DE102007016391A1 - Detergent or cleaning agent for preventing transfer of textile color of colored textiles from uncolored or different colored textiles in laundry, particularly in tenside containing aqueous solution, has color transfer inhibitor - Google Patents

Abstract

The detergent or cleaning agent has a color transfer inhibitor in the form of a compound or another compound of general formula (I). The polymeric substrates are also provided, which have hydroxy, primary or secondary amino group as functional group. The compound having general formula (I), is new. (I) X : CO-CH=CH2, CO-C(CH3)=CH2, CO-O-aryl, 2-6C alkylene-SO2-CH=CH2 or CO-NH-R1>, where R1> is 1-30C alkyl, 1-30C halogenalkyl, 1-30C hydroxyalkyl, 1-6C alkyloxy-1-30C alkyl, 1-6C alkylcarbonyloxy-1-30C alkyl, amino-1-30C-alkyl, mono- or di(1-6C alkyl)amino-1-30C-alkyl, ammonio-1-30C-alkyl, polyoxyalkylene-130C-alkyl, polysiloxanyl-1-30C-alkyl, (meth)acryloyloxy-1-30C-alkyl, sulfono-1-30C-alkyl, phosphono-1-30C-alkyl, di(1-6C alkyl)phosphono-3-30C-alkyl, phosphonato-1-30C-alkyl, di(1-6C-alkyl)phosphonato-1-30C-alkyl or a saccharide residue. An independent claim is also included for a method for washing of textiles in tenside containing aqueous solutions, which involves utilizing tenside containing aqueous solutions, which has a compound or another compound having formula (I) and a polymer. [Image].

Description

The The present invention relates to the use of compounds having certain reactive groups as dye transfer inhibiting Active ingredients in the washing and / or cleaning of textiles and washing or Detergents containing such compounds.

washing and detergents contain, in addition to the detergents or cleaning process indispensable ingredients like surfactants and builders usually other ingredients, which can be summarized by the term washing aids and the different drug classes such as foam regulators, Graying inhibitors, bleaching agents, bleach activators and enzymes include. Such excipients also include substances which are intended to prevent dyed textile fabrics 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 from the textile by the washing or cleaning process (fade), on the other hand may be different in color Apply textiles to precipitated dyes on the textile ( "Coloring"). The discoloration aspect can also in undyed laundry items a role Play this together 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 however, have such a high affinity for dyes that they pull this reinforced from the dyed fiber, so that it comes in their use to color losses.

Surprisingly has now been found that certain reactive cyclic carbonates and ureas to unexpectedly high color transfer inhibitions lead when used in detergents. Especially pronounced is the prevention of staining of white or otherwise colored textiles through Textiles washed out dyes. It is conceivable that the below Still further defined compounds when washing on the Tighten textiles and thereby on the one hand effectively detachment which will prevent dyes from the textiles and they to another repellent to dye molecules already in the liquor Act.

worin
R für C₁-C₁₂-Alkylen steht;
k für eine Zahl größer als 0 steht,
X für CO-CH=CH₂, CO-C(CH₃)=CH₂, CO-O-Aryl, C₂-C₆-Alkylen-SO₂-CH=CH₂, oder CO-NH-R¹ steht; und R¹ für C₁-C₃₀-Alkyl, C₁-C₃₀-Halogenalkyl, C₁-C₃₀-Hydroxyalkyl, C₁-C₆-Alkyloxy-C₁-C₃₀-alkyl, C₁-C₆-Alkylcarbonyloxy-C₁-C₃₀-alkyl, Amino-C₁-C₃₀-alkyl, Mono- oder Di(C₁-C₆-alkyl)amino-C₁-C₃₀-alkyl, Ammonio-C₁-C₃₀-alkyl, Polyoxyalkylen-C₁-C₃₀-alkyl, Polysiloxanyl-C₁-C₃₀-alkyl, (Meth)acryloyloxy-C₁-C₃₀-alkyl, Sulfono-C₁-C₃₀-alkyl, Phosphono-C₁-C₃₀-alkyl, Di(C₁-C₆-alkyl)phosphono-C₁-C₃₀-alkyl, Phosphonato-C₁-C₃₀-alkyl, Di(C₁-C₆-alkyl)phosphonato-C₁-C₃₀-alkyl oder einen Saccharidrest steht, wobei in Formel I X diese Bedeutung nur dann hat, wenn k für 1 steht, oder
X für

• (i) den Rest eines Polyamins, an das der in Klammern stehende Formelteil über (CO)NH-Gruppen gebunden ist, oder
• (ii) ein polymeres Gerüst, an das der in Klammern stehende Formelteil über (CO)-, NH-C₂-C₆-Alkylen-O(CO)- oder (CO)-O-C₂-C₆-Alkylen-O(CO)-Gruppen gebunden ist, oder
• (iii) ein polymeres Gerüst, an das der in Klammern stehende Formelteil über (CO)-Polysiloxanyl-C₁-C₃₀-alkyl-Gruppen gebunden ist,

steht, wenn k für eine Zahl von mehr als 1 steht,
zur Vermeidung der Übertragung von Textilfarbstoffen von gefärbten Textilien auf ungefärbte oder andersfarbige Textilien bei deren gemeinsamer Wäsche in insbesondere tensidhaltigen wäßrigen Lösungen.The invention relates to the use of compounds of general formulas I or II,

wherein
R is C ₁ -C ₁₂ alkylene;
k is a number greater than 0,
X is CO-CH = CH ₂ , CO-C (CH ₃ ) = CH ₂ , CO-O-aryl, C ₂ -C ₆ -alkylene-SO ₂ -CH = CH ₂ , or CO-NH-R ¹ ; and R ^{1 is} C ₁ -C ₃₀ -alkyl, C ₁ -C ₃₀ -haloalkyl, C ₁ -C ₃₀ -hydroxyalkyl, C ₁ -C ₆ -alkyloxy-C ₁ -C ₃₀ -alkyl, C ₁ -C ₆ - Alkylcarbonyloxy-C ₁ -C ₃₀ -alkyl, amino-C ₁ -C ₃₀ -alkyl, mono- or di (C ₁ -C ₆ -alkyl) amino-C ₁ -C ₃₀ -alkyl, ammonio-C ₁ -C ₃₀ alkyl, polyoxyalkylene C ₁ -C ₃₀ alkyl, polysiloxanyl C ₁ -C ₃₀ alkyl, (meth) acryloyloxy C ₁ -C ₃₀ alkyl, sulfono C ₁ -C ₃₀ alkyl, phosphonoC ₁ C ₃₀ alkyl, di (C ₁ -C ₆ alkyl) phosphono C ₁ -C ₃₀ alkyl, phosphonato C ₁ -C ₃₀ alkyl, di (C ₁ -C ₆ alkyl) phosphonato C ₁ -C ₃₀ alkyl or a saccharide radical, wherein in formula IX this meaning has only if k is 1, or
X for

• (i) the residue of a polyamine to which the parenthesized part of the formula is linked via (CO) NH groups, or
• (ii) a polymeric backbone to which the parenthesized part of the formula is attached via (CO) -, NH-C ₂ -C ₆ -alkylene-O (CO) - or (CO) -OC ₂ -C ₆ -alkylene-O ( CO) groups, or
• (iii) a polymeric backbone to which the parenthetical formula part is attached via (CO) polysiloxanyl-C ₁ -C ₃₀ -alkenoyl kyl groups is bound,

stands if k stands for a number of more than 1,
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.

worin
R für C₁-C₁₂-Alkylen steht;
k für eine Zahl größer als 0 steht,
X für CO-CH=CH₂, CO-C(CH₃)=CH₂, CO-O-Aryl, C₂-C₆-Alkylen-SO₂-CH=CH₂, oder CO-NH-R¹ steht; und R¹ für C₁-C₃₀-Alkyl, C₁-C₃₀-Halogenalkyl, C₁-C₃₀-Hydroxyalkyl, C₁-C₆-Alkyloxy-C₁-C₃₀-alkyl, C₁-C₆-Alkylcarbonyloxy-C₁-C₃₀-alkyl, Amino-C₁-C₃₀-alkyl, Mono- oder Di(C₁-C₆-alkyl)amino-C₁-C₃₀-alkyl, Ammonio-C₁-C₃₀-alkyl, Polyoxyalkylen-C₁-C₃₀-alkyl, Polysiloxanyl-C₁-C₃₀-alkyl, (Meth)acryloyloxy-C₁-C₃₀-alkyl, Sulfono-C₁-C₃₀-alkyl, Phosphono-C₁-C₃₀-alkyl, Di(C₁-C₆-alkyl)phosphono-C₁-C₃₀-alkyl, Phosphonato-C₁-C₃₀-alkyl, Di(C₁-C₆-alkyl)phosphonato-C₁-C₃₀-alkyl oder einen Saccharidrest steht, wobei in Formel I X diese Bedeutung nur dann hat, wenn k für 1 steht, oder
X für

• (i) den Rest eines Polyamins, an das der in Klammern stehende Formelteil über (CO)NH-Gruppen gebunden ist, oder
• (ii) ein polymeres Gerüst, an das der in Klammern stehende Formelteil über (CO)-, NH-C₂-C₆-Alkylen-O(CO)- oder (CO)-O-C₂-C₆-Alkylen-O(CO)-Gruppen gebunden ist, oder
• (iii) ein polymeres Gerüst, an das der in Klammern stehende Formelteil über (CO)-Polysiloxanyl-C₁-C₃₀-alkyl-Gruppen gebunden ist,

steht, wenn k für eine Zahl von mehr als 1 steht,
zur Vermeidung der Übertragung von Textilfarbstoffen von gefärbten Textilien auf ungefärbte oder andersfarbige Textilien bei deren gemeinsamer Wäsche in insbesondere tensidhaltigen wäßrigen Lösungen.Another object of the invention is the use of polymers, which are obtainable by reacting a polymeric substrate having functional groups which are selected from hydroxy groups, primary and secondary amino groups, with a compound of general formulas I or II,

wherein
R is C ₁ -C ₁₂ alkylene;
k is a number greater than 0,
X is CO-CH = CH ₂ , CO-C (CH ₃ ) = CH ₂ , CO-O-aryl, C ₂ -C ₆ -alkylene-SO ₂ -CH = CH ₂ , or CO-NH-R ¹ ; and R ^{1 is} C ₁ -C ₃₀ -alkyl, C ₁ -C ₃₀ -haloalkyl, C ₁ -C ₃₀ -hydroxyalkyl, C ₁ -C ₆ -alkyloxy-C ₁ -C ₃₀ -alkyl, C ₁ -C ₆ - Alkylcarbonyloxy-C ₁ -C ₃₀ -alkyl, amino-C ₁ -C ₃₀ -alkyl, mono- or di (C ₁ -C ₆ -alkyl) amino-C ₁ -C ₃₀ -alkyl, ammonio-C ₁ -C ₃₀ alkyl, polyoxyalkylene C ₁ -C ₃₀ alkyl, polysiloxanyl C ₁ -C ₃₀ alkyl, (meth) acryloyloxy C ₁ -C ₃₀ alkyl, sulfono C ₁ -C ₃₀ alkyl, phosphonoC ₁ C ₃₀ alkyl, di (C ₁ -C ₆ alkyl) phosphono C ₁ -C ₃₀ alkyl, phosphonato C ₁ -C ₃₀ alkyl, di (C ₁ -C ₆ alkyl) phosphonato C ₁ -C ₃₀ alkyl or a saccharide radical, wherein in formula IX this meaning has only if k is 1, or
X for

• (i) the residue of a polyamine to which the parenthesized part of the formula is linked via (CO) NH groups, or
• (ii) a polymeric backbone to which the parenthesized part of the formula is attached via (CO) -, NH-C ₂ -C ₆ -alkylene-O (CO) - or (CO) -OC ₂ -C ₆ -alkylene-O ( CO) groups, or
• (iii) a polymeric backbone to which the parenthesized part of the formula is attached via (CO) polysiloxanyl-C ₁ -C ₃₀ -alkyl groups,

stands if k stands for a number of more than 1,
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.

To The suitable polymeric substrates include in particular Polyvinyl alcohols, polyalkyleneamines such as polyethylenimine, polyvinylamines, Polyallylamines, polyethylene glycols, chitosan, polyamide-epichlorohydrin resins, Polyaminostyrenes, with aminoalkyl groups terminal or as a side group substituted polysiloxanes such as polydimethylsiloxanes, peptides, polypeptides, and proteins and mixtures thereof.

Particularly preferred polymeric substrates are selected from polyethyleneimines having molecular weights in the range of 5,000 to 100,000, in particular 15,000 to 50,000,
Compounds of the formula where m = 1 to 10, preferably 1 to 5, particularly preferably 1 to 3, where n = 1 to 50, preferably 30 to 50, where o = 0 to 10, preferably 1 to 5, particularly preferably 1 to 3 and wherein R '= H, C _1-22 -alkyl, an amino or ammonium group, and / or
Compounds of the formula NH ₂ - [CH (CH ₃ ) -CH ₂ O] ₁ - [CH ₂ -CH ₂ O] _m - [CH ₂ -CH (CH ₃ ) O] _n -R ", where 1, m and n independently of each other are numbers from 0 to 50 with the proviso that the sum of l + m + n = 5 to 100, in particular 10 to 50, preferably 10 to 30, particularly preferably 10 to 20, and R "= H , is a C _1-22 alkyl, C _1-22 aminoalkyl or C _1-22 ammonium alkyl group, and mixtures thereof.

Preferred among the polymers are those obtainable by reacting the polymeric substrate with a compound of the general formula I where k = 1 or 11. Further preferred are those Polymers obtainable by reaction of the polymeric substrate with molar amounts of compounds of the general formulas I where k = 1 or II, based on their content of hydroxy groups, primary and secondary amino groups.

The compound of formula I is preferably selected from
4-phenyloxycarbonyloxymethyl-2-oxo-1,3-dioxolane,
4- (4-Phenyloxycarbonyloxy) butyl-2-oxo-1,3-dioxolane,
2-oxo-1,3-dioxolan-4-yl-methyl,
2-oxo-1,3-dioxolan-4-yl-methyl,
4- (2-oxo-1,3-dioxolan-4-yl) butyl acrylate,
4- (2-oxo-1,3-dioxolan-4-yl) -butyl methacrylate and
4- (Vinylsulfonylethyloxy) butyl-2-oxo-1,3-dioxolane.

The preparation of compounds of the general formulas I and II and their reaction with polymeric substrates are described in the international patent application WO 2005/058863 described.

Of the desired color transfer inhibiting effect occurs however, even if such compounds are used in a laundering step, for example as part of a fabric softener, in contact with the textile and the textile thus treated next washing, the one with the inventively used Active substance-containing agent or one which is free of it, can be carried out in the presence of different-colored Laundry washes.

One Another object of the invention is therefore a color protective Cleaning, washing or laundry aftertreatment compositions containing a color transfer inhibitor in the form of a compound the general formulas I or II and / or one defined above by reaction of a polymeric substrate, the functional over Has groups which are among hydroxy groups, primary and secondary amino groups are selected with a compound of the general formulas I or II available Polymers in addition to conventional compatible with this component Ingredients.

One Inventive agent preferably contains 0.01% by weight to 5% by weight, in particular 0.1% by weight to 1% by weight, the said polymer or the dye transfer inhibiting Compound of 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 general formula I or II as well as by their reaction with polymeric substrate available polymers achieve color consistency in both aspects mentioned above a contribution, that is, they reduce both the discoloration as well as the fading, though the effect of the prevention staining, especially when washing white Textiles, most pronounced. Another item The invention therefore relates to the use of a corresponding compound to avoid the change in the color impression of textiles in their washing in particular surfactant-containing aqueous solutions. Under the change of the color impression is by no means to understand the difference between polluted and clean textile but the color 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, the one compound of general formula I and / or II and / or one by reaction of a polymeric substrate, over has functional groups, which among hydroxy groups, primary and secondary amino groups selected are, with a compound of the general formulas I or II available polymer contains. In such a process it is possible along with the dyed textile also white respectively to wash undyed textiles without the white or undyed textile is dyed.

An inventive composition can, in addition to the compound of formula I or II or said polymer obtainable from them, if desired, a known dye transfer inhibitor, then preferably in amounts of 0.01 wt .-% to 5 wt .-%, in particular 0.1 wt. % to 1% by weight, which in a preferred embodiment of the invention is a polymer of vinylpyrrolidone, vinylimidazole, vinylpyridine-N-oxide or a copolymer thereof. Useful are both polyvinylpyrrolidones having molecular weights of 15,000 to 50,000 and also polyvinylpyrrolidones having molecular weights above 1,000,000, in particular of 1 500,000 to 4,000,000, N-vinylimidazole / N-vinylpyrrolidone copolymers, polyvinyloxazolidones, copolymers based on vinyl monomers and carboxylic acid amides, polyesters containing polyesters containing polyarylamines and polyamides, grafted polyamidoamines and polyethyleneimines, polymers containing amide groups from secondary amines, 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. But you can also use other known low-foam nonionic surfactants, such as C ₁₂ -C ₁₈ alkylpolyethylene glycol polybutylenglykolether each with up to 8 moles of ethylene oxide and butylene oxide in the molecule and endgruppenverschlossene alkylpolyalkylene glycol mixed. Also particularly preferred are the hydroxyl-containing alkoxylated alcohols, as described in 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 degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number - that of ana lytically determinable size can also assume broken values - between 1 and 10; preferably x is 1.2 to 1.4. Also suitable are polyhydroxy fatty acid amides of the formula (III) in which R ¹ CO is an aliphatic acyl radical having 6 to 22 carbon atoms, R ^{2 is} hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl radical having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups:

in der R³ für einen linearen oder verzweigten Alkyl- oder Alkenylrest mit 7 bis 12 Kohlenstoffatomen, R⁴ für einen linearen, verzweigten oder cyclischen Alkylenrest oder einen Arylenrest mit 2 bis 8 Kohlenstoffatomen und R⁵ für einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest oder einen Oxy-Alkylrest mit 1 bis 8 Kohlenstoffatomen steht, wobei C₁-C₄-Alkyl- oder Phenylreste bevorzugt sind, und [Z] für einen linearen Polyhydroxyalkylrest, dessen Alkylkette mit mindestens zwei Hydroxylgruppen substituiert ist, oder alkoxylierte, vorzugsweise ethoxylierte oder propoxylierte Derivate dieses Restes steht. [Z] wird auch hier vorzugsweise durch reduktive Aminierung eines Zuckers wie Glucose, Fructose, Maltose, Lactose, Galactose, Mannose oder Xylose erhalten. Die N-Alkoxy- oder N-Aryloxy-substituierten Verbindungen können dann beispielsweise nach der Lehre der internationalen Patentanmeldung WO 95/07331 durch Umsetzung mit Fettsäuremethylestern in Gegenwart eines Alkoxids als Katalysator in die gewünschten Polyhydroxyfettsäureamide 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, wie sie beispielsweise in der japanischen Patentanmeldung JP 58/217598 beschrieben sind oder die vorzugsweise nach dem in der internationalen Patentanmeldung WO 90/13533 beschriebenen Verfahren hergestellt werden. Auch nichtionische Tenside vom Typ der Aminoxide, beispielsweise N-Kokosalkyl-N,N-dimethylaminoxid und N-Talgalkyl-N,N-dihydroxyethylaminoxid, und der Fettsäurealkanolamide können geeignet sein. Die Menge dieser nichtionischen Tenside beträgt vorzugsweise nicht mehr als die der ethoxylierten Fettalkohole, insbesondere nicht mehr als die Hälfte davon. Als weitere Tenside kommen sogenannte Gemini-Tenside in Betracht. Hierunter werden im Allgemeinen solche Verbindungen verstanden, die zwei hydrophile Gruppen pro Molekül besitzen. Diese Gruppen sind in der Regel durch einen sogenannten "Spacer" voneinander getrennt. Dieser Spacer ist in der Regel eine 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 gemäß der deutschen Patentanmeldung DE 43 21 022 oder Dimeralkohol-bis- und Trimeralkohol-tris-sulfate und -ethersulfate gemäß der deutschen Patentanmeldung DE 195 03 061 . Endgruppenverschlossene dimere und trimere Mischether gemäß der deutschen Patentanmeldung DE 195 13 391 zeichnen sich insbesondere durch ihre Bi- und Multifunktionalität aus. So besitzen die genannten endgruppenverschlossenen Tenside gute Netzeigenschaften und sind dabei schaumarm, so dass sie sich insbesondere für den Einsatz in maschinellen Wasch- oder Reinigungsverfahren eignen. Eingesetzt werden können aber auch Gemini-Polyhydroxyfettsäureamide oder Poly-Polyhydroxyfettsäureamide, wie sie in den internationalen Patentanmeldungen WO 95/19953 , WO 95/19954 und den US-amerikanischen Patentschriften US 3 234 258 oder US 5 075 041 hergestellt werden und als Handelsprodukte der Shell Oil Company unter dem Namen DAN^® erhalten werden können, sind geeignete Aniontenside. Geeignet sind auch die Schwefelsäuremonoester der mit 1 bis 6 Mol Ethylenoxid ethoxylierten geradkettigen oder verzweigten C₇-C₂₁-Alkohole, wie 2-Methylverzweigte C₉-C₁₁-Alkohole mit im Durchschnitt 3,5 Mol Ethylenoxid (EO) oder C₁₂-C₁₈-Fettalkohole mit 1 bis 4 EO. Zu den bevorzugten Aniontensiden gehören auch die Salze der Alkylsulfobernsteinsäure, die auch als Sulfosuccinate oder als Sulfobernsteinsäureester bezeichnet werden, und die Monoester und/oder Diester der Sulfobernsteinsäure mit Alkoholen, vorzugsweise Fettalkoholen und insbesondere ethoxylierten Fettalkoholen darstellen. Bevorzugte Sulfosuccinate enthalten C₈- bis C₁₈-Fettalkoholreste oder Mischungen aus diesen. Insbesondere bevorzugte Sulfosuccinate enthalten einen Fettalkoholrest, der sich von ethoxylierten Fettalkoholen ableitet, die für sich betrachtet nichtionische Tenside darstellen. Dabei sind wiederum Sulfosuccinate, deren Fettalkohol-Reste sich von ethoxylierten Fettalkoholen mit eingeengter Homologenverteilung ableiten, besonders bevorzugt. Ebenso ist es auch möglich, Alk(en)ylbernsteinsäure mit vorzugsweise 8 bis 18 Kohlenstoffatomen in der Alk(en)ylkette oder deren Salze einzusetzen. Als weitere anionische Tenside kommen Fettsäure-Derivate von Aminosäuren, beispielsweise von N-Methyltaurin (Tauride) und/oder von N-Methylglycin (Sarkoside) in Betracht. Insbesondere bevorzugt sind dabei die Sarkoside beziehungsweise die Sarkosinate und hier vor allem Sarkosinate von höheren und gegebenenfalls einfach oder mehrfach ungesättigten Fettsäuren wie Oleylsarkosinat. Als weitere anionische Tenside kommen insbesondere Seifen in Betracht. Geeignet sind insbesondere gesättigte Fettsäureseifen, wie die Salze der Laurinsäure, Myristinsäure, Palmitinsäure, Stearinsäure, hydrierten Erucasäure und Behensäure sowie insbesondere aus natürlichen Fettsäuren, zum Beispiel Kokos-, Palmkern- oder Talgfettsäuren, abgeleitete Seifengemische. Zusammen mit diesen Seifen oder als Ersatzmittel für Seifen können auch die bekannten Alkenylbernsteinsäuresalze eingesetzt werden.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 then be used, for example, according to the teaching of the international patent application WO 95/07331 be converted by conversion with fatty acid methyl esters in the presence of an alkoxide as catalyst into the desired Polyhydroxyfettsäureamide. Another class of preferred nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants, in particular together with alkoxylated fatty alcohols and / or alkyl glycosides, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably from 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl ester, as described for example in the Japanese patent application JP 58/217598 are described or preferably according to the in the international patent application WO 90/13533 be prepared described methods. Nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof. Other suitable surfactants are so-called gemini surfactants. These are generally understood as meaning those compounds which have two hydrophilic groups per molecule. These groups are usually separated by a so-called "spacer". This spacer is typically a carbon chain that should be long enough for the hydrophilic groups to be spaced sufficiently apart for them to act independently of each other. Such surfactants are generally characterized by an unusually low critical micelle concentration and the ability to greatly reduce the surface tension of the water. In exceptional cases, the term gemini surfactants not only such "dimer", but also corresponding to "trimeric" surfactants understood. Suitable gemini surfactants are, for example, sulfated hydroxy mixed ethers according to the German patent application DE 43 21 022 or dimer alcohol bis and trimer alcohol tris sulfates and ether sulfates according to the German patent application DE 195 03 061 , End-capped dimeric and trimeric mixed ethers according to the German patent application DE 195 13 391 They are characterized by their bi- and multi-functionality. Thus, the end-capped surfactants mentioned have good wetting properties and are low foaming, so that they are particularly suitable for use in machine washing or cleaning processes. However, it is also possible to use gemini-polyhydroxy fatty acid amides or poly-polyhydroxy fatty acid amides, as described in international patent applications WO 95/19953 . WO 95/19954 and the US patents US 3,234,258 or US 5 075 041 are manufactured and can be obtained as commercial products from 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 represent. 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 of the European patent specification obtainable by oxidation of polysaccharides or dextrins EP 0 625 992 or the international patent application WO 92/18542 or the European patent specification EP 0 232 202 , polymeric acrylic acids, methacrylic acids, maleic acids and copolymers thereof, which may also contain small amounts of polymerizable substances copolymerized without carboxylic acid functionality. The 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, albeit less preferred, compounds of this class are copolymers of acrylic or methacrylic acid with vinyl ethers, such as vinylmethyl ethers, vinyl esters, ethylene, propylene and styrene, in which the 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 can be prepared in particular by methods described in the German patent DE 42 21 381 and the German patent application DE 43 00 772 are generally described, and generally have a molecular weight between 1,000 and 200,000. Further preferred copolymers are those described in the German patent applications DE 43 03 320 and DE 44 17 734 be described and as monomers preferably acrolein and acrylic acid / acrylic acid salts or vinyl acetate. The organic builder substances can be used, in particular for the preparation of liquid agents, in the form of aqueous solutions, preferably in the form of 30 to 50 percent by weight aqueous solutions. All of the acids mentioned are generally used in the form of their water-soluble salts, in particular their alkali metal salts.

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 near the mentioned upper limit are preferably used in pasty or liquid, especially hydrous, inventive compositions.

Suitable water-soluble inorganic builder materials are, in particular, alkali metal silicates, alkali metal carbonates and alkali metal phosphates, which may be in the form of their alkaline, neutral or acidic sodium or potassium salts. Examples of these are trisodium phosphate, tetrasodium diphosphate, disodium dihydrogen diphosphate, pentasodium triphosphate, so-called sodium hexametaphosphate, oligomeric trisodium phosphate with degrees of oligomerization of from 5 to 1000, in particular from 5 to 50, and the corresponding potassium salts or mixtures of sodium and potassium salts. Crystalline or amorphous alkali metal aluminosilicates, in amounts of up to 50% by weight, preferably not more than 40% by weight, and in liquid agents, in particular from 1% by weight to 5% by weight, are particularly suitable as water-insoluble, water-dispersible inorganic builder materials. used. Among these, 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. Those with a molar ratio Na ₂ O: SiO ₂ of 1: 1.9 to 1: 2.8 can be prepared by the process of European patent application EP 0 425 427 getting produced. The crystalline silicates which may be present alone or in admixture with amorphous silicates, are crystalline layer silicates with the general formula Na ₂ Si _x O _{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. Crystalline layered silicates which fall under this general formula are described, for example, in the European patent application EP 0 164 514 described. Preferred crystalline phyllosilicates are those in which x in the abovementioned general formula assumes the values 2 or 3.

In particular, both β- and δ-sodium disilicates (Na ₂ Si ₂ O ₅ .yH ₂ O) are preferred, whereby β-sodium disilicate can be obtained, for example, by the process described in International Patent Application WO 91/08171 is described. δ-Sodium silicates with a modulus between 1.9 and 3.2 can according to Japanese Patent Applications JP 04/238 809 or JP 04/260 610 getting produced. Also prepared from amorphous alkali metal silicates, practically anhydrous crystalline alkali metal silicates of the above general formula in which x is a number from 1.9 to 2.1, preparable as in the European patent applications EP 0 548 599 . EP 0 502 325 and EP 0 452 428 can be used in agents according to the invention. In a further preferred embodiment of the composition according to the invention, a crystalline sodium layer silicate with a modulus of 2 to 3 is used, as it is by the process of European patent application EP 0 436 835 made from sand and soda. Crystalline sodium silicates with a modulus ranging from 1.9 to 3.5, as prepared by the methods of European patents EP 0 164 552 and or EP 0 294 753 are available are used in a further preferred embodiment of the invention means. Crystalline layer-form silicates of formula (I) given above are sold by Clariant GmbH under the trade name Na-SKS, eg. Na-SKS-1 (Na ₂ Si ₂₂ O ₄₅ .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 ). An overview of crystalline phyllosilicates, for example, in the "Hoechst High Chem Magazine 14/1993" on pages 33-38 and in "Soap-Oils-Fat-Waxes, 116 Volume, No. 20 / -1990" on pages 805-808 published article. In a preferred embodiment of compositions according to the invention, a granular compound of crystalline phyllosilicate and citrate, of crystalline phyllosilicate and of the abovementioned (co) polymeric polycarboxylic acid, as described, for example, in the German patent application DE 198 19 187 or from alkali metal silicate and alkali metal carbonate, as described for example in the international patent application WO 95/22592 described or 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.

As bleach activators, it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups. Preference is given to polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate, 2,5-diacetoxy- 2,5-dihydrofuran and from the German patent applications DE 196 16 693 and DE 196 16 767 known enol esters and acetylated sorbitol and mannitol or their in the European patent application EP 0 525 239 mixtures described (SORMAN), acylated sugar derivatives, in particular pentaacetylglucose (PAG), pentaacetylfruktose, tetraacetylxylose and octaacetyllactose as well as acetylated, optionally N-alkylated glucamine and gluconolactone, and / or N-acylated lactams, for example N-benzoylcaprolactam, which are known from international patent applications WO 94/27970 . WO 94/28102 . WO 94/28103 . WO 95/00626 . WO 95/14759 and WO 95/17498 are known. The from the German patent application DE 196 16 769 known hydrophilic substituted acyl acetals and in the German patent application DE 196 16 770 as well as the international patent application WO 95/14075 Acyllactame described are also preferably used. Also from the German patent application DE 44 43 177 known combinations of conventional bleach activators can be used. Such bleach activators can, in particular in the presence of the abovementioned hydrogen peroxide-producing bleach, in the usual amount range, preferably in amounts of from 0.5 wt .-% to 10 wt .-%, in particular 1 wt .-% to 8 wt .-%, based on However, total agent, be included, missing when using percarboxylic acid as the sole bleach, preferably completely.

In addition to or instead of the conventional bleach activators, it is also possible to use those from European patents EP 0 446 982 and EP 0 453 003 be known sulphonic imines and / or bleach-enhancing transition metal salts or transition metal complexes as so-called bleach catalysts.

Suitable enzymes which can be used in the compositions are those from the class of amylases, proteases, lipases, cutinases, pullulanases, hemicellulases, cellulases, oxidases, laccases and peroxidases and mixtures thereof. Particularly suitable are from fungi or bacteria, such as Bacillus subtilis, Bacillus licheniformis, Bacillus lentus, Streptomyces griseus, Humicola lanuginosa, Humicola insolens, Pseudomonas pseudoalcaligenes, Pseudomonas cepacia or Coprinus cinereus derived enzymatic agents. The enzymes can be as described, for example, in the European patent EP 0 564 476 or in the international patent application WO 94/23005 be adsorbed to carriers and / or embedded in encapsulating substances to protect against premature inactivation. They are preferably present in the detergents or cleaners according to the invention in amounts of up to 5% by weight, in particular from 0.2% by weight to 4% by weight. If the agent of the invention contains protease, it preferably has a proteolytic activity in the range of about 100 PE / g to about 10,000 PE / g, in particular 300 PE / g to 8000 PE / g. If several enzymes are to be used in the agent according to the invention, this can be achieved by incorporation of the two or more separate or separately synthesized enzymes or by two or more enzymes synthesized together in a granulate, for example from international patent applications WO 96/00772 or WO 96/00773 known, performed become.

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, hydroxyalkyl cellulose and mixed ethers, such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, Methylcarboxymethylcellulose and mixtures thereof, for example in amounts of 0.1 to 5 wt .-%, based on the means used.

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 solid compositions according to the invention presents no difficulties and can be carried out in a known manner, for example by spray-drying or granulation, enzymes and possibly other thermally sensitive ingredients such as, for example, bleaching agents optionally being added separately later. For the preparation of inventive agent with increased bulk density, in particular in the range of 650 g / l to 950 g / l, is one of the European patent EP 0 486 592 known method comprising an extrusion step is preferred. Another preferred preparation by means of a granulation process is in the European patent specification EP 0 642 576 described.

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, For example, eccentric or rotary presses, pressed with compressive forces in the range of about 50 to 100 kN, preferably at 60 to 70 kN. Particularly in the case of multilayer tablets, it may be advantageous if at least one layer is pre-compressed. This is preferably carried out at pressing forces between 5 and 20 kN, in particular at 10 to 15 kN. This gives fracture-resistant, yet sufficiently rapidly soluble tablets under application conditions with fracture and flexural strengths of normally 100 to 200 N, but preferably above 150 N. Preferably, a tablet produced in this way has a weight of 10 g to 50 g, in particular 15 g up to 40 g. The spatial form of the tablets is arbitrary and can be round, oval or angular, with intermediate forms are also possible. Corners and edges are advantageously rounded. Round tablets preferably have a diameter of 30 mm to 40 mm. In particular, the size of rectangular or cuboid-shaped tablets, which are introduced predominantly via the metering device, for example the dishwasher, is dependent on the geometry and the volume of this metering device. Exemplary preferred embodiments have a base area of (20 to 30 mm) × (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

Example 1: Color transfer inhibition

• * In E1: Umsetzungsprodukt erhalten aus einer Verbindung der Formel I mit k = 1, R = CH₂, X = CO-NH-(CH₂CH₂)₁₉(CH₂CH(CH₃)O)CH₃ durch Umsetzung mit Polyethylenimin (MW = 25.000) im Gemisch mit dem Umsetzungsprodukt erhalten aus einer Verbindung der Formel I mit k = 1, R = CH₂, X = CO-NH-(CH₂)₁₁CH₃ durch Umsetzung mit Polyethylenimin (MW = 25.000) (Molverhältnis der beiden Umsetzungsprodukte zueinander: 1:1) In E2 und E3: Umsetzungsprodukt erhalten aus einer Verbindung der Formel I mit k = 1, R = CH₂, X = CO-NH-(CH₂CH₂)₁₉(CH₂CH(CH₃)O)CH₃ durch Umsetzung mit Polyethylenimin (MW = 25.000) im Gemisch mit dem Umsetzungsprodukt erhalten aus einer Verbindung der Formel I mit k = 1, R = CH₂, X = CO-NH-(CH₂)₁₁CH₃ durch Umsetzung mit Polyethylenimin (MW = 25.000) (Molverhältnis der beiden Umsetzungsprodukte zueinander: 1:3,6)
• ** Mischung aus Cellulase, Amylase und Protease

The following table shows the compositions of washing or cleaning agents E1, E2 and E3 according to the invention and those of a comparative example V1: TABLE 1 V1 E1 E2 E3 C _12-18 fatty alcohol with 7 EO 10 10 10 10 C _12-14 alkylpolyglycoside 3 3 3 3 Polyacrylate thickener 0.2 0.2 0.2 0.2 ethanol 3 3 3 3 citric acid 5 5 5 5 phosphonic 0.4 0.4 0.4 0.4 Polymer* - 0.4 0.4 0.4 PVP / PVI 0.1 - 0.1 0.2 Caustic soda (50%) 3.2 3.2 3.2 3.2 propylene glycol 9 9 9 9 boric acid 1 1 1 1 Silicone antifoam 0,003 0,003 0,003 0,003 Perfume 1.5 1.5 1.5 1.5 Enzymes **, dye + + + + water Ad 100 Ad 100 Ad 100 Ad 100

• * In E1: Reaction product obtained from a compound of the formula I where k = 1, R = CH ₂ , X = CO-NH- (CH ₂ CH ₂ ) ₁₉ (CH ₂ CH (CH ₃ ) O) CH ₃ by reaction with Polyethyleneimine (MW = 25,000) in a mixture with the reaction product obtained from a compound of the formula I where k = 1, R = CH ₂ , X = CO-NH- (CH ₂ ) ₁₁ CH ₃ by reaction with polyethyleneimine (MW = 25,000) (Molar ratio of the two reaction products to each other: 1: 1) In E2 and E3: reaction product obtained from a compound of formula I with k = 1, R = CH ₂ , X = CO-NH- (CH ₂ CH ₂ ) ₁₉ (CH ₂ CH (CH ₃ ) O) CH ₃ by reaction with polyethyleneimine (MW = 25,000) in a mixture with the reaction product obtained from a compound of the formula I where k = 1, R = CH ₂ , X = CO-NH- (CH ₂ ) ₁₁ CH ₃ by reaction with polyethyleneimine (MW = 25,000) (molar ratio of the two reaction products to one another: 1: 3.6)
• ** Mixture of cellulase, amylase and protease

All Detergent compositions were stable and showed no precipitations.

to Determination of dye transfer inhibiting properties the individual washing or cleaning agent became a staining scale Rating (SSR), which is based on the ISO 105A04 performed. To were two white tissues (so-called accompanying tissue) with a colored fabric using each of the above Detergent or detergent compositions in a Lini tester (ex Atlas) at 60 ° C, then washed with Rinsed water and dried hanging at room temperature. Subsequently, the degree of discoloration of the both accompanying tissues determined spectrophotometrically.

Of the Degree of discoloration was then in values of 1 (strong Discoloration) to 5 (no discoloration).

Out SSR it became clear that the invention Means better color transfer inhibiting properties with respect to several textile dyes than the comparison formulation.

Example 2: color retention

The The agents mentioned in Example 1 were among the otherwise examples 1 corresponding conditions on the colored testicles tested:

Washing conditions:

• Cooking / color washing program, 60 ° C / Miele W 985
• Number of wash / dry cycles: 5
• Water hardness: 16 ° dH
• Dosage: 75 g

Test textiles:

Dyed textiles:

• Red textile
• Yellow textile
• Black textile

Measurement and evaluation of the results:

The Color changes of the textiles are made with a Spectraflash Device (with UV without gloss) measured and the dL, da, db, dE values converted into GSC values; Scale 1-5 (1 = bad, 5 = no change)

Of the Use of a composition according to the invention led when comparing the averages of all 5 test textiles to a number higher by at least 1 value than the stake of the agent V1.

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

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• - EP 0300305 [0020]
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• - JP 58/217598 [0021]
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• WO 95/19953 [0021]
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• US 3234258 [0021]
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• - DE 4417734 [0024]
• - DE 2412837 [0026]
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• EP 0164514 [0027]
• WO 91/08171 [0028]
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• - JP 04/260610 [0028]
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• - EP 0502325 [0028]
• EP 0452428 [0028]
• - EP 0436835 [0028]
• EP 0164552 [0028]
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• WO 94/27970 [0031]
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• WO 94/28103 [0031]
• WO 95/00626 [0031]
• WO 95/14759 [0031]
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Cited non-patent literature

• - "Hoechst High Chem Magazine 14/1993" on pages 33-38 [0028]
• - "Soap-Oils-Grease-Waxes, 116 Volume, No. 20 / -1990" on pages 805-808 [0028]

Claims (10)

Washing or cleaning compositions containing a dye transfer inhibitor in the form of a compound of the general formulas I or II,

wherein R is C ₁ -C ₁₂ alkylene; k is a number greater than 0, X is CO-CH = CH ₂ , CO-C (CH ₃ ) = CH ₂ , CO-O-aryl, C ₂ -C ₆ -alkylene-SO ₂ -CH = CH ₂ , or CO-NH-R ¹ ; and R ^{1 is} C ₁ -C ₃₀ -alkyl, C ₁ -C ₃₀ -haloalkyl, C ₁ -C ₃₀ -hydroxyalkyl, C ₁ -C ₆ -alkyloxy-C ₁ -C ₃₀ -alkyl, C ₁ -C ₆ - Alkylcarbonyloxy-C ₁ -C ₃₀ -alkyl, amino-C ₁ -C ₃₀ -alkyl, mono- or di (C ₁ -C ₆ -alkyl) amino-C ₁ -C ₃₀ -alkyl, ammonio-C ₁ -C ₃₀ alkyl, polyoxyalkylene C ₁ -C ₃₀ alkyl, polysiloxanyl C ₁ -C ₃₀ alkyl, (meth) acryloyloxy C ₁ -C ₃₀ alkyl, sulfono C ₁ -C ₃₀ alkyl, phosphonoC ₁ C ₃₀ alkyl, di (C ₁ -C ₆ alkyl) phosphono C ₃ -C ₃₀ alkyl, phosphonato C ₁ -C ₃₀ alkyl, di (C ₁ -C ₆ alkyl) phosphonato C ₁ C ₃₀ alkyl or a saccharide radical, where in formula IX this meaning has only if k is 1, or X is (i) the radical of a polyamine to which the parenthesized formula part is divided by (CO) NH- Or (ii) a polymeric backbone to which the parenthetical formula portion is attached via (CO) -, NH-C ₂ -C ₆ -alkylene-O (CO) - or (CO) -OC ₂ -C ₆ Alkylene-O (CO) groups, or (iii) a polymeric backbone to which the parenthesis when the formula is attached via (CO) -polysiloxanyl-C ₁ -C ₃₀ -alkyl groups, k represents a number greater than 1, in addition to customary constituents compatible with this constituent. Detergents or cleaning compositions containing a color transfer inhibitor in the form of a polymer which is obtainable by reacting a polymeric substrate having functional groups selected from hydroxy groups, primary and secondary amino groups with a compound of general formulas I or II,

wherein R is C ₁ -C ₁₂ alkylene; k is a number greater than 0, X is CO-CH = CH ₂ , CO-C (CH ₃ ) = CH ₂ , CO-O-aryl, C ₂ -C ₆ -alkylene-SO ₂ -CH = CH ₂ , or CO-NH-R ¹ ; and R ^{1 is} C ₁ -C ₃₀ -alkyl, C ₁ -C ₃₀ -haloalkyl, C ₁ -C ₃₀ -hydroxyalkyl, C ₁ -C ₆ -alkyloxy-C ₁ -C ₃₀ -alkyl, C ₁ -C ₆ - Alkylcarbonyloxy-C ₁ -C ₃₀ -alkyl, amino-C ₁ -C ₃₀ -alkyl, mono- or di (C ₁ -C ₆ -alkyl) amino-C ₁ -C ₃₀ -alkyl, ammonio-C ₁ -C ₃₀ alkyl, polyoxyalkylene C ₁ -C ₃₀ alkyl, polysiloxanyl C ₁ -C ₃₀ alkyl, (meth) acryloyloxy C ₁ -C ₃₀ alkyl, sulfono C ₁ -C ₃₀ alkyl, phosphonoC ₁ C ₃₀ alkyl, di (C ₁ -C ₆ alkyl) phosphono C ₁ -C ₃₀ alkyl, phosphonato C ₁ -C ₃₀ alkyl, di (C ₁ -C ₆ alkyl) phosphonato C ₁ -C ₃₀ alkyl or a saccharide radical, wherein in formula IX this meaning has only if k is 1, or X is (i) the residue of a polyamine to which the parenthesized formula part is attached via (CO) NH groups, or (ii) a polymeric backbone to which the parenthesized formula part is attached via (CO) -, NH- C ₂ -C ₆ alkylene-O (CO) or (CO) -OC ₂ -C ₆ alkylene-O (CO) groups, or (iii) a polymeric backbone to which is attached the parenthesized formula part is attached via (CO) -polysiloxanyl-C ₁ -C ₃₀ -alkyl groups, if k stands for a number of more than 1. Agent according to claim 1 or 2, characterized that the color transfer inhibitor among the compounds of formula I is selected 4-phenyloxycarbonyloxymethyl-2-oxo-1,3-dioxolane, 4- (4-Phenyloxycarbonyloxy) butyl-2-oxo-1,3-dioxolane, 2-oxo-1,3-dioxolan-4-yl-methyl, 2-oxo-1,3-dioxolan-4-yl-methyl, 4- (2-oxo-1,3-dioxolan-4-yl) butyl acrylate, 4- (2-oxo-1,3-dioxolan-4-yl) butyl methacrylate and 4- (Vinylsulfonylethyloxy) butyl-2-oxo-1,3-dioxolane. Agent according to claim 2 or 3, characterized that the polymeric substrate is selected from the group including polyvinyl alcohols, polyalkylene amines such as polyethyleneimine, Polyvinylamines, polyallylamines, polyethylene glycols, chitosan, polyamide-epichlorohydrin resins, Polyaminostyrenes, with aminoalkyl groups terminal or as a side group substituted polysiloxanes, peptides, polypeptides, and proteins and their Mixtures. Composition according to claim 4, characterized in that the polymeric substrate is selected from the polyethyleneimines having molecular weights in the range of 5,000 to 100,000, compounds of the formula NH ₂ - [CH ₂ ] _m - (Si (CH ₃ ) ₂ O) _n -Si (CH ₃ ) ₂ - [CH ₂ ] _o -R ', where m = 1 to 10, preferably 1 to 5, more preferably 1 to 3, wherein n = 1 to 50, preferably 30 to 50, wherein o = 0 to 10, preferably 1 to 5, more preferably 1 to 3, and wherein R '= H, C _1-22 -alkyl, an amino or ammonium group, and compounds of the formula NH ₂ - [CH ( CH ₃ ) -CH ₂ O] _l - [CH ₂ -CH ₂ O] _m - [CH ₂ -CH (CH ₃ ) O] _n -R ", where 1, m and n are independently from 0 to 50 with the proviso that the sum l + m + n = 5 to 100, in particular 10 to 50, preferably 10 to 30, particularly preferably 10 to 20, and R '' = H, a C _1-22 alkyl , C _1-22 -aminoalkyl or C _1-22 -ammoniumalkyl group, and mixtures thereof. Agent according to one of claims 1 to 5, characterized in that it is 0.01 wt .-% to 5 wt .-%, in particular From 0.1% to 1% by weight of the polymer and / or the dye transfer inhibiting Compound of the general formula I and / or II ent holds. 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 a compound of the general formulas I or II,

wherein R is C ₁ -C ₁₂ alkylene; k is a number greater than 0, X is CO-CH = CH ₂ , CO-C (CH ₃ ) = CH ₂ , CO-O-aryl, C ₂ -C ₆ -alkylene-SO ₂ -CH = CH ₂ , or CO-NH-R ¹ ; and R ^{1 is} C ₁ -C ₃₀ -alkyl, C ₁ -C ₃₀ -haloalkyl, C ₁ -C ₃₀ -hydroxyalkyl, C ₁ -C ₆ -alkyloxy-C ₁ -C ₃₀ -alkyl, C ₁ -C ₆ - Alkylcarbonyloxy-C ₁ -C ₃₀ -alkyl, amino-C ₁ -C ₃₀ -alkyl, mono- or di (C ₁ -C ₆ -alkyl) amino-C ₁ -C ₃₀ -alkyl, ammonio-C ₁ -C ₃₀ -alkyl, polyoxyalkylene-C ₁ -C ₃₀ -alkyl, polysiloxanyl-C ₁ -C ₃₀ -alkyl, (meth) acryloyloxy-C ₁ -C ₃₀ -alkyl, sulfono-C ₁ -C ₃₀ -alkyl, Phosphono-C ₁ -C ₃₀ -alkyl, di (C ₁ -C ₆ -alkyl) phosphono-C ₁ -C ₃₀ -alkyl, phosphonato-C ₁ -C ₃₀ -alkyl, di (C ₁ -C ₆ -alkyl) phosphonato-C ₁ -C ₃₀ -alkyl or a saccharide radical, where in formula IX this meaning has only if k is 1, or X is (i) the radical of a polyamine to which the formula part in parentheses ( CO) NH groups or (ii) a polymeric backbone to which the parenthesized part of the formula is attached via (CO) -, NH-C ₂ -C ₆ -alkylene-O (CO) - or (CO) -OC ₂ -C ₆ alkylene-O (CO) group is attached, or (iii) a polymeric backbone to which the bracketed portion formula above (CO) - Polysiloxanyl-C1-C30-alkyl groups is bonded, if k is a number greater than 1, 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 a polymer obtainable by reacting a polymeric substrate having functional groups selected from hydroxy groups, primary and secondary amino groups, with a compound of general formulas I or II,

wherein R is C ₁ -C ₁₂ alkylene; k is a number greater than 0, X is CO-CH = CH ₂ , CO-C (CH ₃ ) = CH ₂ , CO-O-aryl, C ₂ -C ₆ -alkylene-SO ₂ -CH = CH ₂ , or CO-NH-R ¹ ; and R ^{1 is} C ₁ -C ₃₀ -alkyl, C ₁ -C ₃₀ -haloalkyl, C ₁ -C ₃₀ -hydroxyalkyl, C ₁ -C ₆ -alkyloxy-C ₁ -C ₃₀ -alkyl, C ₁ -C ₆ - Alkylcarbonyloxy-C ₁ -C ₃₀ -alkyl, amino-C ₁ -C ₃₀ -alkyl, mono- or di (C ₁ -C ₆ -alkyl) amino-C ₁ -C ₃₀ -alkyl, ammonio-C ₁ -C ₃₀ alkyl, polyoxyalkylene C ₁ -C ₃₀ alkyl, polysiloxanyl C ₁ -C ₃₀ alkyl, (meth) acryloyloxy C ₁ -C ₃₀ alkyl, sulfono C ₁ -C ₃₀ alkyl, phosphonoC ₁ C ₃₀ alkyl, di (C ₁ -C ₆ alkyl) phosphono C ₁ -C ₃₀ alkyl, phosphonato C ₁ -C ₃₀ alkyl, di (C ₁ -C ₆ alkyl) phosphonato C ₁ C ₃₀ alkyl or a saccharide radical, where in formula IX this meaning has only if k is 1, or X is (i) the radical of a polyamine to which the parenthesized formula part is divided by (CO) NH- Or (ii) a polymeric backbone to which the parenthetical formula portion is attached via (CO) -, NH-C ₂ -C ₆ -alkylene-O (CO) - or (CO) -OC ₂ -C ₆ Alkylene-O (CO) groups, or (iii) a polymeric backbone to which the parenthesis When formula I is bonded via (CO) polysiloxanyl-C ₁ -C ₃₀ -alkyl groups, when k is a number greater than 1, in order to avoid the transfer of textile dyestuffs from dyed textiles to undyed or differently colored textiles common laundry in particular surfactant-containing aqueous solutions. Process for washing textiles in surfactant-containing aqueous solutions, characterized in that a surfactant-containing aqueous solution used, which is a compound of the general formulas I and / or II and / or a polymer which is obtainable by reaction a polymeric substrate that has functional groups which is among hydroxy groups, primary and secondary amino groups are selected with a compound of the general formulas I or II.