EP1994133A1

EP1994133A1 - Colour-protecting laundry detergent composition

Info

Publication number: EP1994133A1
Application number: EP07703336A
Authority: EP
Inventors: Josef Penninger; Birgit GLÜSEN
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 2006-03-14
Filing date: 2007-02-08
Publication date: 2008-11-26
Anticipated expiration: 2027-02-08
Also published as: JP5143752B2; EP1994133B1; PL1994133T3; DE102006012018B3; US7947087B2; WO2007104392A1; ATE507279T1; JP2009529593A; ES2362017T3; US20090069210A1

Abstract

Detergent compositions comprising a color transfer inhibitor and optionally surfactant(s), the color transfer inhibitor comprising one or more compounds selected from the group consisting of triazine derivatives corresponding to general formulae I and II: T(NH—Ar(CO2M)a)bHalc (I) X—NH—CH2CH2—(NY—CH2CH2—)nNH—X (II) wherein T represents a 1,3,5-triazinyl group; Ar represents a phenyl group; each M independently represents a substituent selected from the group consisting of H, Na, Li, and K; each Hal independently represents a halogen selected from the group consisting of Cl, Br, and I; each a independently represents 1, 2 or 3; b and c each represent 1 or 2 wherein b+c=3; each X represents a T(NH—Ar(CO2M)a)bHalc−1 group; each Y independently represents H or X; and n represents a number of 0 to 50, and uses therefor in washing and treating dyed and/or undyed textiles.

Description

Color protecting detergent

The present invention relates to the use of carboxylated triazine derivatives as dye transfer inhibiting agents in the washing of textiles and detergents containing such compounds.

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 unwanted side effects of removing dirt from textiles by treatment with usually surfactant-containing aqueous systems, detergents, especially if they are provided as so-called color or colored laundry detergents for colored textiles, contain active ingredients that 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.

Surprisingly, it has now been found that certain carboxylated triazine derivatives lead to unexpectedly high color transfer inhibition when used in detergents. Particularly pronounced is the prevention of the staining 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, by virtue of their carboxylic acid group content, have a repellent effect on dye molecules present in the liquor.

The invention therefore provides the use of triazine derivatives of the general

Formulas I or II,

T (NH-Ar (CO ₂ M) _a ) _b Hal _c (I)

X-NH-CH ₂ CH ₂ - (NY-CH ₂ CH ₂ -) _n NH-X (II) in which

T is a 1,3,5-triazinyl group,

Ar is a phenyl group,

M for H, Na, Li or K,

Hal is Cl, Br or I, a is 1, 2 or 3, b is 1 and c is 2 or b is 2 and c is 1,

X is -T (NH-Ar (CO ₂ M) _a ) _b Hal _c-1 ,

Y is H or X, and n is a number from 0 to 50, to avoid the transfer of textile dyes of dyed textiles on undyed or other-colored textiles in their common washing in particular surfactant-containing aqueous solutions.

Another object of the invention is a color-protective detergent, comprising a color transfer inhibitor in the form of a triazine derivative of the above-defined general formulas I or II in addition to conventional ingredients compatible with this ingredient.

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 carries at least 1 carboxy substituent. It is preferably a 1 to 3-fold carboxylic acid or carboxylate-substituted benzene unit. Suitable aminoaryl compounds are for example 2- Aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 3-amino-1,2-benzenedicarboxylic acid, 4-amino-1,2-benzenedicarboxylic acid, 2-amino-1,3-benzenedicarboxylic acid, 4-aminobenzoic acid 1, 3-benzenedicarboxylic acid, 5-amino-1,3-benzenedicarboxylic acid, 2-amino-1,4-benzenedicarboxylic acid, 4-amino-1,2,3-benzenetricarboxylic acid, 3-amino-1, 2,4- benzenetricarboxylic acid, 5-amino-1, 2,4-benzenetricarboxylic acid, 6-amino-1, 2,4-benzenetricarboxylic acid and 2-amino-1,3,5-benzenetricarboxylic acid, wherein their carboxylic acid groups may also be present in salt form. It is also possible to use mixtures of the aminoaryl compounds mentioned.

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 ethylenediamine, compounds of the formula II where n = 0 are obtained. Oligo- or polyethyleneimines can also be used instead of ethylenediamine, in which case 1 additional equivalent of the compound according to formula I is preferably used for each internal N atom of the oligo- or polyethyleneimine. Preferred oligo- or polyethylenimines 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 30, in particular 2 to 20, whereby 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.

In the simultaneous use of different aminoaryl compounds or simultaneous use of different oligo- or polyethyleneimines obtained in the described preparation process informally compounds according to the formula I or II, in which the respective variables a, b, c, n, X and Y are not always the same are.

An agent according to the invention preferably contains from 0.05% by weight to 2% by weight, in particular from 0.2% by weight to 1% by weight, of dye transfer inhibiting compound of the general formula I and / or II. or "formulation is to be made clear that the joint use of compounds which each correspond to one of the above formulas, is possible.

The compounds of the general formula I or II contribute to both aspects of the color constancy mentioned above, ie they reduce it both discoloration and fading, although the effect of preventing staining, especially when washing white textiles, is most pronounced. Another object of the invention is therefore the use of a corresponding compound to prevent the change in the color impression of textiles in their washing in particular surfactant-containing aqueous solutions. Under the change in the color impression is by no means the difference between dirty and clean textile to understand, but the difference between each clean textile before and after the washing process.

Another object of the invention is a process for washing dyed textiles in surfactant-containing aqueous solutions, which is characterized in that one uses a surfactant-containing aqueous solution containing a compound of general formula I and / or II. 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.

An agent according to the invention, in addition to the compound according to formula I or II, if desired, a known dye transfer inhibitor, then preferably in amounts of 0.1 wt .-% to 2 wt .-%, in particular 0.2 wt .-% to 1 wt. %, which in a preferred embodiment of the invention is a polymer of vinylpyrrolidone, vinylimidazole, vinylpyridine-N-oxide or a copolymer thereof. Usable are both the polyvinylpyrrolidones known from European patent application EP 0 262 897 and having molecular weights of from 15,000 to 50,000, and also the polyvinylpyrrolidones known from international patent application WO 95/06098 having molecular weights above 1,000,000, in particular from 1,500,000 to 4 000 000, the N-vinylimidazole / N-vinylpyrrolidone copolymers known from German Patent Applications DE 28 14 287 or DE 38 03 630 or international patent applications WO 94/10281, WO 94/26796, WO 95/03388 and WO 95/03382 , the polyvinyloxazolidones known from the German patent application DE 28 14 329, the copolymers based on vinyl monomers and carboxylic acid amides known from the European patent application EP 610 846, the polyesters containing pyrrolidone groups and polyamides known from the international patent application WO 95/09194, which are disclosed in the international patent application WO 94/29422 known grafted polyamidoamines and polyethyleneimines, the polymers known from the German patent application DE 43 28 254 with amide groups from secondary amines, the polyamine N-oxide polymers known from the international patent application WO 94/02579 or the European patent application EP 0 135 217, which are known from European Patent application EP 0 584 738 and the copolymers based on acrylamidoalkenylsulfonic acids known from the European patent application EP 0 584 709. However, it is also possible to use enzymatic systems comprising a peroxidase and hydrogen peroxide or a hydrogen peroxide-yielding substance in water, as are known, for example, from international patent applications WO 92/18687 and WO 91/05839. The addition of a mediator compound for the peroxidase, for example an acetosyringone known from international patent application WO 96/10079, a phenol derivative known from international patent application WO 96/12845 or a phenotiazine or phenoxazine known from international patent application WO 96/12846, is disclosed in US Pat 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.

The detergents according to the invention, which may be in the form of homogeneous solutions or suspensions, especially in powdered solids, in densified particle form, may in principle contain, in addition to the active ingredient used in accordance with 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, scorch inhibitors, foam regulators and dyes and fragrances. 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.

Suitable nonionic surfactants are in particular alkyl glycosides and ethoxylation and / or propoxylation of alkyl glycosides or linear or branched alcohols each having 12 to 18 carbon atoms in the alkyl moiety and 3 to 20, preferably 4 to 10 alkyl ether groups. Also suitable are ethoxylation and / or propoxylation products of N-alkylamines, vicinal diols, fatty acid esters and fatty acid amides which correspond to said long-chain alcohol derivatives with respect to the alkyl moiety and of alkylphenols having 5 to 12 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 residue is linear or preferably methyl-branched in the 2-position may be or contain linear and methyl-branched radicals in the mixture, as they are usually present in Oxoalkoholresten. In particular, however, alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred. Preferred ethoxylated alcohols include, for example, Ci ₂ -C ₄ alcohols containing 3 EO or 4 EO, C ₉ Cn alcohols with 7 EO, C ₃ -d ₅ alcohols containing 3 EO, 5 EO, 7 EO or 8 EO , C _J2 -C -alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C] ₂ -Ci ₄ -alcohol with 3 EO and Ci ₂ -Ci ₈ -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 rank ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples of these are (TaIg) 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 Cj ₂ -C ig alkylpolyethylene glycol polypropylene glycol ethers each with at 8 mol ethylene oxide and propylene oxide in the molecule. But you can also Other known low-foam nonionic surfactants use, such as, for example, Ci ₂ -Ci ₈ - alkylpolyethylene glycol polybutylenglykolether with up to 8 moles of ethylene oxide and butylene oxide in the molecule and endgruppenverschlossene alkylpolyalkylene glycol mixed. Also particularly preferred are the hydroxyl-containing alkoxylated alcohols, as described in European Patent Application EP 0 300 305, so-called hydroxy mixed ethers. The nonionic surfactants also include alkyl glycosides of the general formula RO (G) _x in which R is a primary straight-chain or methyl-branched, in particular 2-methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G represents a glycose unit having 5 or 6 C atoms, preferably glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is 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 (III) 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:

R ^z

R -CO-N- [Z] (III)

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 (IV)

R ⁴ -OR ⁵

I (IV)

R ³ -CO-N- [Z]

in the R ^{3 is} a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R is a linear, branched or cyclic alkylene radical or a Arylene radical having 2 to 8 carbon atoms and R ^{5 is} a linear, branched or cyclic alkyl radical or an aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, wherein C] -C ₄ alkyl or phenyl radicals are preferred, and [Z] is a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this radical. [Z] is also obtained here preferably by reductive amination of a sugar such as glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy- or N-aryloxy-substituted compounds can then be converted into the desired polyhydroxy fatty acid amides, for example according to the teaching of international patent application WO 95/07331, by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst. 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 esters, as described for example in Japanese Patent Application JP 58/217598 or which are preferably prepared according to the method described in International Patent Application WO 90/13533. 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 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, under the Expression Gemini surfactants not only such "dimeric", but also understood according to "trimeric" surfactants. Suitable gemini surfactants are, for example, sulfated hydroxy mixed ethers according to German patent application DE 43 21 022 or dimer alcohol bis- and trimer alcohol tris sulfates and ether sulfates according to German patent application DE 195 03 061. End group-capped dimeric and trimeric mixed ethers according to German patent application DE 195 13 391 are characterized by their bi- and multi-functionality. Thus, the end-capped surfactants mentioned have good wetting properties and are low foaming, 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 polyhydroxy fatty acid amides, as are produced in International Patent Applications WO 95/19953, WO 95/19954 and US Pat. Nos. 3,234,258 or 5,075,041, and as Shell's commercial products OiI Company under the name DAN® are suitable anionic surfactants. Also suitable are the Schwefelsäuremonoester the ethoxylated with 1 to 6 moles of ethylene oxide, linear or branched C ₇ -C _2] alcohols, such as 2-methyl-branched C ₉ -C11- alcohols containing on average 3.5 mol ethylene oxide (EO) or C ₂ - Ci ₈ 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] ₈ 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 possibly simple 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 lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid and, in particular, soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids. Together with these soaps or as a substitute for soaps, it is also possible to use the known alkenylsuccinic acid salts.

The anionic surfactants, including the soaps, may be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di-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, diphosphonic acid, polymeric hydroxy compounds such as dextrin and also polymeric (poly) carboxylic acids, in particular the polycarboxylates obtainable by oxidation of polysaccharides or dextrins of the European patent EP 0 625 992 or the international patent application WO 92/18542 or the European patent EP 0 232 202, polymeric acrylic acids, methacrylic acids, maleic acids and copolymers of these, the polymerized even small amounts of polymerizable substances without carboxylic acid ent can hold. The molecular weight of the homopolymers of unsaturated carboxylic acids is generally between 3,000 and 200,000, of the copolymers between 2,000 and 200,000, preferably 30,000 to 120,000, each based on the free acid. A particularly preferred Acrylic acid-maleic acid copolymer has a molecular weight of 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 vinyl methyl 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 their salts 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 6 -dicarboxylic acid, with maleic acid being particularly preferred, and / or a derivative of an alkylsulfonic acid which is substituted in the 2-position by an alkyl or aryl radical, be. Such polymers can be prepared in particular by methods which are described in German Patent DE 42 21 381 and German Patent Application DE 43 00 772, and generally have a molecular weight between 1,000 and 200,000. Further preferred copolymers are those which are described in the German patent applications DE 43 03 320 and DE 44 17 734 and preferably have as monomers acrolein and acrylic acid / acrylic acid salts or vinyl acetate. The organic builder substances can be used, in particular for the preparation of liquid agents, in the form of aqueous solutions, preferably in the form of 30 to 50 percent by weight aqueous solutions. All of the acids mentioned are generally used in the form of their water-soluble salts, in particular their alkali metal salts.

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.

As water-soluble inorganic builder materials are in particular alkali metal silicates, alkali metal carbonates and alkali metal phosphates, in the form of their alkaline, neutral or acidic Sodium or potassium salts may be present, into consideration. Examples of these are trisodium phosphate, tetrasodium diphosphate, disodium dihydrogen diphosphate, pentanetrium 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. In particular, crystalline or amorphous alkali metal aluminosilicates, in amounts of up to 50% by weight, preferably not more than 40% by weight and in liquid agents, in particular from 1% by weight to 5% by weight, are used as water-insoluble, water-dispersible inorganic builder materials. used. Among these, 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 (Vegobond® 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, which can be determined according to the specifications of the German patent DE 24 12 837, is generally 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 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 of 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. The crystalline silicates which may be present alone or in admixture with amorphous silicates, are crystalline layer silicates with the general formula of Na ₂ Si _x O _{2x + I} y H ₂ O used in the 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 phyllosilicate cations which fall under this general formula are described, for example, in European patent application EP 0 164 514. Preferred crystalline phyllosilicates are those in which x in the abovementioned general formula assumes the values 2 or 3. In particular, both are .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 International Patent Application WO 91/08171. δ-Sodium silicates with a modulus between 1.9 and 3.2 can be prepared according to Japanese patent applications JP 04/238 809 or JP 04/260 610. Also prepared from amorphous alkali metal silicates, practically anhydrous crystalline alkali metal silicates of the abovementioned general formula in which x is a number from 1.9 to 2.1, 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 having a modulus of 2 to 3 is used, as can be produced from sand and soda by the process of European patent application EP 0 436 835. Crystalline sodium silicates with a modulus in the range of 1.9 to 3.5, as obtainable by the processes of European patents EP 0 164 552 and / or EP 0 294 753, are used in a further preferred embodiment of compositions according to the invention. 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 XH ₂ O, kenyaite), Na-SKS-2 (Na ₂ Si) ₄ O ₂₉ XH ₂ O, magadiite), Na-SKS-3 (Na ₂ Si ₈ Oi ₇ XH ₂ O) or Na-SKS-4 (Na ₂ Si ₄ O ₉ XH ₂ O, makatite) , Of these, especially Na-SKS-5 ((X-Na ₂ Si ₂ O ₅ ), Na-SKS-7 (B-Na ₂ Si ₂ O ₅ , natrosilite), Na-SKS-9 (NaHSi ₂ O ₅ 3H ₂ O), Na-SKS-IO (NaHSi ₂ O ₅ 3H ₂ O, kanemite), Na-SKS-1 1 (t-Na ₂ Si ₂ 0 ₅₎ and Na-SKS-13 (NaHSi ₂ O ₅ But, in particular, Na-SKS-6 (6-Na ₂ Si ₂ O ₅ ) An overview of crystalline phyllosilicates can be found, for example, in "Hoechst High Chem Magazine 14/1993" on pages 33-38 and in "Soap Chemistry". Oils-Fats-Waxes, 116 Volume, No. 20/1990 ", pages 805 - 808. 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 German Patent Application DE 198 19 187, or from alkali metal silicate and alkali metal carbonate, as it Example in the international patent application WO 95/22592 is described 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.

Peroxygen compounds which are suitable for use in compositions according to the invention are, in particular, organic peracids or persalts of organic acids, such as phthalimidopercaproic acid, perbenzoic acid or salts of diperdoecanedioic acid, hydrogen peroxide and inorganic salts which release hydrogen peroxide under the washing conditions, including perborate, percarbonate, persilicate and / or Persulfate such as caroate, into consideration. If solid peroxygen compounds are to be used, these can be used in the form of powders or granules, which can also be coated 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.

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 those from German patent applications DE 196 16 693 and DE 196 16 767 known enol esters and acetylated sorbitol and mannitol or their mixtures described in the European patent application EP 0 525 239 (SORMAN), acylated sugar derivatives, in particular pentaacetylglucose (PAG), pentaacetylfruktose, tetraacetylxylose and octaacetyllactose as well as 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. The hydrophilic substituted acyl acetals known from the German patent application DE 196 16 769 and the acyllactams described in the German patent application DE 196 16 770 and the international patent application WO 95/14075 are also preferably used. The combinations of conventional bleach activators known from German patent application DE 44 43 177 can also 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.

In addition to the conventional bleach activators or in their place, the sulfone imines and / or bleach-enhancing transition metal salts or transition metal complexes known from European patents EP 0 446 982 and EP 0 453 003 may also be present as so-called bleach catalysts.

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 adsorbed on carriers and / or embedded in encapsulants, as described, for example, in European patent EP 0 564 476 or in international patent application WO 94/23005, and / or embedded in encapsulating substances in order to protect them against premature inactivation. They are in the washing or Detergents preferably in amounts up to 5 wt .-%, in particular from 0.2 wt .-% to 4 wt .-%, contain. 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 formulated together in a granulate, for example from International Patent Applications WO 96/00772 or WO 96/00773.

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 derivable from the said classes of compounds ethers. 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.

In order to establish a desired pH, which does not naturally result from the mixture of the other components, the compositions according to the invention may contain systemic and environmentally acceptable acids, in particular citric acid, acetic acid, tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid and / or adipic acid, but also mineral acids, in particular sulfuric acid, or bases, in particular ammonium or alkali metal hydroxides. Such pH regulators are 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. Also water-soluble, containing acidic groups Polyamides are suitable for this purpose. Furthermore, other than the above-mentioned starch derivatives can be used, for example aldehyde starches. Preference is given to using cellulose ethers, such as carboxymethylcellulose (Na salt), methylcellulose, hydroxyalkylcellulose and mixed ethers, such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof, for example in amounts of from 0.1 to 5% by weight, based on the compositions ,

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-l, 3,5-triazinyl-6-amino) stilbene-2,2'-disulphonic acid or compounds of similar structure 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.

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 1 ₈ -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. Preferably, the foam inhibitors, in particular silicone and / or paraffin-containing foam inhibitors, are bound to a granular, water-soluble or dispersible carrier substance. In particular, mixtures of paraffins and bistearylethylenediamide are preferred. 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 of compositions according to the invention having an increased bulk density, in particular in the range from 650 g / l to 950 g / l, preference is given to a process known from the European patent EP 0 486 592 which has an extrusion step. Another preferred preparation by means of a granulation process is described in the European patent EP 0 642 576.

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. 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.

Examples

Example 1: Preparation of 2,4-bis (3-carboxyphenylamino) -6-chlorotriazine.

Cyanuric chloride (13.6 g, 0.073 mol), suspended in a mixture of ice and acetone (50 ml) was added (20 g, 0.146 mol) at 0 ° C to 5 ⁰ C to a stirred aqueous solution of 3- aminobenzoic acid pH 8 (sodium carbonate). The mixture was stirred at this temperature for 5 hours, then heated to 30 ° C and stirred at 30 ° C for a further 16 hours. Phosphate buffer mixture (pH 6.5, 2g) and then acetone were added. The precipitated colorless solid was separated (yield 49 g, 46.7% purity).

Example 2: Preparation of 2,4-bis (3,5-dicarboxyphenylamino) -6-chlorotriazine

5-Aminoisophthalic acid (98%, 20g, 0.108 mol) was dissolved in a mixture of water (200 ml) and ice (20 g) and sodium hydroxide. A freshly prepared suspension of cyanuric chloride (10 g, 0.054 mol) in ice / acetone (about 50 ml) was added with stirring at 0 ^° C. to 5 ^° C. and the pH was maintained at 6.5. After 4 hours, the mixture was warmed to 30 ° C. and the temperature was kept there for 16 hours, at pH 6.5. Phosphate buffer mixture and then acetone were added. The precipitated colorless solid was separated (yield 57 g, 53% purity).

Example 3: Preparation of N, N'-bis [2-chloro (3,5-dicarboxyphenylamino) triazine-6-ylamino] -1,2-diaminoethane

5-Aminoisophthalic acid (15.4 g) was reacted with 1 molar equivalent of cyanuric chloride at 0 ° C to 5 ⁰ C as described in Example 2. To the resulting solution of 2,4-bis (3,5-dicarboxyphenylamino) -6-chlorotriazine was added 1, 2-diaminoethane and the reaction mixture was stirred at pH 8 and a temperature of 30 ⁰ C for 4 hours. Acetone was added with stirring and the precipitated product was separated (yield 22.1 g, 56% purity). Example 4: Preparation of N, N'-bis [2-chloro (3-carboxyphenylamino) triazine-6-ylamino] -1,2-diaminoethane

Otherwise, as described in Example 3, but using 3-aminobenzoic acid (11.5 g) instead of the 5-Aminoisophthalsäure this was reacted with cyanuric chloride (15.4 g) at 0 ° C to 5 ⁰ C. To the resulting solution of 4,6-dichloro-6- (3-carboxyphenylamino) triazine was added 1, 2-diaminoethane and the reaction mixture at pH 8 and 30 ⁰ C to 35 ⁰ C for 4 hours. Acetone was added with stirring and the precipitated product was separated (yield 20.2 g, 59% purity).

Example 5: Preparation of N-poly (4-chloro-6- [3,5-dicarboxyphenylamino] triazinyl) polyethyleneimine

As described in Example 2, 5-aminoisophthalic acid (10 g) was reacted at 0 ^° C. to 5 ^° C. with cyanuric chloride. Oligomeric ethyleneimine (2.9 g, 432 weight average molecular weight) was added to the resulting solution of 2- (3,5-dicarboxyphenylamino) -4,6-dichlorotriazine and the reaction mixture was stirred at 35 ° C for 6 hours. Work-up as described gave 17.5 g of product.

Example 6:

Each of the triazine derivatives prepared in Examples 1 to 5 was applied by force to dipping on white cotton fabrics with the aid of an aqueous solution and the white textile was then washed with dyed textiles at 60 ° C. with a powder transfer detergent-free powder detergent.

The white textiles were not stained, the washed-out color remained completely in the fleet.

Claims

claims

1. Detergent containing a color transfer inhibitor in the form of a triazine derivative of the general formulas I or II,

T (NH-Ar (CO ₂ M) _a ) _b Hal _c (I)

X-NH-CH ₂ CH ₂ - (NY-CH ₂ CH ₂ -) _n NH-X (II) in which

T is a 1,3,5-triazinyl group,

Ar is a phenyl group,

M for H ₅ Na, Li or K,

Hal is Cl, Br or I, a is 1, 2 or 3, b is 1 and c is 2 or b is 2 and c is 1,

X is -T (NH-Ar (CO ₂ M) _a ) _b Hal _c-1 ,

Y is H or X, and n is a number from 0 to 50, besides conventional ingredients compatible with this ingredient.

2. Composition according to claim 1, characterized in that the triazine derivative of the general formula I and is obtainable by reaction of 2,4,6-trihalo-1,3,5-triazines with 1 or 2 equivalents of aminoaryl compound, wherein the aryl group of Aminoarylverbindung carries at least 1 carboxy substituent.

3. Composition according to claim 1, characterized in that the triazine derivative of the general formula II and is obtainable by reacting 2 equivalents of compounds of formula I with 1,2-diaminoethane or an oligo- or polyethylenimine.

4. Composition according to claim 3, characterized in that the oligo- or polyethylenimine of the formula NH ₂ -CH ₂ CH ₂ - (NH-CH ₂ CH ₂ -) _n NH ₂ corresponds, in which n is a number from 1 to 30, especially 2 to 20, is.

5. Composition according to one of claims 2 to 4, characterized in that the Aminoaryl compound is selected from 2-amino-benzoic acid, 3-amino-benzoic acid, 4-amino-benzoic acid, 3-amino-l, 2-benzenedicarboxylic acid, 4-amino-l, 2-benzenedicarboxylic acid, 2-aminobenzoic acid 1, 3-benzenedicarboxylic acid, 4-amino-1,3-benzenedicarboxylic acid, 5-amino-1,3-benzenedicarboxylic acid, 2-amino-1,4-benzenedicarboxylic acid, 4-amino-1,2,3-benzenetricarboxylic acid, 3 Amino-l, 2,4-benzenetricarboxylic acid, 5-amino-l, 2,4-benzenetricarboxylic acid, 6-amino-l, 2,4-benzenetricarboxylic acid and 2-amino-l, 3,5-benzenetricarboxylic acid, wherein the carboxylic acid groups also may be in salt form, and mixtures of these.

6. Composition according to one of claims 1 to 5, characterized in that it is 0.05 wt .-% to 2 wt .-%, in particular 0.2 wt .-% to 1 wt .-%, color transfer inhibiting triazine derivative of the general formula I and / or II contains.

7. Composition according to one of claims 1 to 6, characterized in that it additionally contains a polymer of vinylpyrrolidone, vinylimidazole, vinylpyridine-N-oxide or a copolymer of these.

8. Use of triazine derivatives of the general formulas I or II,

T (NH-Ar (CO ₂ M) _a ) _b Hal _c (I)

X-NH-CH ₂ CH ₂ - (NY-CH ₂ CH ₂ -) _n NH-X (II) in which

T is a 1,3,5-triazinyl group,

Ar is a phenyl group,

M for H, Na, Li or K,

Hal is Cl, Br or I, a is 1, 2 or 3, b is 1 and c is 2 or b is 2 and c is 1,

X is -T (NH-Ar (CO ₂ M) _a ) _b Hal _c- i,

Y is H or X, and n is a number from 0 to 50, to prevent the transfer of textile dyes from dyed textiles to undyed or other colored textiles when they are washed together in particular surfactant-containing aqueous solutions.

9. Use of triazine derivatives of the general formulas I or II,

T (NH-Ar (CO ₂ M) _a ) _b Hal _c (I)

X-NH-CH ₂ CH ₂ - (NY-CH ₂ CHr) _n NH-X (II) in which

T is a 1,3,5-triazinyl group,

Ar is a phenyl group,

M for H, Na, Li or K,

Hal is Cl, Br or I, a is 1, 2 or 3, b is 1 and c is 2 or b is 2 and c is 1,

X is -T (NH-Ar (CO ₂ M) _a ) _b Hal _c-1 ,

Y is H or X, and n is a number from 0 to 50, to avoid the change in the color impression of dyed textiles in their

Laundry in particular surfactant-containing aqueous solutions.

10. A process for washing textiles in surfactant-containing aqueous solutions, characterized in that one uses a surfactant-containing aqueous solution containing a triazine derivative of the general formulas I and / or II.