WO2012095354A1

WO2012095354A1 - Color-protecting detergents

Info

Publication number: WO2012095354A1
Application number: PCT/EP2012/050155
Authority: WO
Inventors: Mareile Job; Birgit GLÜSEN; Silvia Sauf
Original assignee: Henkel Ag & Co. Kgaa
Priority date: 2011-01-13
Filing date: 2012-01-05
Publication date: 2012-07-19
Also published as: DE102011008526A1

Abstract

The aim of the invention is to improve the color protection of detergents when used to wash colored textiles. Said aim is achieved substantially in that triazine derivatives having at least one aniline substitution on the triazine ring are used.

Description

Color protecting detergents

The present invention relates to the use of certain triazine derivatives as color transfer inhibiting agents in the washing of textiles and detergents containing these triazine derivatives.

In addition to the ingredients indispensable for the washing process, such as surfactants and builder materials, laundry detergents generally comprise further constituents which can be summarized under the term laundry detergents and which comprise such different active ingredient groups as foam regulators, grayness inhibitors, bleaches, 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 fact that dye components are removed by the washing process from the textile ("fading"), on the other hand, from other colored textiles detached dyes on the textile precipitate ("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 washing colored textiles, Wrkstoffe 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.

International patent applications WO 2008/1 10469 A1 and WO 2007/019981 A1 disclose the dye transfer-inhibiting properties of certain triazine derivatives which contain aryl substituents carrying sulfonic acid groups.

Surprisingly, it has now been found that certain triazine derivatives defined below with at least one aniline substitution on the triazine ring lead to unexpectedly high color transfer inhibitions when used in detergents. Particularly pronounced is the prevention of dyeing of white or other colored fabrics by washed out of textiles dyes. The invention relates to the use of triazine derivatives of the general formulas I or II,

(ArNH) _a T (NH-Z (S0 ₃ Y) _b) _c Z X3-a (NH-T (NHAr) _a X ₂ _a.) _D (S0 ₃ Y) _b in which

Ar for a benzene moiety,

Z is a naphthalene or benzene moiety or a straight-chain, branched or cyclic, saturated or mono- or polyethylenically unsaturated hydrocarbon radical having 1 to 22 carbon atoms,

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

X is -OH, -OR, -NH ₂ , NHR, -H, chlorine, bromine or iodine,

R is a C 1-5 alkyl, aryl, aralkyl or alkaryl group,

Y for H, Li, Na or K,

a is 1 or 2 and c is 1 or 2 and the sum of a + c is 2 or 3,

b is O, 1, 2 or 3, and

d is 2, 3, 4 or 5,

and the -NH- as well as the -X- substituents are located in positions 2, 4 and 6 of the triazinyl ring,

to avoid the transfer of textile dyes of dyed textiles to undyed or differently colored textiles when they are washed together in particular surfactant-containing aqueous solutions.

Triazine derivatives of general formula I are obtainable by reacting di- or trihalo-1, 3,5-triazines with 1 or 2 equivalents of an aminoaryl or aminoalkyl compound H ₂ N-Z (S0 ₃ Y) _b and 2 or 1 equivalents of aniline, wherein the meanings of Z, Y and b are as defined above and wherein the aryl group of the aminoaryl compound is an optionally 1 to 3 times sulfonate-substituted benzene or naphthalene unit. 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, the sulfonic acid groups of which may also be in salt form; Particularly preferred is 3-amino-benzenesulfonic acid or its sodium salt. The aminoalkyl compounds contain 1 to 22, especially 1 to 18, carbon atoms; she may be straight-chain, cyclic or branched, as well as saturated or unsaturated and are optionally 1 to 3 times sulfonate substituted. Suitable aminoalkyl compounds are, for example, 1-amino-hexanesulfonic acid, 3-aminopentanesulfonic acid and 2-aminobutanesulfonic acid, their sulfonic acid groups also being able to be present in salt form. It is also possible to use mixtures of the aminoaryl compounds mentioned and / or of the aminoalkyl compounds mentioned.

By reacting 2 equivalents of trihalo-1, 3,5-triazine with 1 equivalent of diaminoaryl or diaminoalkyl H ₂ NZ (S0 ₃ Y) _b NH ₂ , wherein the meanings of Z, Y and b are as defined above, and If the aminoaryl or aminoalkyl compound has more than two amino groups (and as oligoaminoaryl- or Oligoaminoalkylverbindung thus the formula (H ₂ N) _d Z (S0 ₃ Y) _b . NH ₂ with 2 or 4 equivalents of aniline d greater than 2), correspondingly more than 2 equivalents of trihalo-1, 3,5-triazine can be used per equivalent of the aminoaryl or aminoalkyl compound. Among the diaminoaryl compounds, 2,5-diaminobenzenesulfonic acid or its alkali metal salt, in particular sodium salt, is particularly preferred.

With simultaneous use of different aminoaryl or aminoalkyl compounds or with simultaneous use of different di- or Oligoaminoaryl- or -aminoalkylverbindungen or simultaneous use of optionally different aniline-substituted triazines obtained in the described preparation process casually compounds according to the formula I or II, in which the respective Variables a, b, c, d, X, Z and Ar are not always the same.

Color transfer inhibiting compounds of the general formula I and / or II are preferably used in amounts of from 0.05% by weight to 2% by weight, in particular from 0.2% by weight to 1% by weight, in detergents. The "and / or" formulation is intended to make it clear that the joint use of compounds which each correspond to one of the above formulas is also possible.

The compounds of the general formula I or II contribute to both of the above-mentioned aspects of color constancy, that is, they reduce both discoloration and fading, although the effect of preventing staining, especially when washing white textiles, is most pronounced. Further objects of the invention are therefore the use of a compound according to formulas I or II as defined above for avoiding the change in the color impression of textiles during their washing in particular surfactant-containing aqueous solutions, and detergents comprising a compound according to the above-defined formulas I or II II included. The change in the color impression is not the result of difference between soiled and clean textiles, but the difference between clean textiles before and after the washing process. A further advantage is that the compounds according to the above-defined formulas I or II have a particularly pronounced color-protecting effect on polyamide textiles and prevent dyeing of textiles made of polyamide or with polyamide content. The color transfer inhibitors according to the invention are therefore preferably used to avoid the transfer of color to textiles made of polyamide or with polyamide content.

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 or II. In such a method, it is possible to wash white or undyed textiles together with the dyed textile without the white or undyed textile being dyed.

A detergent may contain, in addition to the compound of formula I or formula II or mixtures thereof, conventional ingredients compatible with this ingredient. Thus, it may, for example, additionally contain a further color transfer inhibitor, then preferably in amounts of 0.1 wt .-% to 2 wt .-%, in particular 0.2 wt .-% to 1 wt .-%, containing in one preferred embodiment is selected from the polymers of vinylpyrrolidone, vinylimidazole, vinylpyridine-N-oxide or the copolymers thereof. Useful are both Polyvinylpyrroli- done with molecular weights of 15 000 to 50 000 as well as polyvinylpyrrolidones having higher molecular weights of, for example, up to more than 1 000 000, in particular from 1 500 000 to 4 000 000, N-vinylimidazole / N-vinylpyrrolidone copolymers, Polyvinyloxazolidone , Copolymers based on vinyl monomers and carboxamides, pyrrolidone-containing polyesters and polyamides, grafted polyamidoamines and polyethyleneimines, polyamine-N-oxide polymers, polyvinyl alcohols and copolymers based on acrylamidoalkenylsulfonic acids. However, it is also possible to use enzymatic systems comprising a peroxidase and hydrogen peroxide or a substance which gives off hydrogen peroxide in water. The addition of a mediator compound for the peroxidase, for example an acetosyringone, a phenol derivative or a phenotiazine or phenoxazine, is preferred in this case, whereby also above-mentioned polymeric Farbübertragungsinhibitorwirkstoffe can be used. Polyvinylpyrrolidone preferably has an average (weight 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 (weight average) molecular weight in the range of 5,000 to 50,000, especially 10,000 to 20,000 are preferred. Detergents, which may be in the form of homogeneous solutions or suspensions, in particular in powdered solids, in densified particle form, may 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 as well as dyes and fragrances.

The agents may contain 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 carbon 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 an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol residue 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, 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. The preferred ethoxylated alcohols include, for example, C ₂ -C ₁₄ -alcohols with 3 EO or 4 EO, Cg-C-alcohols with 7 EO, C ₁₃ -C ₁₅ -alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C ₂ -C ₈ -alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C ₂ -C ₄ -alcohol with 3 EO and C ₂ -C ₈ -alcohol with 7 EO. The stated degrees of ethoxylation represent statistical averages, 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 include (tallow) fatty alcohols with 14 EO, 16 EO, 20 EO, 25 EO, 30 EO or 40 EO. In particular, in means for use in mechanical processes usually extremely low-foam compounds are used puts. These include preferably C ₂ -C ₈ -alkylpolyethylenglykol-polypropylene glycol ethers, each with at 8 mol ethylene oxide and propylene oxide in the molecule. However, it is also possible to use other known low-foam nonionic surfactants, such as, for example, C ₂ -C ₈ -alkylpolyethylene glycol polybutylene glycol ethers having up to 8 mol of ethylene oxide and butylene oxide units in the molecule and end-capped alkylpolyalkylene glycol mixed ethers. Also particularly preferred are the hydroxyl-containing alkoxylated alcohols, 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 is CO for 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 ²

₁ I

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 -0-R 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 ^{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 an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, wherein

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 radical. [Z] is also here preferably by reductive amination of a sugar such as glucose, fructose, maltose, lactose, galactose, mannose or xylose receive. The N-alkoxy- or N-aryloxy-substituted compounds can be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst. 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 having 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl ester. 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 to act independently of one another 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 is understood to mean not only such "dimeric" but also corresponding "trimeric" surfactants Gemini surfactants are, for example, sulfated hydroxy mixed ethers or dimer alcohol bis- and trimer alcohol tris sulfates and ether sulfates End-capped dimeric and trimeric mixed ethers are notable in particular for their bi- and multifunctional nature there 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 poly-polyhydroxy fatty acid amides.

Suitable anionic surfactants are in particular soaps and those which contain sulfate or sulfonate groups. Preferred surfactants of the sulfonate type are C ₉ -C ₃ -alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and also disulfonates, such as are obtained, for example, from C ₂ -C ₈ -monoolefins having terminal or internal groups Double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation obtained. Also suitable are alkanesulfonates which are obtained from C ₂ -C ₈ -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 nach- following 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, preferred are α-sulfofatty acid alkyl esters 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 α-sulfofatty acids (MES), but also their saponified salts, are used with particular advantage. 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. Alk (en) ylsulfates are the alkali metal salts and, in particular, the sodium salts of the sulfuric monoesters of C ₂ -C ₈ fatty alcohols, for example, coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or C ₀ -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, produced on a petrochemical basis straight-chain alkyl radical, which have an analogous degradation behavior as the adequate compounds based on oleochemical raw materials. Of washing-technical interest, C ₂ -C ₆ -alkyl sulphates and C ₂ -C ₅ -alkyl sulfates and C ₄ -C ₅ -alkyl sulfates are particularly preferred. 2,3-alkyl sulfates, 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 ₂ -alcohols ethoxylated with from 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C 9 -C -alcohols having on average 3.5 mol of ethylene oxide (EO) or C ₂ -C 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 which are 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 optionally monounsaturated or polyunsaturated fatty acids such as oleyl sarcosinate. As further anionic surfactants are particularly soaps into consideration. In particular are suitable 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 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. Surfactants are present in detergents in proportions of normally from 1% by weight to 50% by weight, in particular from 5% by weight to 30% by weight.

A detergent preferably contains at least one water-soluble and / or water-insoluble, organic and / or inorganic builder. The water-soluble organic builder substances include polycarboxylic acids, in particular citric acid and sugar acids, monomeric and polymeric aminopolycarboxylic acids, in particular 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 -diphosphonic acid, polymeric hydroxy compounds such as dextrin and polymeric (poly) carboxylic acids, in particular the accessible by oxidation of polysaccharides or dextrins polycarboxylates, polymeric acrylic acids, methacrylic acids, maleic acids and copolymers of these, which may also contain polymerized small amounts of polymerizable substances without carboxylic acid functionality. 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 from 30,000 to 100,000. Commercially available products are, for example, Sokalan® CP 5, CP 10 and PA 30 from BASF. Suitable, although less preferred compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinyl methyl ethers, vinyl esters, ethylene, propylene and styrene, in which the proportion of 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, be. Such polymers generally have a molecular weight between 1,000 and 200,000. Further preferred copolymers are those which have as monomers acrolein and acrylic acid / acrylic acid salts or vinyl acetate. The organic builders can, in particular for the preparation of liquid agents, in the form of aqueous solutions, preferably in the form of 30 to 50 weight percent aqueous solutions are used. 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.

Suitable water-soluble inorganic builder materials are, in particular, alkali metal silicates, alkali metal carbonates and alkali metal phosphates which may be present in the form of their alkaline, neutral or acidic sodium or potassium salts. Examples thereof are trisodium phosphate, tetrasodium diphosphate, disodium dihydrogen diphosphate, pentasodium triphosphate, so-called sodium hexametaphosphate, oligomeric trisodium phosphate having 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. As water-insoluble, water-dispersible inorganic builder materials are in particular crystalline or amorphous alkali metal aluminosilicates, in amounts of up to 50 wt .-%, preferably not more than 40 wt .-% and in liquid agents, in particular from 1 wt .-% to 5 wt .-%, 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. Suitable aluminosilicates have, in particular, no particles with a particle size of more than 30 μm and preferably consist of at least 80% by weight of particles having a size of less than 10 μm. 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 metal oxide to SiO _{2 of} less than 0.95, in particular of 1: 1, 1 to 1: 12, and may be amorphous or crystalline. Preferred alkali silicates are the sodium silicates, in particular the amorphous sodium silicates, with a molar ratio Na ₂ 0: Si0 ₂ of 1: 2 to 1: 2.8. When crystalline silicates, which may be present alone or in a mixture with amorphous silicates, preferably crystalline phyllosilicates of the general formula Na ₂ Si _x 0 ₂ x ₊ iy H ₂ 0 are 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. Preferred crystalline phyllosilicates are those in which x in the abovementioned general formula assumes the values 2 or 3. In particular, both β- and δ-sodium disilicates (Na ₂ Si ₂ O ₅ y H ₂ O) are preferred. Also prepared from amorphous alkali silicates, practically anhydrous crystalline alkali silicates of the abovementioned general formula in which x is a number from 1, 9 to 2.1, can be used in inventive compositions. 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. Crystalline sodium silicates with a modulus in the range of 1.9 to 3.5 are used in a further preferred embodiment of compositions according to the invention. Crystalline layered silicates are marketed 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 ₁₄ O ₂₉ xH 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 .xH ₂ O, Makatite). Of these, especially Na-SKS-5 (a-Na ₂ Si ₂ 0 ₅ ), Na-SKS-7 (ß-Na ₂ Si ₂ 0 ₅ , Natrosilit), Na-SKS-9 (NaHSi ₂ 0 ₅ 3H ₂ 0), Na-SKS-10

(NaHSi ₂ 0 ₅ 3H ₂ 0, kanemite), Na-SKS-1 1 (t-Na ₂ Si ₂ 0 ₅ ) and Na-SKS-13 (NaHSi ₂ 0 ₅ ), but especially Na-SKS-6 (5 -Na ₂ Si ₂ O ₅ ). In a preferred embodiment of the composition according to the invention, a granular compound of crystalline phyllosilicate and citrate, of crystalline phyllosilicate and of the above-mentioned (co-) polymeric polycarboxylic acid, or of alkali silicate and alkali metal carbonate, such as, for example, commercially available under the name Nabion® 15, is used , Builders are usually contained in amounts of up to 75 wt .-%, in particular 5 wt .-% to 50.

Peroxygen compounds which are suitable for use in detergents are, in particular, organic peracids or persalts of organic acids, such as phthalimidopercaproic acid, perbenzoic acid or salts of diperdodecanedioic acid, hydrogen peroxide and inorganic salts which release hydrogen peroxide under the washing conditions, including perborate, percarbonate, persilicate and / or persulphate like Caroat belong. 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.

As bleach activators, it is possible to use compounds which, under perhydrolysis conditions, comprise aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid, can be used. 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, enol ester and acetylated sorbitol and mannitol or mixtures thereof (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-benzoylcaprolactam. The hydrophilic substituted acyl acetals and the acyl lactams are also preferably used. Also combinations of conventional

Bleach activators can be used. Such bleach activators can, in particular in the presence of the abovementioned hydrogen peroxide-supplied 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, sulfone imines and / or bleach-enhancing transition metal salts or transition metal complexes 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 enzymatic agents obtained 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. The enzymes may be adsorbed to carriers and / or embedded in encapsulants 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 in a known manner separately prepared enzymes or by two or more enzymes formulated together in a granulate be performed.

Among the detergents, in particular when they are in liquid or pasty form, usable organic solvents in addition to water include alcohols having 1 to 4 carbon atoms, in particular methanol, ethanol, isopropanol and tert-butanol, diols having 2 to 4 C Atoms, in particular ethylene glycol and propylene glycol, and mixtures thereof and derived 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.

To establish a desired, not by the mixture of the other components resulting pH itself, the compositions of the invention system and environmentally friendly acids, especially 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 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 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 from 0.1 to 5% by weight, based on the compositions used.

Detergents 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 washing agents. 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 are substituted for 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. Suitable foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of C ₈ -C ₂₄ -fatty acids. Suitable non-surfactant foam inhibitors are, for example, organopolysiloxanes and mixtures thereof with microfine, optionally signed silica and paraffins, waxes, microcrystalline waxes and mixtures thereof with signed silica 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.

The preparation of solid agents presents no difficulties and may be accomplished in a known manner, for example by spray-drying or granulation, with enzymes and any other thermally-sensitive ingredients, such as bleach, optionally added separately later. For the production of compositions having an increased bulk density, in particular in the range from 650 g / l to 950 g / l, a process comprising an extrusion step is preferred.

For the preparation of compositions 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 components - optionally one layer at a time - in a 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 of the washing machine, is dependent on the geometry and the volume of this metering device. exemplary preferred embodiments have a footprint of (20 to 30 mm) x (34 to 40 mm), in particular of 26x36 mm or 24x38 mm.

Liquid or pasty compositions in the form of conventional solvent-containing solutions are usually prepared by simply mixing the ingredients, which can be added in bulk or as a solution in an automatic mixer.

Examples

Triazine derivatives A or B of the structures shown below

B were added to wash baths used at 60 ° C. The score for the staining of white polyamide fabrics treated with these in the presence of dyed (Acid Blue 1 13, previously poorly washed) fabrics was 4 to 5. The use of wash baths lacking the active ingredient produced grades from 1 to 2, each on a scale of 1 (= strongly stained) to 5 (= no discernible staining).

Claims

claims

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

Ar for a benzene moiety,

Z is a naphthalene or benzene moiety or a straight-chain, branched or cyclic, saturated or mono- or polyethylenically unsaturated

Hydrocarbon radical having 1 to 22 carbon atoms,

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

X is -OH, -OR, -NH ₂ , NHR, -H, chlorine, bromine or iodine,

R is a C 1-5 alkyl, aryl, aralkyl or alkaryl group,

Y for H, Li, Na or K,

a is 1 or 2 and c is 1 or 2 and the sum of a + c is 2 or 3,

b is O, 1, 2 or 3, and

d is 2, 3, 4 or 5,

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

Ar for a benzene moiety,

Z is a naphthalene or benzene moiety or a straight-chain, branched cyclic, saturated or mono- or polyethylenically unsaturated

Hydrocarbon radical having 1 to 22 carbon atoms,

T is a 1, 3,5-triazinyl radical, X is -OH, -OR, -NH ₂ , NHR, -H, chlorine, bromine or iodine,

R is a C 1-5 alkyl, aryl, aralkyl or alkaryl group,

Y for H, Li, Na or K,

a is 1 or 2 and c is 1 or 2 and the sum of a + c is 2 or 3,

b is O, 1, 2 or 3, and

d is 2, 3, 4 or 5,

to avoid the change in the color impression of dyed textiles during their washing in particular surfactant-containing aqueous solutions.

Use according to claim 1 or 2, characterized in that the triazine derivative corresponds to the general formula I and is obtainable by reacting di- or trihalo-1, 3,5-triazines with 1 or 2 equivalents of an aminoaryl or aminoalkyl compound H ₂ N- Z (S0 ₃ Y) _b and 1 equivalent of aniline, wherein the aminoaryl compound is selected from 2-amino-benzenesulfonic acid, 3-amino-benzenesulfonic acid, 4-amino-benzenesulfonic acid, 2-amino-1,

3-benzenedisulfonic acid,

4-amino-1,3-benzenedisulfonic acid, 2-amino-1,3,5-benzenetrisulfonic acid, 2-amino-4-sulfonic acid acetanilide, 2-amino-1-naphthalenesulfonic acid, 2-amino-1,5-naphthalenedisulfonic acid, 7-amino-1,6-naphthalenedisulfonic acid, 7-amino-1,3,6-naphthalene-trisulfonic acid and mixtures thereof, and wherein the aminoalkyl compound is selected from 1-amino-hexanesulfonic acid, 3-aminopentanesulfonic acid and 2-aminobutanesulfonic acid and mixtures thereof , wherein the sulfonic acid groups are in salt form.

Use according to claim 1 or 2, characterized in that the triazine derivative corresponds to the general formula II in which Z is the 2,5-diaminobenzenesulfonic acid group or its alkali metal salt.

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 or II

(ArNH) _a T (NH-Z (S0 ₃ Y) _b) _c X ₃ -ac (I) Z (NH-T (NHAr) _a X ₂ _a.) _D (S0 ₃ Y) _b (II) in to those

Ar for a benzene moiety,

Z is a naphthalene or benzene moiety or a straight, branched or straight chain cyclic, saturated or mono- or polyethylenically unsaturated

Hydrocarbon radical having 1 to 22 carbon atoms,

T for a 1, 3,

5-triazinyl,

X is -OH, -OR, -NH ₂ , NHR, -H, chlorine, bromine or iodine,

R is a C _1-18 alkyl, aryl, aralkyl or alkaryl group,

Y for H, Li, Na or K,

a is 1 or 2 and c is 1 or 2 and the sum of a + c is 2 or 3,

b is O, 1, 2 or 3, and

d is 2, 3, 4 or 5,

contains.

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

Ar for a benzene moiety,

Hydrocarbon radical having 1 to 22 carbon atoms,

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

X is -OH, -OR, -NH ₂ , NHR, -H, chlorine, bromine or iodine,

R is a C 1-5 alkyl, aryl, aralkyl or alkaryl group,

Y for H, Li, Na or K,

a is 1 or 2 and c is 1 or 2 and the sum of a + c is 2 or 3,

b is O, 1, 2 or 3, and

d is 2, 3, 4 or 5,

and the -NH- as well as the -X- substituents are located in positions 2, 4 and 6 of the triazinyl ring.

7. Composition according to claim 6, characterized in that it is color transfer inhibiting

Compounds of general formula I and / or II in amounts of 0.05 wt .-% to 2 wt .-%, in particular 0.2 wt .-% to 1 wt .-%. Composition according to claim 6 or 7, characterized in that it additionally contains a further color transfer inhibitor selected from the polymers of vinylpyrrolidone, vinylimidazole, vinylpyridine-N-oxide or the copolymers thereof.