DE102007012975A1 - Color protecting detergent - Google Patents

Abstract

The color-saving of detergents, in their use for washing colored textiles should be improved. This was achieved essentially by using a non-reactive triazine derivative carrying sulfonic acid salt groups in the agent.

Description

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

laundry detergent included besides the indispensable for the washing process Ingredients such as surfactants and builder materials usually other ingredients, which are referred to as washing aids can summarize and the so different drug groups such as foam regulators, grayness inhibitors, bleaches, bleach activators and enzymes. Such adjuvants include also substances that should prevent colored Textiles after washing a changed color impression cause. This color impression change washed, d. H. cleaner, textiles can be based on the fact that dye content removed by the washing process from the textile ("fading"), on the other hand, you can get rid of differently colored textiles Precipitate dyes on the textile ("discolouring") Discolouration aspect can also be with undyed laundry items play a role when combined with colored laundry items getting washed. To avoid these unwanted side effects of Remove dirt from textiles by treating with usual to avoid surfactant-containing aqueous systems contain detergents, especially if they are used as so-called or colored laundry detergents are provided for washing colored textiles, Active ingredients that are the removal of dyes from the textile prevent or at least the deposition of detached, Avoid dyes on textiles in the wash liquor should. Many of the commonly used polymers have such a high affinity to dyes that they pull these reinforced from the dyed fiber, so that it comes to increased color losses.

Surprisingly has now been found that certain triazine derivatives defined below unexpectedly cause high color transfer inhibition, if you use them in detergents. Particularly pronounced is the prevention of staining white ones or other colored textiles washed out of textiles Dyes. It is conceivable that the below defined in more detail When washing, apply triazine derivatives to the textiles and - possibly by their sulfonic acid group content - repugnant act on dye molecules in the liquor.

The invention therefore provides the use of triazine derivatives of the general formulas I or II, T (NH-Ar (SO ₃ M) _a ) _b H _3-b (I) X (-T (NH-Ar (SO ₃ M) _c -NH-T (NH-Ar (SO ₃ M) _c ) ₂ ) _d (NH-Ar (SO ₃ M) _c ) _2-d ) ₂ (II ) in which
T is a 1,3,5-triazinyl radical,
Ar for a naphthalene, aniline, acetanilide or benzene moiety,
X is an optionally mono- or polysubstituted -SO ₃ M-substituted diaminostilbene, diaminobiphenyl, m-, o- or p-diaminobenzene or piperazine grouping,
M is H, Na, Li or K, preferably Na,
a for 1, 2 or 3,
b for 1, 2 or 3,
c for 0, 1, 2 or 3 and
d is 0, 1 or 2,
and the -NH substituents as well as the substituents X bound via the amino function are in the 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 in their common washing in particular surfactant-containing aqueous Solutions.

One Another object of the invention is a color protective Detergent containing a color transfer inhibitor in the form of a triazine derivative of the general defined above Formulas I or II besides usual with this ingredient compatible ingredients.

Triazine derivatives of general formula I are obtainable by reacting mono-, di- or trihalo-1,3,5-triazines with 1, 2 or 3 equivalents of aminoaryl compound, wherein the aryl group of the aminoaryl compound is a 1 to 3-fold sulfonate-substituted naphthalene , Acetanilide or benzene unit is. Suitable aminoaryl compounds are, for example, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 2-amino-1,3-benzenedisulfonic acid, 4-amino-1,3-benzenedisulfonic acid, 2-amino-1, 3,5-benzenedisulfonic acid, 2-amino-4-sulfonic acid acetanilide, 2-amino-1-naphthalenesulfonic acid, 2-amino-1,5-naphthalenedisulfonic acid, 7-amino-1,6-naphthalenedisulfonic acid and 7-amino-1,3, 6-naphthalene trisulfonic acid, wherein the sulfonic acid groups are in salt form. It is also possible to use mixtures of the aminoaryl compounds mentioned.

By Reaction of 1 equivalent of trihalo-1,3,5-triazine with 1 equivalent On aminoaryl compound is obtained compounds such those of the formula I are constructed with b = 1, but the Place the 2 H atoms still each 2 halogens on Triazinrest wear. By reacting 2 equivalents of these latter compounds with 1 equivalent of diaminostilbene or diaminobiphenyl (X) and subsequent Reaction with 2 equivalents of aminoaryl compound, wherein it is in the aryl group of the aminoaryl compound by a 0 to 3 fold sulfonate-substituted naphthalene, acetanilide or benzene unit one arrives at connections according to formula II (with d = 0). Contain one or more of the aryl groups one Acetamide grouping, so you get by reaction with alkali carbonate, for example, sodium carbonate, followed by reaction with 2 equivalents of triazine derivative analogous to the general formula I, which, however, carries 2 halogens on the triazine residue, and subsequent reaction with 2 equivalents of aminoaryl compound, wherein the aryl group of the aminoaryl compound is a 0 to 3 times sulfonate-substituted naphthalene, acetanilide or Benzene unit is, to compounds of the formula II (with d = 1 or 2). It is preferred if the diaminostilbene, diaminobiphenyl, Diaminobenzene and / or piperazine also additionally at least 1, in particular 2 sulfonic acid salt substituents, such as 4,4'-diamino-2,2'-biphenyldisulfonic acid disodium salt or 4,4'-diamino-2,2'-stilbenedisulfonic acid disodium salt. In particular, in this case, the aryl compound (Ar), different of the compounds of formula I, also free of sulfonic acid salt substituents be (c = 0 in formula II)). Preferably, it is trans-configured Style levels, but possibly also the cis-configured Stilbene and mixtures of these can be used. Also mixtures of Diaminostilbenen, Diaminobiphenylen, Diaminobenzolen and piperazines can be used.

at simultaneous use of various aminoaryl compounds or with simultaneous use of different diaminoaryl compounds or, if necessary, different at the same time substituted diaminostilbene diaminobiphenyls, diaminobenzenes and / or piperazines are obtained in the described preparation process casual compounds according to the formula I or II, in which the respective variables a, b, c, d, X and Ar are not always the same.

One Inventive agent preferably contains From 0.05% by weight to 2% by weight, in particular from 0.2% by weight to 1% by weight, dye transfer inhibiting compound of the general Formula I and / or II. Through the "and / or" formulation should be made clear that the joint use of Compounds which each correspond to one of the stated formulas, is possible.

The Compounds of the general formula I or II afford in both previously discussed aspects of color consistency, a contribution that It means diminish both the discoloration as well also the fading, although the effect of preventing the Staining, especially when washing white textiles, most pronounced. Another object of the invention is therefore the use of an appropriate compound to avoid the change in the color impression of textiles in their Laundry in particular surfactant-containing aqueous Solutions. Under the change of the color impression is by no means the difference between polluted and clean textile, but the difference between each clean Textile before and after the washing process.

One Another object of the invention is a method for washing of dyed textiles in surfactant-containing aqueous Solutions, which is characterized in that one uses a surfactant-containing aqueous solution, which contains a compound of general formula I or II. In such a procedure it is possible together with the dyed textile also white respectively to wash undyed textiles without the white or undyed textile is dyed. It is noteworthy that the compounds of the general formula I or II also have a positive effect on the color transfer on polyamide, and have a staining of textiles Polyamide or prevent polyamide content.

In addition to the compound of the formula I or formula II or mixtures thereof, an agent according to the invention may additionally comprise a known dye transfer inhibitor, then preferably in amounts of from 0.1% by weight to 2% by weight, in particular 0.2% by weight. to 1 wt .-%, containing in a preferred embodiment of the invention, a polymer of vinylpyrrolidone, vinylimidazole, vinylpyridine-N-oxide or a Co Polymer is made of these. Useful are both polyvinylpyrrolidones having molecular weights of 15,000 to 50,000 as well as polyvinylpyrrolidones having molecular weights above 1 000 000, in particular from 1 500 000 to 4 000 000, the known N-vinylimidazole / N-vinylpyrrolidone copolymers, the known Polyvinyloxazolidone, copolymers Base of vinyl monomers and carboxylic acid amides, pyrrolidone group-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 delivers 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 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, as particular powdered solids, in post-compacted particulate form, may be present as homogeneous solutions or suspensions, can except the inventively used Active substance in principle all known and customary in such agents Contain ingredients. The invention In particular, builders, surface-active agents can be used Surfactants, bleaching agents based on organic and / or inorganic Peroxygen compounds, bleach activators, water-miscible organic Solvents, enzymes, sequestrants, electrolytes, pH regulators and other auxiliaries, such as optical brighteners, Grayness inhibitors, foam regulators and dyes and perfumes contain.

The Agents according to the invention can be a surfactant or more surfactants, especially anionic surfactants, nonionic surfactants and their mixtures, but also cationic, zwitterionic and amphoteric surfactants come into question.

suitable Nonionic surfactants are, in particular, alkyl glycosides and ethoxylation and / or propoxylation products 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. Farther are corresponding ethoxylation and / or propoxylation products of N-alkylamines, vicinal diols, fatty acid esters and fatty acid amides, with respect to the alkyl part said long-chain alcohol derivatives correspond, and of alkylphenols having 5 to 12 carbon atoms in the alkyl radical useful.

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

in der R³ für einen linearen oder verzweigten Alkyl- oder Alkenylrest mit 7 bis 12 Kohlenstoffatomen, R⁴ für einen linearen, verzweigten oder cyclischen Alkylenrest oder einen Arylenrest mit 2 bis 8 Kohlenstoffatomen und R⁵ für einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest oder einen Oxy-Alkylrest mit 1 bis 8 Kohlenstoffatomen steht, wobei C₁-C₄-Alkyl- oder Phenylreste bevorzugt sind, und [Z] für einen linearen Polyhydroxyalkylrest, dessen Alkylkette mit mindestens zwei Hydroxylgruppen substituiert ist, oder alkoxylierte, vorzugsweise ethoxylierte oder propoxylierte Derivate dieses Restes steht. [Z] wird auch hier vorzugsweise durch reduktive Aminierung eines Zuckers wie Glucose, Fructose, Maltose, Lactose, Galactose, Mannose oder Xylose erhalten. Die N-Alkoxy- oder N-Aryloxy-substituierten Verbindungen können durch Umsetzung mit Fettsäuremethylestern in Gegenwart eines Alkoxids als Katalysator in die gewünschten Polyhydroxyfettsäureamide überführt werden. Eine weitere Klasse bevorzugt eingesetzter nichtionischer Tenside, die entweder als alleiniges nichtionisches Tensid oder in Kombination mit anderen nichtionischen Tensiden, insbesondere zusammen mit alkoxylierten Fettalkoholen und/oder Alkylglykosiden, eingesetzt werden, sind alkoxylierte, vorzugsweise ethoxylierte oder ethoxylierte und propoxylierte Fettsäurealkylester, vorzugsweise mit 1 bis 4 Kohlenstoffatomen in der Alkylkette, insbesondere Fettsäuremethylester. Auch nichtionische Tenside vom Typ der Aminoxide, beispielsweise N-Kokosalkyl-N,N-dimethylaminoxid und N-Talgalkyl-N,N-dihydroxyethylaminoxid, und der Fettsäurealkanolamide können geeignet sein. Die Menge dieser nichtionischen Tenside beträgt vorzugsweise nicht mehr als die der ethoxylierten Fettalkohole, insbesondere nicht mehr als die Hälfte davon. Als weitere Tenside kommen sogenannte Gemini-Tenside in Betracht. Hierunter werden im Allgemeinen solche Verbindungen verstanden, die zwei hydrophile Gruppen pro Molekül besitzen. Diese Gruppen sind in der Regel durch einen sogenannten „Spacer" voneinander getrennt. Dieser Spacer ist in der Regel eine Kohlenstoffkette, die lang genug sein sollte, dass die hydrophilen Gruppen einen ausreichenden Abstand haben, damit sie unabhängig voneinander agieren können. Derartige Tenside zeichnen sich im Allgemeinen durch eine ungewöhnlich geringe kritische Micellkonzentration und die Fähigkeit, die Oberflächenspannung des Wassers stark zu reduzieren, aus. In Ausnahmefällen werden unter dem Ausdruck Gemini-Tenside nicht nur derartig „dimere", sondern auch entsprechend „trimere" Tenside verstanden. Geeignete Gemini-Tenside sind beispielsweise sulfatierte Hydroxymischether oder Dimeralkohol-bis- und Trimeralkohol-tris-sulfate und -ethersulfate. Endgruppenverschlossene dimere und trimere Mischether zeichnen sich insbesondere durch ihre Bi- und Multifunktionalität aus. So besitzen die genannten endgruppenverschlossenen Tenside gute Netzeigenschaften und sind dabei schaumarm, so dass sie sich insbesondere für den Einsatz in maschinellen Wasch- oder Reinigungsverfahren eignen. Eingesetzt werden können aber auch Gemini-Polyhydroxyfettsäureamide oder Poly-Polyhydroxyfettsäureamide.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)

in the R ^{3 is} a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{4 is} a linear, branched or cyclic alkylene radical or an arylene radical having 2 to 8 carbon atoms and R ^{5 is} a linear, branched or cyclic alkyl radical or a Aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, wherein C ₁ -C ₄ alkyl or phenyl radicals are preferred, and [Z] is a linear polyhydroxyalkyl radical whose alkyl chain is substituted with at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this group. [Z] is also 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 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 from 1 to 4 carbon atoms in the alkyl chain, especially 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 by an unusually low critical micelle concentration and the ability to greatly reduce the surface tension of the water In exceptional cases, the term gemini surfactants not only such "dimer", but also corresponding to "trimeric" surfactants understood. Surfactants are, for example, sulfated hydroxymix ethers or dimer alcohol bis- and trimer sulfo-tris sulfates and ether sulfates End-capped dimeric and trimeric mixed ethers are notable in particular for their bi- and multifunctional nature low in cholesterol 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. As surfactants of the sulfonate type are preferably C ₉ -C ₁₃ alkylbenzenesulfonates, Olefinsulfonate, that is, mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as they are, for example, from C ₁₂ -C ₁₈ monoolefins with terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation obtained. Also suitable are alkanesulfonates which are obtained from C ₁₂ -C ₁₈ -alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. Geeig net are also 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 methyl esters of fatty acids of plant and / or animal origin with 8 to 20 C -Atomen in the fatty acid molecule and subsequent neutralization to water-soluble mono-salts are prepared, into consideration. These are preferably the α-sulfonated esters of hydrogenated coconut, palm, palm kernel or tallow fatty acids, although sulfonated products of unsaturated fatty acids, for example oleic acid, in small amounts, preferably in amounts not above about 2 to 3 wt. %, can be present. In particular, α-sulfofatty acid alkyl esters are preferred which have an alkyl chain with not more than 4 C atoms in the ester group, for example, methyl ester, ethyl ester, propyl ester and butyl ester. With particular advantage, the methyl esters of α-sulfo fatty acids (MES), but also their saponified disalts are used. Other suitable anionic surfactants are sulfated fatty acid glycerol esters, which are mono-, di- and triesters and mixtures thereof, as in the preparation by esterification by a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol to be obtained. Examples of alk (en) ylsulfates are the alkali metal salts and, in particular, the sodium salts of the sulfuric monoesters of C ₁₂ -C ₁₈ fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁₀ -C ₂₀ oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) ylsulfates of said chain length, which contain a synthetic, 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 ₁₂ -C ₁₆ -alkyl sulfates and C ₁₂ -C ₁₅ -alkyl sulfates and C ₁₄ -C ₁₅ -alkyl sulfates are particularly preferred. Also 2,3-alkyl sulfates, which can be obtained as commercial products of Shell Oil Company under the name DAN ^® , are suitable anionic surfactants. Also suitable are the sulfuric acid monoesters of straight-chain or branched C ₇ -C ₂₁ -alcohols ethoxylated with from 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C ₉ -C ₁₁ -alcohols having on average 3.5 mol of ethylene oxide (EO) or C ₁₂ - C ₁₈ -fatty alcohols with 1 to 4 EO. The preferred anionic surfactants also include the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters, and the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contain C ₈ to C ₁₈ fatty alcohol residues or mixtures of these. Particularly preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty alcohols, which by themselves are nonionic surfactants. Sulfosuccinates, whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are again particularly preferred. Likewise, it is also possible to use alk (en) ylsuccinic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof. Suitable further anionic surfactants are fatty acid derivatives of amino acids, for example N-methyltaurine (Tauride) and / or N-methylglycine (sarcosides). Particularly preferred are the sarcosides or the sarcosinates and here especially sarcosinates of higher and optionally monounsaturated or polyunsaturated fatty acids such as oleyl sarcosinate. As further anionic surfactants are particularly soaps into consideration. Particularly suitable are saturated fatty acid soaps, such as the salts of 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 in the form of their sodium, potassium or ammonium salts and as soluble Salts of organic bases, such as mono-, di- or triethanolamine, are present. The anionic surfactants are preferably in the form of their sodium or potassium salts, especially in the form of the sodium salts.

surfactants are in proportions according to the invention in detergents of preferably 5% by weight to 50% by weight, in particular 8% by weight to 30 wt .-%, contained.

An agent according to the invention preferably contains at least one water-soluble and / or water-insoluble, organic and / or inorganic builder. The water-soluble organic builder substances include polycarboxylic acids, in particular citric acid and sugar acids, monomeric and polymeric aminopolycarboxylic acids, in particular methylglycinediacetic acid, nitrilotriacetic acid and ethylenediaminetetraacetic acid and polyaspartic acid, polyphosphonic acids, in particular aminotris (methylenephosphonic acid), ethylenediaminetetrakis (methylenephosphonic acid) and 1-hydroxyethane-1,1-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, polymeric acrylic acids, methacrylic acids, maleic acids and copolymers thereof, 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. Commercial 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 vinylmethyl ethers, vinyl esters, ethylene, propylene and styrene, in which the proportion of acid is at least 50% by weight. It is also possible to use terpolymers which contain two unsaturated acids and / or salts thereof as monomers and also vinyl alcohol and / or an esterified vinyl alcohol or a carbohydrate as the third monomer as water-soluble organic builder substances. The first acidic monomer or its salt is derived from a monoethylenically unsaturated C ₃ -C ₈ -carboxylic acid and preferably from a C ₃ -C ₄ -monocarboxylic acid, in particular from (meth) -acrylic acid. The second acidic monomer or its salt may be a derivative of a C ₄ -C ₈ -dicarboxylic acid, with maleic acid being particularly preferred, and / or a derivative of an allylsulfonic acid which is substituted in the 2-position by an alkyl or aryl radical. Such polymers generally have a molecular weight between 1,000 and 200,000. Further preferred copolymers are those which have as monomers acrolein and acrylic acid / acrylic acid salts or vinyl acetate. The organic builder substances can be used, in particular for the preparation of liquid agents, in the form of aqueous solutions, preferably in the form of 30 to 50 percent by weight aqueous solutions. All of the acids mentioned are generally used in the form of their water-soluble salts, in particular their alkali metal salts.

such If desired, organic builders may be used in amounts up to 40 wt .-%, in particular up to 25 wt .-% and preferably from 1% by weight to 8% by weight. Quantities near the mentioned Upper limit are preferably in pasty or liquid, in particular hydrous, inventive Funds used.

Suitable water-soluble inorganic builder materials are, in particular, alkali metal silicates, alkali metal carbonates and alkali metal phosphates, which may be in the form of their alkaline, neutral or acidic sodium or potassium salts. Examples of these are trisodium phosphate, tetrasodium diphosphate, disodium dihydrogen diphosphate, pentasodium triphosphate, so-called sodium hexametaphosphate, oligomeric trisodium phosphate with degrees of oligomerization of from 5 to 1000, in particular from 5 to 50, and the corresponding potassium salts or mixtures of sodium and potassium salts. 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, the crystalline sodium aluminosilicates in detergent quality, more particularly zeolite A, P and optionally X, alone or in mixtures, for example in the form of a co-crystals of zeolites A and X (VEGOBOND ^® AX, a commercial product of Condea Augusta SpA), preferably , Amounts near the above upper limit are preferably used in solid, particulate agents. In particular, suitable aluminosilicates have no particles with a particle size greater than 30 .mu.m and preferably consist of at least 80% by weight of particles having a size of less than 10 .mu.m. Their calcium binding capacity, according to the information of the German Patent DE 24 12 837 can be determined, is usually in the range of 100 to 200 mg CaO per gram.

Suitable substitutes or partial substitutes for the said aluminosilicate are crystalline alkali silicates which may be present alone or in a mixture with amorphous silicates. The alkali metal silicates useful as builders in the compositions according to the invention preferably have a molar ratio of alkali metal oxide to SiO ₂ below 0.95, in particular from 1: 1.1 to 1:12, and may be present in amorphous or crystalline form. Preferred alkali metal silicates are the sodium silicates, in particular the amorphous sodium silicates, with a molar ratio of Na ₂ O: SiO ₂ of 1: 2 to 1: 2.8. The crystalline silicates which may be present alone or in admixture with amorphous silicates, are crystalline layer silicates with the general formula Na ₂ Si _x O _{2x + 1} · are used yH ₂ O, in which x, the so-called module, a number from 1.9 to 22, in particular 1.9 to 4 and y is a number from 0 to 33 and preferred values for x are 2, 3 or 4. 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 .yH 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 from 1.9 to 3.5 are used in a further preferred embodiment of compositions according to the invention. Crystalline layered silicates are marketed by the Clariant GmbH under the trade name Na-SKS, z. 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 (α-Na ₂ Si ₂ O ₅ ), Na-SKS-7 (β-Na ₂ Si ₂ O ₅ , natrosilite), Na-SKS-9 (NaHSi ₂ O ₅ · 3H ₂ O), Na-SKS-10 (NaHSi ₂ O ₅ · 3H ₂ O, kanemite), Na-SKS-11 (t-Na ₂ Si ₂ O ₅₎ and Na-SKS-13 (NaHSi ₂ O ₅ ), but especially Na-SKS-6 (δ-Na ₂ Si ₂ O ₅ ). In a preferred embodiment of inventive compositions is a granular compound of crystalline phyllosilicate and citrate, of crystalline layered silicate and aforementioned (co) polymeric polycarboxylic acid or of alkali silicate and alkali metal as it is available, for example under the name Nabion ^® 15 commercially ,

builders are preferred in the compositions according to the invention in amounts up to 75 wt .-%, in particular 5 wt .-% to 50 included.

When for use in the invention Means of suitable peroxygen compounds come in particular organic peracids or peracid salts organic Acids, such as phthalimidopercaproic acid, perbenzoic acid or salts of diperdodecanedioic acid, hydrogen peroxide and under the washing conditions hydrogen peroxide-releasing inorganic Salts, which include perborate, percarbonate, persilicate and / or persulfate like Caroat belong. If solid peroxygen compounds can be used, they can be in the form of powders or granules are used, which are also known in principle Wrapped up. If an inventive Agent contains peroxygen compounds, these are in Amounts of preferably up to 50% by weight, in particular of 5% by weight to 30 wt .-%, present. The addition of small amounts of known bleach stabilizers such as phosphonates, bristles or metaborates and metasilicates and magnesium salts such as magnesium sulfate be expedient.

When Bleach activators may be compounds that are under perhydrolysis conditions aliphatic peroxycarboxylic acids with preferably 1 to 10 C-atoms, in particular 2 to 4 C-atoms, and / or optionally substituted Perbenzoic acid, are used. Are suitable Substances which contain O- and / or N-acyl groups of said C atomic number and / or optionally substituted benzoyl groups. Preferred are multiply acylated 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, especially N-nonanoylsuccinimide (NOSI), acylated Phenolsulfonates, especially 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, Enolester as well as acetylated sorbitol and mannitol, respectively their mixtures (SORMAN), acylated sugar derivatives, in particular Pentaacetylglucose (PAG), Pentaacetylfruktose, Tetraacetylxylose and octaacetyl lactose and acetylated, optionally N-alkylated Glucamine and gluconolactone, and / or N-acylated lactams, for example N-benzoyl. The hydrophilic substituted acylacetals and The acyl lactams are also preferably used. Also combinations Conventional bleach activators can be used. Such bleach activators can, especially in the presence above-mentioned hydrogen peroxide-supplying bleach, in the usual quantity range, preferably in amounts of 0.5 wt .-% to 10 wt .-%, in particular 1 wt .-% to 8 wt .-%, based on total agent, be included are missing when using percarboxylic acid as the sole bleach but preferably completely.

additionally to the conventional bleach activators or in their place also sulfonimines and / or bleach-enhancing transition metal salts or transition metal complexes as so-called Be included bleach catalysts.

When Enzymes useful in the compositions are those of the class of Amylases, proteases, lipases, cutinases, pullulanases, hemicellulases, Cellulases, oxidases, laccases and peroxidases and mixtures thereof in question. 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 bind to carriers adsorbed and / or embedded in enveloping substances, to protect against premature inactivation. she are in the washing or cleaning agents according to the invention preferably in amounts of up to 5% by weight, in particular of 0.2% by weight to 4 wt .-%, contained. If the inventive Contains medium 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 be used in the agent according to the invention This can be done by incorporating the two or more separate ones or in a known manner separately prepared enzymes or by two or more together assembled in a granule Enzymes are performed.

To in the inventive compositions, in particular if they are in liquid or pasty form, include water-usable organic solvents 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, as well as mixtures thereof and those mentioned Classes of derivable ether. Such water-miscible Solvents are in the inventive Preferably in amounts not exceeding 30% by weight, in particular from 6% to 20% by weight.

to Setting a desired, through the mixture the remaining components are not self-generating pH the agents according to the invention can be and environmentally friendly 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, especially sulfuric acid, or bases, in particular ammonium or alkali hydroxides. Such pH regulators are in the inventive compositions in amounts of preferably not more than 20% by weight, in particular from 1.2% by weight to 17% by weight, contain.

graying have the task of removing the dirt from the textile fiber to keep suspended in the fleet. These are water-soluble Colloids mostly organic nature suitable, such as starch, Glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids starch or cellulose or salts of acidic sulfuric acid esters cellulose or starch. Also water-soluble, Acidic group-containing polyamides are for this purpose suitable. Furthermore, other than the above-mentioned starch derivatives can be used use, for example, aldehyde levels. To be favoured Cellulose ethers, such as carboxymethyl cellulose (Na salt), methyl cellulose, Hydroxyalkylcellulose and mixed ethers, such as methylhydroxyethylcellulose, Methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and their Mixtures, for example in amounts of 0.1 to 5 wt .-%, based on the means used.

invention Textile detergents can be used as optical brighteners, for example Derivatives of Diaminostilbendisulfonsäure or their alkali metal salts, although they are for the Use as a color detergent preferably free of optical brighteners are. For example, salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid are suitable or similar compounds, instead of the morpholino group a diethanolamino group, a methylamino group, an anilino group or carry a 2-methoxyethylamino group. Furthermore you can Brighteners of the type of substituted diphenylstyrene may be present for example, the alkali salts of 4,4'-bis (2-sulfostyryl) -diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) -diphenyls, or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl) -diphenyls. 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 ₁₈ -C ₂₄ fatty acids. Suitable non-surfactant foam inhibitors are, for example, organopolysiloxanes and mixtures thereof with microfine, optionally silanized silica and paraffins, waxes, microcrystalline waxes and mixtures thereof with silanated silicic acid or bis-fatty acid alkylenediamides. It is also advantageous to use mixtures of various foam inhibitors, for example those of silicones, paraffins or waxes. The foam inhibitors, in particular silicone- and / or paraffin-containing foam inhibitors, are preferably bound to a granular, water-soluble or dispersible carrier substance. In particular, mixtures of paraffins and bistearylethylenediamide are preferred.

The Preparation of inventive solid means provides no difficulties and can be done in a known way, for example by spray-drying or granulation, enzymes being used and any other thermally sensitive ingredients like for example bleach, if appropriate later separately be added. For the production fiction, according to Agents with increased bulk density, in particular in the range of 650 g / l to 950 g / l, is an extrusion step preferred method.

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. You get so easily unbreakable, yet under In general, a tablet produced in this way has a weight of from 10 g to 50 g, in particular from 15 g to 40 g, with sufficiently fast-dissolving tablets having breaking and bending strengths of from 100 to 200 N, preferably more than 150 N. 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) × (34 to 40 mm), in particular of 26 × 36 mm or of 24 × 38 mm.

liquid or pasty invention Agent in the form of common solvents Solutions are usually made by simply mixing the Ingredients that are in substance or as a solution in one automatic mixer can be given.

Examples

wurde in Mengen von 0,5 Gew.-% Waschbädern, die bei 40°C oder 60°C zum Einsatz kamen, zugesetzt. Die Note für die Anfärbung weißer Baumwolltextilien, die mit diesen in Gegenwart gefärbter (Cibacron^® Navy-LS; zuvor schlecht ausgewaschen) Textilien behandelt wurden, lag bei 4 bis 5. Beim Einsatz von Waschbädern, denen der Wirkstoff fehlte, ergaben sich Noten von 1 bis 2, jeweils auf einer Skala von 1 (= stark angefärbt) bis 5 (= keine erkennbare Anfärbung).Procedure: A triazine derivative of structure A given below, obtained as indicated in the reaction scheme below,

was added in amounts of 0.5% by weight of wash baths used at 40 ° C or 60 ° C. The grade for the staining of white cotton textiles with these dyed in the presence of (Cibacron ^® Navy LS; previously poorly washed) fabrics were treated was 4 to 5. When using washing baths lacking the active ingredient, to a scale of 1 revealed to 2, each on a scale of 1 (= strongly stained) to 5 (= no discernible staining).

QUOTES INCLUDE IN THE DESCRIPTION

This list The documents listed by the applicant have been automated generated and is solely for better information recorded by the reader. The list is not part of the German Patent or utility model application. The DPMA takes over no liability for any errors or omissions.

Cited patent literature

• - EP 0300305 [0016]
• - DE 2412837 [0024]

Claims (10)

Detergent containing a color transfer inhibitor in the form of a triazine derivative of general formulas I or II, T (NH-Ar (SO ₃ M _a ) _b H _{3 -b} (I) X (-T (NH-Ar (SO ₃ M) _c -NH-T (NH-Ar (SO ₃ M)) ₂ ) _d (NH-Ar (SO ₃ M) _c ) _2-d ) ₂ (II) in which T is a 1,3,5-triazinyl, Ar is a naphthalene, aniline, acetanilide or benzene moiety, X is an optionally mono- or polysubstituted -SO ₃ M-substituted diaminostilbene, diaminobiphenyl, diaminobenzene or piperazine moiety, M is H, Na, Li or K, a is 1, 2 or 3, b is 1, 2 or 3, c is 0, 1, 2 or 3 and d is 0, 1 or 2 , and the -NH substituents as well as the substituents X bound via the amino function are located in positions 2, 4 and 6 of the triazinyl ring, in addition to customary constituents compatible with this constituent. Means according to claim 1, characterized in that the triazine derivative of general formula I corresponds and is available is by reaction of mono-, di- or trihalo-1,3,5-triazines with 1, 2 or 3 equivalents of aminoaryl compound from 2-amino-benzenesulfonic acid, 3-amino-benzenesulfonic 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-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-naphthalenetrisulfonic acid and mixtures thereof, wherein the sulfonic acid groups are in salt form available. Composition according to claim 1, characterized in that the triazine derivative of general formula II corresponds to d = 0 and is obtainable by reacting 1 equivalent of trihalo-1,3,5-triazine with 1 equivalent of aminoaryl NH ₂ -Ar (SO ₃ M ) _c , further reaction of 2 equivalents of the compound thus obtainable with 1 equivalent of optionally mono- or polysubstituted -SO ₃ M-substituted diaminostilbene, diaminobiphenyl, diaminobenzene or piperazine (X) and subsequent reaction with 2 equivalents of aminoaryl compound Ar (SO ₃ M) _c wherein the aryl group of the aminoaryl compounds are each independently a 0 to 3-fold sulfonate-substituted naphthalene, acetanilide or benzene unit. Means according to claim 3, characterized in that the diaminostilbene, diaminobiphenyl, diaminobenzene or pipierazine at least 1, in particular 2 Sulfonsäuresalzsubstituenten having. Means according to claim 1, characterized in that the triazine derivative of general formula II with d = 1 or 2 corresponds. Agent according to one of claims 1 to 5, characterized in that it is 0.1 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. Agent according to one of claims 1 to 6, characterized in that it additionally comprises a polymer from vinylpyrrolidone, vinylimidazole, vinylpyridine-N-oxide or a Contains copolymer of these. Use of triazine derivatives of the general formulas I or II, T (NH-Ar (SO ₃ M) _a ) _b H _3-b (I) X (-T (NH-Ar (SO ₃ M) NH-T (NH-Ar (SO ₃ M) _c ) ₂ ) _d (NH-Ar (SO ₃ M) _C ) _2-d ) ₂ (II) in which T is a 1,3,5-triazinyl radical, Ar is a naphthalene, aniline, acetanilide or benzene moiety, X is an optionally mono- or polysubstituted -SO ₃ M-substituted diaminostilbene, diaminobiphenyl, diaminobenzene or piperazine moiety, M is H, Na, Li or K. , a is 1, 2 or 3, b is 1, 2 or 3, c is 0, 1, 2 or 3 and d is 0, 1 or 2, and the -NH substituents as well as the substituents bonded via the amino function X are in the positions 2, 4 and 6 of the triazinyl ring, 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. Use of triazine derivatives of the general formulas I or II, T (NH-Ar (SO ₃ M) _a ) _b H _3-b (I) X (-T (NH-Ar (SO ₃ M) _c -NH-T (NH-Ar (SO ₃ M) _c ) ₂ ) _d (NH-Ar (SO ₃ M) _c ) _2-d ) ₂ (II ) in which T is a 1,3,5-triazinyl radical, Ar is a naphthalene, aniline, acetanilide or benzene moiety, X is an optionally mono- or polysubstituted -SO ₃ M-substituted diaminostilbene, diaminobiphenyl, diaminobenzene or Piperazine moiety, M is H, Na, Li or K, a is 1, 2 or 3, b is 1, 2 or 3, c is 0, 1, 2 or 3 and d is 0, 1 or 2, and the -NH substituents as well as the substituents X bound via the amino function are in positions 2, 4 and 6 of the triazinyl ring to avoid the change in the color impression of dyed textiles during their washing in particular surfactant-containing aqueous solutions. Process for washing textiles in surfactant-containing aqueous solutions, characterized in that a surfactant-containing aqueous solution which is a triazine derivative of the general formulas I or II contains.