1984-05-12 1985-11-14 Hoechst Ag, 6230 Frankfurt METHOD FOR PRODUCING CRYSTALLINE SODIUM SILICATES
FR2597473B1 (en) 1986-01-30 1988-08-12 Roquette Freres PROCESS FOR THE OXIDATION OF DI-, TRI-, OLIGO- AND POLYSACCHARIDES TO POLYHYDROXYCARBOXYLIC ACIDS, CATALYST IMPLEMENTED AND PRODUCTS THUS OBTAINED.
US4954292A (en) 1986-10-01 1990-09-04 Lever Brothers Co. Detergent composition containing PVP and process of using same
JPS63184589A (en) * 1987-01-28 1988-07-30 株式会社シマノ Derailer for bicycle
DE3719467A1 (en) 1987-06-11 1988-12-29 Hoechst Ag ORGANICALLY SUBSTITUTED AMMONIUM SILICATES AND METHOD FOR THE PRODUCTION THEREOF
DE3723873A1 (en) 1987-07-18 1989-01-26 Henkel Kgaa USE OF HYDROXYALKYLPOLYETHYLENE GLYCOLETHERS IN RINSE AID FOR MACHINE CLEANING
DE3803630A1 (en) 1988-02-06 1989-08-17 Henkel Kgaa DETERGENT ADDITIVE
DE3914131A1 (en) 1989-04-28 1990-10-31 Henkel Kgaa USE OF CALCINATED HYDROTALCITES AS CATALYSTS FOR ETHOXYLATION OR PROPOXYLATION OF FATTY ACID ESTERS
DE4010533A1 (en) 1990-04-02 1991-10-10 Henkel Kgaa Prodn. of high-density detergent granules
WO1991002047A1 (en) 1989-08-09 1991-02-21 Henkel Kommanditgesellschaft Auf Aktien Manufacture of compacted granules for washing agents
DE3927758A1 (en) 1989-08-23 1991-02-28 Saarberg Interplan Gmbh DEVICE FOR PREVENTING LEAKAGE GAS DURING THE ENTERING OF COAL CAKE IN HORIZONTAL COOKING CHAMBERS
US5571444A (en) * 1989-09-11 1996-11-05 Invicta Group Industries Pty Ltd. Textile treatment
PE14291A1 (en) 1989-10-13 1991-04-27 Novo Nordisk As PROCEDURE TO INHIBIT THE TRANSFER OF DYES
CA2025073C (en) 1989-10-25 1995-07-18 Gunther Schimmel Process for producing sodium silicates
US5236682A (en) 1989-10-25 1993-08-17 Hoechst Aktiengesellschaft Process for producing crystalline sodium silicates having a layered structure
YU221490A (en) 1989-12-02 1993-10-20 Henkel Kg. PROCEDURE FOR HYDROTHERMAL PRODUCTION OF CRYSTAL SODIUM DISILICATE
DE4000705A1 (en) 1990-01-12 1991-07-18 Hoechst Ag METHOD FOR PRODUCING CRYSTALLINE SODIUM SILICATES
US5047163A (en) 1990-03-16 1991-09-10 Lever Brothers Company, Division Of Conopco, Inc. Activation of bleach precursors with sulfonimines
US5041232A (en) 1990-03-16 1991-08-20 Lever Brothers Company, Division Of Conopco, Inc. Sulfonimines as bleach catalysts
US5075041A (en) 1990-06-28 1991-12-24 Shell Oil Company Process for the preparation of secondary alcohol sulfate-containing surfactant compositions
DE59106971D1 (en) * 1990-07-12 1996-01-11 Ciba Geigy Ag Process for the photochemical and thermal stabilization of polyamide fiber materials.
DE4041752A1 (en) 1990-12-24 1992-06-25 Henkel Kgaa ENZYME PREPARATION FOR WASHING AND CLEANING AGENTS
JP3293636B2 (en) 1991-01-10 2002-06-17 日本化学工業株式会社 Method for producing crystalline layered sodium silicate
JP3299763B2 (en) 1991-02-14 2002-07-08 日本化学工業株式会社 Method for producing modified sodium disilicate
DE4107230C2 (en) 1991-03-07 1995-04-06 Hoechst Ag Process for the production of sodium silicates
IT1245063B (en) 1991-04-12 1994-09-13 Ferruzzi Ricerca & Tec PROCEDURE FOR OXIDATION OF CARBOHYDRATES
ATE155539T1 (en) 1991-04-12 1997-08-15 Novo Nordisk As REMOVAL OF EXCESS DYE FROM NEW TEXTILES
ATE155165T1 (en) 1991-07-31 1997-07-15 Ausimont Spa METHOD FOR INCREASING THE BLEACHING EFFECTIVENESS OF AN INORGANIC PER SALT
DE4142711A1 (en) 1991-12-21 1993-06-24 Hoechst Ag METHOD FOR PRODUCING CRYSTALLINE SODIUM DISILICATES
DE4221381C1 (en) 1992-07-02 1994-02-10 Stockhausen Chem Fab Gmbh Graft copolymers of unsaturated monomers and sugars, process for their preparation and their use
DE4203923A1 (en) 1992-02-11 1993-08-12 Henkel Kgaa METHOD FOR PRODUCING POLYCARBOXYLATES ON A POLYSACCHARIDE BASE
DE4216774A1 (en) 1992-05-21 1993-11-25 Henkel Kgaa Process for the continuous production of a granular washing and / or cleaning agent
ES2125969T3 (en) 1992-07-15 1999-03-16 Procter & Gamble COMPOSITIONS TO INHIBIT THE TRANSFER OF DYE WITH CONTENT IN IMPROVERS.
JP3339884B2 (en) 1992-08-21 2002-10-28 津田駒工業株式会社 Defective weft removal device for loom
ES2123601T3 (en) 1992-08-22 1999-01-16 Clariant Gmbh USE OF WATER-SOLUBLE COPOLYMERS BASED ON ACRYLAMIDALKYLENSULPHONIC ACIDS AS AN ADDITIVE TO DETERGENTS.
DE4235798A1 (en) 1992-10-23 1994-04-28 Basf Ag Use of vinylpyrrolidone and vinylimidazole copolymers as detergent additive, novel polymers of vinylpyrrolidone and of vinylimidazole and process for their preparation
DE4300772C2 (en) 1993-01-14 1997-03-27 Stockhausen Chem Fab Gmbh Water-soluble, biodegradable copolymers based on unsaturated mono- and dicarboxylic acids, process for their preparation and their use
DE4303320C2 (en) 1993-02-05 1995-12-21 Degussa Detergent composition having improved soil carrying power, process for its preparation and use of a suitable polycarboxylate therefor
DE4304313A1 (en) 1993-02-12 1994-08-18 Hoechst Ag Use of copolymers based on vinyl monomers and carboxylic acid amides as detergent additive
DE4310506A1 (en) 1993-03-31 1994-10-06 Cognis Bio Umwelt Enzyme preparation for detergents and cleaning agents
DE4316023A1 (en) 1993-05-13 1994-11-17 Basf Ag Process for the preparation of low molecular weight polymers of 1-vinylimidazole
CN1065563C (en) 1993-05-20 2001-05-09 普罗格特-甘布尔公司 Bleaching compounds comprising N-acyl caprolactam for use in hand-wash or other low-water cleaning systems
DE69412092T2 (en) 1993-05-20 1999-04-01 Procter & Gamble FIBER WHICH CONTAINS A SUBSTITUTED BENZOYL CAPROLACTAM BLEACH ACTIVATOR
JP3347734B2 (en) 1993-05-20 2002-11-20 ザ、プロクター、エンド、ギャンブル、カンパニー Bleach composition comprising N-acylcaprolactam activator
EP0635566B1 (en) 1993-07-23 1998-06-17 The Procter & Gamble Company Detergent compositions inhibiting dye transfer
DE4319934A1 (en) 1993-06-16 1994-12-22 Basf Ag Grafted polyamidoamines and grafted polyethyleneimines, process for their preparation and their use as additives to detergents
US5405413A (en) 1993-06-24 1995-04-11 The Procter & Gamble Co. Bleaching compounds comprising acyl valerolactam bleach activators
DE4321022A1 (en) 1993-06-24 1995-01-05 Henkel Kgaa Sulphated mixed hydroxy ethers
EP0635565B1 (en) 1993-07-23 1997-11-12 The Procter & Gamble Company Detergent compositions inhibiting dye transfer
DE4328254A1 (en) 1993-08-23 1995-03-02 Henkel Kgaa Discoloration inhibitors for detergents
GB9317803D0 (en) 1993-08-27 1993-10-13 Cussons Int Ltd Laundry detergent composition
AU7716094A (en) 1993-09-09 1995-03-27 Procter & Gamble Company, The Liquid detergents with n-alkoxy or n-aryloxy polyhydroxy fatty acid amide surfactants
DE4333238A1 (en) 1993-09-30 1995-04-06 Basf Ag Polyesters and polyamides containing pyrrolidone groups
US5466802A (en) * 1993-11-10 1995-11-14 The Procter & Gamble Company Detergent compositions which provide dye transfer inhibition benefits
DE4338922A1 (en) 1993-11-15 1995-05-18 Degussa Activators for inorganic peroxygen compounds
WO1995014759A1 (en) 1993-11-25 1995-06-01 Warwick International Group Limited Bleaching compositions
DE4405511A1 (en) 1994-02-22 1995-08-24 Henkel Kgaa Detergent with amorphous silicate builder substances
DE4417734A1 (en) 1994-05-20 1995-11-23 Degussa Polycarboxylates
DE4422433A1 (en) 1994-06-28 1996-01-04 Cognis Bio Umwelt Multi-enzyme granules
EP0703227A1 (en) * 1994-09-19 1996-03-27 Ciba-Geigy Ag Watersoluble antioxidants, process of their preparation, and their use for the photochemical and thermical stabilisation of polyamide fibers
DE4443177A1 (en) 1994-12-05 1996-06-13 Henkel Kgaa Activator mixtures for inorganic per compounds
DE19503061A1 (en) 1995-02-01 1996-08-08 Henkel Kgaa Dimer alcohol bis- and trimer alcohol tris-sulfates and ether sulfates
DE19513391A1 (en) 1995-04-08 1996-10-10 Henkel Kgaa End gp.-capped dimer alcohol- and trimer alcohol alkoxylate(s)
US5569645A (en) * 1995-04-24 1996-10-29 The Procter & Gamble Company Low dosage detergent composition containing optimum proportions of agglomerates and spray dried granules for improved flow properties
DE19519339A1 (en) 1995-05-26 1996-11-28 Basf Ag Water-soluble copolymers containing copolymerized crosslinkers, process for their preparation and their use
EP0798413A1 (en) * 1996-03-04 1997-10-01 Ciba SC Holding AG Method for dyeing fibrous materials containing natural or synthetic polyamide
CN1085247C (en) * 1996-03-08 2002-05-22 普罗格特-甘布尔公司 Secondary alkyl sulfate surfactant with improved solubility by compacting/coating process
DE19616769A1 (en) 1996-04-26 1997-11-06 Henkel Kgaa Acylacetals as bleach activators for detergents and cleaning agents
DE19616693A1 (en) 1996-04-26 1997-11-06 Henkel Kgaa Enol esters as bleach activators for detergents and cleaning agents
DE19616770A1 (en) 1996-04-26 1997-11-06 Henkel Kgaa Acyl lactams as bleach activators for detergents and cleaning agents
DE19616767A1 (en) 1996-04-26 1997-11-06 Henkel Kgaa Bleach activators for detergents and cleaning agents
DE19819187A1 (en) 1998-04-30 1999-11-11 Henkel Kgaa Solid dishwasher detergent with phosphate and crystalline layered silicates
WO2001023660A1 (en) * 1999-09-30 2001-04-05 The Procter & Gamble Company Cotton fabric with durable properties

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ATE538196T1 (en) 2012-01-15
US8263541B2 (en) 2012-09-11
US20080234167A1 (en) 2008-09-25
PL1915438T3 (en) 2012-05-31
EP1915438A1 (en) 2008-04-30
WO2007019981A1 (en) 2007-02-22
US8785362B2 (en) 2014-07-22
DE102005039580A1 (en) 2007-02-22

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