EP1492863B2 - Textile cleaning agent which is gentle on textiles - Google Patents

Abstract

The invention relates to a liquid cleaning agent, a mild detergent, a liquid detergent and a non-aqueous liquid detergent, said products containing constituents for reducing fluffing and being designed in such a way that they are gentle on textiles. The invention also relates to a method and the use of said products for reducing fluffing and pilling on textile fabric.

Description

The invention relates to a liquid textile cleaning agent, a mild detergent, a liquid detergent and a nonaqueous liquid detergent containing at least one lint reduction component. Furthermore, the invention relates to the use of lint reduction components in liquid laundry detergents and the use of mild detergents, liquid detergents and non-aqueous liquid detergents for reducing the linting and pilling of textile fabrics. Furthermore, the invention relates to a method for reducing the formation of lint.

The modern textile cleaning makes high demands on the laundry to be cleaned. For example, the frequent washing of garments in a washing machine and the subsequent drying in a tumble dryer is associated with a high mechanical stress on the fabric. The frictional forces often lead to damage to the textile fabric, recognizable by a fluff and pilling. With each washing or drying cycle, but also by wearing the garments, a further abrasion and / or breakage of tiny fibers takes place on the surface of the textile fabric fabrics. The conventional textile cleaners are unable to reduce this damage to the fabric or try to eliminate only resulting textile damage.

The WO 99/16956 A1 describes the elimination of lint or pills through the use of cellulases. The cellulases thereby digest microfibers protruding from the textile fabrics and thus ensure a smooth and therefore pill-free textile surface.

From the WO 99/14295 A1 detergents containing modified cellulose polymers are known.

In the WO 98/28339 A1 become water-insoluble polymer particles having a core of (meth) acrylic acid monomer units and having free hydroxyl groups on the surface of the particles.

In the WO 03/062361 A1 describes a liquid conditioning agent containing lint reduction components such as celluloses, hydrogels and acrylic acid polymers.

The object of the present invention is therefore to reduce the linting and pilling of textile fabrics, in particular the reduction of this formation during textile cleaning.

Surprisingly, it has been found that the use of certain lint reduction components in textile cleaners can significantly reduce fluffing and pilling of textile fabrics.

The present invention is therefore in a first embodiment, a liquid textile cleaning agent according to claim 1.

The invention in a second embodiment is a mild detergent according to claim 9.

The invention in a third embodiment is a liquid detergent according to claim 18.

The invention in a fourth embodiment is a nonaqueous liquid detergent according to claim 24.

In the context of this invention, mild detergents are understood as meaning textile cleaners which additionally condition the textile fabrics to be cleaned. For the purposes of this invention, conditioning is understood to mean the scavenging treatment of textile fabrics, fabrics, yarns and fabrics. By conditioning the textiles are given positive properties, such as an improved softness, increased gloss and color brilliance, a fragrance refreshment, reducing the creasing and static charge and a facilitated ironing behavior. Furthermore, the conditioning in the context of this invention leads to a textile protection, detectable at a reduced lint and Pillbildung. Detergents are preferably used for cleaning sensitive textiles, such as linen, wool, silk or cotton.

Liquid detergents in the context of this invention are liquid to gel-form textile cleaners at 20 ° C., which can be used universally.

Non-aqueous liquid detergents in the context of this invention are liquid to gel-type textile cleaners which have a low water content and can be packed in portions in water-soluble wraps.

The term "nonaqueous" in the context of the present invention means to understand that contain only small amounts of free, that is not bound as water of crystallization or otherwise, water. Since even nonaqueous solvents and raw materials (especially those of technical qualities) have certain water contents, completely anhydrous compositions can only be produced on an industrial scale with great effort and high costs. In the "nonaqueous" compositions of the present invention, therefore, small amounts of free water are tolerable, which are below 15 wt .-%, preferably below 10 wt .-%, more preferably below 5 wt .-%, each based on the finished agent, lie.

The lint reduction components are present in the liquid textile cleaners or mild detergents or liquid detergents or nonaqueous liquid detergents as finely divided polymer particles or polymer emulsions or polymer dispersions which have a substantivity to textile fabrics or textile fibers. The lint reduction component of the present invention is a microcrystalline cellulose. Microcrystalline cellulose, the microcrystalline cellulose, the erhältlichwaren on 10 April 2002 under the section busbars Arbocel ^® BE 600-10, Arbocel ^® BE 600-20 and Arbocel® ^® BE 600-30 ex Rettenmaier and Cellulon ^® ex Kelco.

The conditioning agents according to the invention contain the lint reduction components in amounts of from 0.005 to 15% by weight, preferably from 0.01 to 10% by weight, more preferably from 0.1 to 7% by weight and in particular from 0.5 to 5% by weight .-%, in each case based on the total agent.

In addition to the lint reduction component, the liquid textile cleaners or mild detergents or liquid detergents or nonaqueous liquid detergents according to the invention additionally contain nonionic surfactants. The use of nonionic surfactants not only increases the washing performance of the compositions according to the invention, but additionally supports the dispersion and homogeneous distribution of the lint reduction component (s).

As nonionic surfactants are preferably alkoxylated, advantageously ethoxylated and / or propoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) and / or 1 to 10 moles of propylene oxide (PO) per mole of alcohol, used. Particular preference is given to C ₈ -C ₁₆ -alcohol alkoxylates, advantageously ethoxylated and / or propoxylated C ₁₀ -C ₁₅ -alcohol alkoxylates, in particular C ₁₂ -C ₁₄ -alcohol alkoxylates, having a degree of ethoxylation of between 2 and 10, preferably between 3 and 8, and / or a degree of propoxylation between 1 and 6, preferably between 1.5 and 5. The alcohol radical may preferably be linear or more preferably methyl-branched in the 2-position or contain linear and methyl-branched radicals in the mixture, as they are usually present in Oxoalkoholresten. In particular, however, alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are preferred. Preferred ethoxylated alcohols include, for example _12-14 alcohols with 3 EO or 4 EO, C _9-11 alcohol with 7 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C _12-18 alcohols with 3 EO , 5 EO or 7 EO and mixtures of these, such as mixtures of C _12-14 -alcohol with 3 EO and C _12-18 -alcohol with 5 EO. The indicated degrees of ethoxylation and propoxylation represent statistical averages which may be an integer or a fractional number for a particular product. Preferred alcohol ethoxylates and propoxylates have a narrow homolog distribution (narrow range ethoxylates / propoxylates, NRE / NRP). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

Also suitable are alkoxylated amines, advantageously ethoxylated and / or propoxylated, in particular primary and secondary amines having preferably 1 to 18 carbon atoms per alkyl chain and an average of 1 to 12 moles of ethylene oxide (EO) and / or 1 to 10 moles of propylene oxide (PO) per Mole of amine.

The end-capped alkoxylated fatty amines and fatty alcohols have proved to be particularly advantageous, in particular for use in the non-aqueous formulations according to the invention. The terminal hydroxy groups of the fatty alcohol alkoxylates and fatty amine alkoxylates are etherified by C ₁ -C ₂₀ -alkyl groups, preferably methyl or ethyl groups, in the end-capped fatty alcohol alkoxylates and fatty amine alkoxylates.

In addition, as further nonionic surfactants and alkyl glycosides of the general formula RO (G) _x. z. B. as compounds, especially with anionic surfactants, are used, in which R is a primary straight-chain or methyl-branched, especially in the 2-position methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol that for a glycose unit having 5 or 6 C atoms, preferably for glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is 1.2 to 1.4.

Another class of preferred nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having from 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl esters as they are 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.

Other suitable surfactants are so-called gemini surfactants. These are generally understood as meaning those compounds which have two hydrophilic groups and two hydrophobic 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 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, however, the term gemini surfactants is understood to mean not only dimeric but also trimeric surfactants.

Suitable gemini surfactants are, for example, sulfated hydroxy mixed ethers according to the German patent application DE-A-43 21 022 or dimer alcohol bis- and trimer alcohol trissulfates and ether sulfates according to the international patent application WO-A-96/23768 , End-capped dimeric and trimeric mixed ethers according to the German patent application DE-A-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 WO 95/19955 to be discribed.

in der RCO für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen, R⁵ für Wasserstoff, einen Alkyl- oder Hydroxyalkylrest mit 1 bis 4 Kohlenstoffatomen und [Z] für einen linearen oder verzweigten Polyhydroxyalkylrest mit 3 bis 10 Kohlenstoffatomen und 3 bis 10 Hydroxylgruppen steht. Bei den Polyhydroxyfettsäureamiden handelt es sich um bekannte Stoffe, die üblicherweise durch reduktive Aminierung eines reduzierenden Zuckers mit Ammoniak, einem Alkylamin oder einem Alkanolamin und nachfolgende Acylierung mit einer Fettsäure, einem Fettsäurealkylester oder einem Fettsäurechlorid erhalten werden können.Further suitable surfactants are polyhydroxy fatty acid amides of the following formula

wherein RCO is an aliphatic acyl radical having 6 to 22 carbon atoms, R ^{5 is} hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl radical having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups. The polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.

in der R für einen linearen oder verzweigten Alkyl- oder Alkenylrest mit 7 bis 12 Kohlenstoffatomen, R⁶ für einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest mit 2 bis 8 Kohlenstoffatomen und R⁷ für einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest oder einen Oxy-Alkylrest mit 1 bis 8 Kohlenstoffatomen steht, wobei C_1-4-Alkyl- oder Phenylreste bevorzugt sind und [Z] für einen linearen Polyhydroxyalkylrest steht, dessen Alkylkette mit mindestens zwei Hydroxylgruppen substituiert ist, oder alkoxylierte, vorzugsweise ethoxylierte oder propoxylierte Derivate dieses Restes.The group of polyhydroxy fatty acid amides also includes compounds of the following formula

R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{6 is} a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R ^{7 is} a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, with C _1-4 alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated Derivatives of this residue.

[Z] is preferably obtained by reductive amination of a reduced sugar, for example 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 application WO-A-95/07331 be converted by conversion with fatty acid methyl esters in the presence of an alkoxide as catalyst into the desired Polyhydroxyfettsäureamide.

In a preferred embodiment, the liquid laundry detergents contain alkoxylated fatty alcohols, more preferably ethoxylated and / or propoxylated fatty alcohols.

For mild detergents, it has proven to be advantageous if nonionic surfactants selected from the group of alkoxylated fatty alcohols and / or alkyl glycosides, in particular mixtures of alkoxylated fatty alcohols and alkyl glycosides are used.

In the light-duty detergents according to the invention, in a preferred embodiment, nonionic surfactants are present in amounts of up to 30% by weight, preferably from 5 to 25% by weight, particularly preferably from 10 to 20% by weight, based in each case on the entire composition ,

In a preferred embodiment, the liquid detergents according to the invention have nonionic surfactants in amounts of up to 30% by weight, preferably from 5 to 20% by weight, in particular from 10 to 15% by weight, based in each case on the total composition.

In one preferred embodiment, the nonaqueous liquid detergents according to the invention have nonionic surfactants in an amount of up to 35% by weight, preferably from 15 to 25% by weight, in each case based on the total agent.

Furthermore, the liquid laundry detergents or mild detergents or liquid laundry detergents or nonaqueous liquid laundry detergents according to the invention may additionally contain anionic surfactants in a preferred embodiment. Through the use of anionic surfactants, the soil release behavior of the compositions according to the invention during the washing process is significantly increased without significantly impairing the development of the lint reduction components.

As anionic surfactants, for example, those of the sulfonate type and sulfates are used. The surfactants of the sulfonate type are preferably C _9-13 -alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as are obtained, for example, from C _12-18 -monoolefins having terminal or internal double bonds by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation products into consideration. Also suitable are alkanesulfonates which are obtained from C _12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. Likewise, 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 are suitable.

Further suitable anionic surfactants are sulfated fatty acid glycerol esters. Fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and mixtures thereof, as obtained in the preparation by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol. Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.

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 these chain lengths 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 technology interest, the C ₁₂ -C ₁₆ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates and C ₁₄ -C ₁₅ alkyl sulfates are preferred. Also 2,3-alkyl sulfates, which, for example, according to the U.S. Patents 3,234,258 or 5,076,041 are manufactured and can be obtained as commercial products from Shell Oil Company under the name DAN ^®, are suitable anionic surfactants.

The sulfuric acid monoesters of straight-chain or branched C _7-21 -alcohols ethoxylated with from 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C _9-11- alcohols having on average 3.5 mol of ethylene oxide (EO) or C _12-18 . Fatty alcohols containing 1 to 4 EO, which are referred to as fatty alcohol ether sulfates, are suitable and particularly preferred anionic surfactants within the scope of this invention.

Further suitable anionic surfactants are also 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 _8-18 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. Again, sulfosuccinates whose fatty alcohol radicals are derived from ethoxylated fatty alcohols with a narrow homolog distribution are particularly preferred. Likewise, it is also possible to use alk (en) yl-succinic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.

As further anionic surfactants are particularly soaps into consideration. 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.

The anionic surfactants, including the soaps, may be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine. The anionic surfactants are preferably present in the form of their sodium or potassium salts, in particular in the form of the sodium salts. For the nonaqueous liquid detergents according to the invention, however, the ammonium salts, in particular the salts of organic bases, such as, for example, isopropylamine, are preferred.

Another class of anionic surfactants is the class of ether carboxylic acids obtainable by the reaction of fatty alcohol ethoxylates with sodium chloroacetate in the presence of basic catalysts. They have the general formula: R ¹⁰ O- (CH ₂ -CH ₂ -O) _p -CH ₂ -COOH with R ¹⁰ = C ₁ -C ₁₈ and p = 0.1 to 20. Ether carboxylic acids are water hardness insensitive and have excellent surfactant properties. Production and use are for example in soaps, Oils, fats, waxes 101, 37 (1975 ); 115, 235 (1989 ) and Surfactants Deterg. 25, 308 (1988 ).

In a preferred embodiment, the textile cleaners according to the invention contain anionic surfactants, preferably selected from the group of fatty alcohol sulfates and / or fatty alcohol ether sulfates and / or alkylbenzenesulfonates and / or soaps.

The fine detergents according to the invention contain in a preferred embodiment anionic surfactants in amounts below 10 wt .-%, preferably below 5 wt .-% and in particular below 1 wt .-%, each based on the total agent.

In one preferred embodiment, the liquid detergents according to the invention comprise anionic surfactants in amounts of up to 30% by weight, preferably up to 25% by weight, particularly preferably from 5 to 20% by weight, in particular from 8 to 15% by weight. , in each case based on the total mean.

In one preferred embodiment, the nonaqueous liquid detergents according to the invention contain anionic surfactants in amounts of up to 60% by weight, preferably from 20 to 50% by weight, in particular from 30 to 45% by weight, based in each case on the entire composition.

Furthermore, the liquid laundry detergents or mild detergents or liquid laundry detergents or nonaqueous liquid laundry detergents according to the invention may additionally contain complexing agents in a preferred embodiment. Complexing agents improve the stability of the agents and protect, for example, from the heavy metals catalyzed decomposition of certain ingredients of washing active formulations.

The group of complexing agents includes, for example, the alkali metal salts of nitrilotriacetic acid (NTA) and derivatives thereof, as well as alkali metal salts of anionic polyelectrolytes such as polyacrylates, polymaleates and polysulfonates. Furthermore, low molecular weight hydroxycarboxylic acids such as citric acid, tartaric acid, malic acid or gluconic acid and their salts are suitable. These preferred compounds include in particular organophosphonates such as 1-hydroxyethane-1,1-diphosphonic acid (HEDP), aminotri (methylenephosphonic acid) (ATMP), diethylenetriamine penta (methylenephosphonic acid) (DTPMP or DETPMP) and 2-phosphonobutane-1,2 , 4-tricarboxylic acid (PBS-AM), which are used mostly in the form of their ammonium or alkali metal salts.

In a preferred embodiment of the liquid laundry detergents or mild detergents or liquid detergents or nonaqueous liquid detergents according to the invention, the complexing agents are present in an amount of up to 10% by weight, preferably from 0.01 to 5% by weight, more preferably from 0.1 to 2 and in particular from 0.3 to 1.0 wt .-%, each based on the total agent before.

Furthermore, in a preferred embodiment, the liquid laundry detergents or mild detergents or liquid laundry detergents or nonaqueous liquid laundry detergents according to the invention may additionally comprise enzymes.

Enzymes support the washing processes in a variety of ways, especially in the removal of poorly bleachable contaminants, such as protein stains.

Particularly suitable enzymes are those from the classes of hydrolases such as the proteases, esterases, lipases or lipolytic enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. All of these hydrolases in the wash contribute to the removal of stains such as proteinaceous, greasy or starchy stains and graying. In addition, cellulases and other glycosyl hydrolases may contribute to color retention and to enhancing the softness of the fabric by removing pilling and microfibrils. Oxireductases can also be used for bleaching or inhibiting color transfer. Particularly suitable are bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus and Humicola insolens derived enzymatic agents. Preferably, subtilisin-type proteases and in particular proteases derived from Bacillus lentus are used. In this case, enzyme mixtures, for example from protease and amylase or protease and lipase or lipolytic enzymes or protease and cellulase or from cellulase and lipase or lipolytic enzymes or from protease, amylase and lipase or lipolytic enzymes or protease, lipase or lipolytic enzymes and cellulase, but in particular protease and / or lipase-containing mixtures or mixtures with lipolytic enzymes of particular interest. Examples of such lipolytic enzymes are the known cutinases. Peroxidases or oxidases have also proved suitable in some cases. Suitable amylases include in particular α-amylases, iso-amylases, pullulanases and pectinases. As cellulases are preferably cellobiohydrolases, endoglucanases and β-glucosidases, which are also called cellobiases, or Mixtures of these used. Since different cellulase types differ by their CMCase and avicelase activities, the desired activities can be set by targeted mixtures of the cellulases.

The enzymes may be adsorbed as a shaped body to carriers or embedded coated to protect against premature decomposition.

In a preferred embodiment, the liquid laundry detergents according to the invention contain enzymes, preferably selected from the group of proteases and / or amylases and / or cellulases.

In a preferred embodiment, the fine detergents according to the invention comprise cellulase, preferably in an amount of 0.005 to 2% by weight, particularly preferably 0.01 to 1% by weight, in particular 0.02 to 0.5% by weight, in each case based on the total mean.

In a preferred embodiment, the liquid detergents according to the invention comprise protease and / or amylase, particularly preferably any mixtures of protease and amylase.

In a preferred embodiment, the nonaqueous liquid detergents according to the invention contain enzymes, preferably selected from the group of proteases and / or amylases and / or cellulases, more preferably any mixtures of proteases, amylases and cellulases.

The liquid laundry detergents or mild detergents or liquid laundry detergents or nonaqueous liquid laundry detergents according to the invention advantageously have a viscosity of from 50 to 5000 mPas, more preferably from 50 to 3000 mPas and in particular from 500 to 1500 mPas (measured at 20 ° C. with a rotational viscometer (Brookfield RV, spindle 2). at 20 rpm (rpm: revolutions per minute)).

The liquid laundry detergents or mild detergents or liquid laundry detergents or nonaqueous liquid laundry detergents according to the invention contain one or more solvents in preferred embodiments.

Solvents that can be used in the compositions according to the invention originate, for example, from the group of monohydric or polyhydric alcohols, alkanolamines or glycol ethers, provided they are miscible with water in the concentration range indicated. The solvents are preferably selected from ethanol, n- or i-propanol, butanols, glycol, propane- or butanediol, glycerol, diglycol, propyl- or butyldiglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol methyl ether , Diethylene glycol ethyl ether, propylene glycol methyl, ethyl or propyl ether, butoxy-propoxy-propanol (BPP), dipropylene glycol monomethyl or ethyl ether, di-isopropylene glycol monomethyl, or ethyl ether, methoxy, ethoxy or butoxy triglycol, 1-butoxyethoxy 2-propanol, 3-methyl-3-methoxybutanol, propylene glycol t-butyl ether and mixtures of these solvents.

Some glycol ethers are available under the trade name Arcosolv ^® (Arco Chemical Co.) or Cellosolve carbitol ^{® ®} or Propasol ^® (Union Carbide Corp.); these include, for example, butyl carbitol ^®, hexyl carbitol ^®, MethylCarbitol® ^®, and carbitol ^® itself, (2- (2-ethoxy) ethoxy) ethanol. The choice of glycol ether can be readily made by one skilled in the art on the basis of its volatility, water solubility, weight percent of the total agent, and the like. Pyrrolidone solvents, such as N-alkylpyrrolidones, for example N-methyl-2-pyrrolidone or NC ₈ -C ₁₂ -alkylpyrrolidone, or 2-pyrrolidone, may also be used. Also preferred as the sole solvent or as part of a solvent mixture are glycerol derivatives, in particular glycerol carbonate.

Alcohols which may be used as cosolvents in the present invention include low molecular weight liquid polyethylene glycols, for example, polyethylene glycols having a molecular weight of 200, 300, 400, or 600. Other suitable cosolvents are other alcohols, for example (a) lower Alcohols such as ethanol, propanol, isopropanol and n-butanol, (b) ketones such as acetone and methyl ethyl ketone, (c) C ₂ -C ₄ polyols such as a diol or a triol, for example ethylene glycol, propylene glycol, glycerol or mixtures thereof. Especially preferred is 1,2-octanediol from the class of diols.

The agents according to the invention may in one preferred embodiment contain one or more water-soluble organic solvents. Water-soluble is understood to mean that the organic solvent is soluble in the amount contained in an optionally aqueous agent.

In a preferred embodiment, the conditioning agent according to the invention contains one or more solvents from the group comprising C ₁ to C ₄ monoalcohols, C ₂ to C ₆ glycols, C ₃ to C ₁₂ glycol ethers and glycerol, in particular ethanol. The C ₃ - to C ₁₂ glycol ethers according to the invention contain alkyl or alkenyl groups having less than 10 carbon atoms, preferably up to 8, in particular up to 6, more preferably 1 to 4 and most preferably 2 to 3 carbon atoms.

Preferred C ₁ to C ₄ monohydric alcohols are ethanol, n- propanol, iso- propanol and tert- butanol. Preferred C ₂ to C ₆ glycols are ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,5-pentanediol, neopentyl glycol and 1,6-hexanediol, in particular ethylene glycol and 1,2-propylene glycol. Preferred C ₃ - to C ₁₂ glycol ethers are di-, tri-, tetra- and pentaethylene glycol, di-, tri- and tetrapropylene glycol, propylene glycol monotertiary butyl ether and propylene glycol monoethyl ether and the solvents designated according to INCI butoxydiglycol, butoxyethanol, butoxyisopropanol, butoxypropanol, butyloctanol, ethoxydiglycol, Ethoxyethanol, ethyl hexanediol, isobutoxypropanol, isopentyldiol, 3-methoxybutanol, methoxyethanol, methoxyisopropanol and methoxymethylbutanol.

Particularly preferred solvents are ethanol, 1,2-propylene glycol and dipropylene glycol and their Mixtures, in particular ethanol and isopropanol.

The mild detergents according to the invention contain in a preferred embodiment up to 95% by weight, particularly preferably 20 to 90% by weight and in particular 50 to 80% by weight of one or more solvents, preferably water-soluble solvents and in particular water.

The liquid detergents according to the invention contain in a preferred embodiment up to 90% by weight, particularly preferably 20 to 85% by weight and in particular 50 to 80% by weight of one or more solvents, preferably water-soluble solvents and in particular water.

In one preferred embodiment, the nonaqueous liquid detergents according to the invention comprise organic solvents in amounts of up to 50% by weight, preferably up to 45% by weight, in particular from 20 to 40% by weight, in each case based on the total agent.

In addition to the aforementioned. Components may contain the inventive liquid laundry detergents or mild detergents or liquid detergents or non-aqueous liquid detergents softener components. Especially for mild detergents, the use of additional plasticizer components has proven to be extremely advantageous. The plasticizer components condition the textile fabrics already in the washing process, so that an additional conditioning rinse cycle is no longer necessary. In particular, when washing delicate textiles, such as silk, wool or linen, which are washed and ironed at low temperatures, the use of plasticizer components has proven itself. The plasticizer components facilitate the ironing of the textiles and reduce the static charge of the textile materials.

Examples of fabric softening components are quaternary ammonium compounds, cationic polymers and emulsifiers, such as those used in hair care products and also in textile saliva.

wobei in (I) R und R¹ für einen acyclischen Alkylrest mit 12 bis 24 Kohlenstoffatomen, R² für einen gesättigten C₁-C₄ Alkyl- oder Hydroxyalkylrest steht, R³ entweder gleich R, R¹ oder R² ist oder für einen aromatischen Rest steht. X^- steht entweder für ein Halogenid-, Methosulfat-,Suitable examples are quaternary ammonium compounds of the formulas (I) and (II,

wherein in (I) R and R ^{1 is} an acyclic alkyl radical having 12 to 24 carbon atoms, R ^{2 is} a saturated C ₁ -C ₄ alkyl or hydroxyalkyl radical, R ^{3 is} either R, R ¹ or R ² or is a aromatic residue stands. X ^- is either a halide, methosulfate,

Methophosphate or phosphate ion as well as mixtures of these. Examples of cationic compounds of the formula (I) are didecyldimethylammonium chloride, ditallowdimethylammonium chloride or dihexadecylammonium chloride.

R²¹ und R²² stehen dabei unabhängig voneinander jeweils für einen aliphatischen Rest mit 12 bis 22 Kohlenstoffatomen mit 0, 1, 2 oder 3 Doppelbindungen.Compounds of formula (II) are so-called ester quats. Esterquats are characterized by excellent biodegradability. Here, R ^{4 is} an aliphatic alkyl radical having 12 to 22 carbon atoms with 0, 1, 2 or 3 double bonds; R ⁵ is H, OH or O (CO) R ⁷ , R ⁶ is independently of R ^{5 is} H, OH or O (CO) R ⁸ , wherein R ⁷ and R ⁸ are each independently an aliphatic alkyl radical having 12 to 22 carbon atoms with 0, 1, 2 or 3 double bonds. m, n and p can each independently be 1, 2 or 3. X ^- may be either a halide, methosulfate, methophosphate or phosphate ion, as well as mixtures of these. Preference is given to compounds which contain the group O (CO) R ⁷ for R ⁵ and to alkyl radicals having 16 to 18 carbon atoms for R ⁴ and R ⁷ . Particularly preferred are compounds in which R ^{6 is} also OH. Examples of compounds of the formula (II) are methyl N- (2-hydroxyethyl) -N, N-di (tallowacyl oxyethyl) ammonium methosulfate, bis (palmitoyl) ethyl hydroxyethyl methyl ammonium methosulfate or methyl N , N-bis (acyloxyethyl) -N- (2-hydroxyethyl) ammonium methosulfate. If quaternized compounds of the formula (II) are used which have unsaturated alkyl chains, the acyl groups whose corresponding fatty acids have an iodine number between 5 and 80, preferably between 10 and 60 and in particular between 15 and 45 and which have a cis / trans isomer ratio are preferred (in wt .-%) of greater than 30: 70, preferably greater than 50: 50 and in particular greater than 70: 30 have. Commercial examples are sold by Stepan under the tradename Stepantex ^® methylhydroxyalkyldialkoyloxyalkylammonium or those known under Dehyquart ^® Cognis products known under or Rewoquat ^® manufactured by Goldschmidt-Witco. Further preferred compounds are the diesterquats corresponding to formula (III) which are obtainable under the name Rewoquat ^® 3099 W 222 LM or CR and provide in addition to the softness also for stability and color protection.

R ²¹ and R ²² are each independently an aliphatic radical having 12 to 22 carbon atoms with 0, 1, 2 or 3 double bonds.

wobei R⁹ für H oder einen gesättigten Alkylrest mit 1 bis 4 Kohlenstoffatomen, R¹⁰ und R¹¹ unabhängig voneinander jeweils für einen aliphatischen, gesättigten oder ungesättigten Alkylrest mit 12 bis 18 Kohlenstoffatomen, R¹⁰ alternativ auch für O(CO)R²⁰ stehen kann, wobei R²⁰ einen aliphatischen, gesättigten oder ungesättigten Alkylrest mit 12 bis 18 Kohlenstoffatomen bedeutet, und Z eine NH-Gruppe oder Sauerstoff bedeutet und X^- ein Anion ist. q kann ganzzahlige Werte zwischen 1 und 4 annehmen.In addition to the quaternary compounds described above, it is also possible to use other known compounds, for example quaternary imidazolinium compounds of the formula (IV),

where R ^{9 is} H or a saturated alkyl radical having 1 to 4 carbon atoms, R ¹⁰ and R ¹¹ are each independently an aliphatic, saturated or unsaturated alkyl radical having 12 to 18 carbon atoms, R ^{10 may} alternatively be O (CO) R ²⁰ wherein R ^{20 is} an aliphatic, saturated or unsaturated alkyl radical having 12 to 18 carbon atoms, and Z is an NH group or oxygen and X ^{- is} an anion. q can take integer values between 1 and 4.

wobei R¹², R¹³ und R¹⁴ unabhängig voneinander für eine C_1-4-Alkyl-, Alkenyl- oder Hydroxyalkylgruppe steht, R¹⁵ und R¹⁶ jeweils unabhängig ausgewählt eine C_8-28-Alkylgruppe darstellt und r eine Zahl zwischen 0 und 5 ist.Further suitable quaternary compounds are described by formula (V),

wherein R ¹² , R ¹³ and R ¹⁴ independently represent a C _1-4 alkyl, alkenyl or hydroxyalkyl group, each of R ¹⁵ and R ¹⁶ independently represents a C _8-28 alkyl group and r is a number between 0 and 5 is.

In addition to the compounds of formulas (I) and (II), short chain, water soluble quaternary ammonium compounds may also be used, such as trihydroxyethylmethylammonium methosulfate or the alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, e.g. Cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldirnethylammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride.

Also protonated alkylamine compounds which have plasticizing effect, as well as the non-quaternized, protonated precursors of cationic emulsifiers are suitable.

Further cationic compounds which can be used according to the invention are the quaternized protein hydrolysates.

Suitable cationic polymers include the polyquaternium polymers as described in the CTFA Cosmetic Ingredient Dictionary (The Cosmetic, Toiletry and Fragrance, Inc., 1997), in particular the Polyquaternium-6, Polyquaternium-7, Polyquaternium, also referred to as Merquats. 10 polymers (Ucare Polymer IR 400, Amerchol), polyquaternium-4 copolymers, such as graft copolymers having a cellulose backbone and quaternary ammonium groups bonded via allyldimethylammonium chloride, cationic cellulose derivatives, such as cationic guar, such as guar hydroxypropyl triammonium chloride, and similar quaternized guar gum. derivatives (eg Cosmedia guar, manufacturer: Cognis GmbH), cationic quaternary sugar derivatives (cationic alkyl polyglucosides), for example the commercial product Glucquat ^® 100, according to CTFA nomenclature a "lauryl methyl Gluceth-10 hydroxypropyl Dimonium Chloride", copolymers of PVP and dimethylaminomethacrylate, copolymers of vinylimidazole and vinylpyrrolidone, aminosilicone polymers and copolymers.

Also employable are polyquatemierte polymers (for example Luviquat Care from BASF) and also cationic biopolymers based on chitin and derivatives thereof, for example, under the trade designation chitosan ^® (manufacturer: Cognis) polymer obtainable.

Also suitable according to the invention are cationic silicone oils such as, for example, the commercially available products Q2-7224 (manufacturer: Dow Coming, a stabilized trimethylsilylamodimethicone), Dowing Coming 929 emulsion (containing a hydroxylamino-modified silicone, also referred to as amodimethicone), SM -2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) Abil ^® -Quat 3270 and 3272 (manufacturer: Goldschmidt-Rewo; diquaternary polydimethylsiloxanes, quaternium-80), and Silicone quat Rewoquat ^® SQ 1 (Tegopren ^® 6922, Manufacturer: Goldschmidt-Rewo).

die Alkylamidoamine in ihrer nicht quatemierten oder, wie dargestellt, ihrer quatemierten Form, sein können. R¹⁷ kann ein aliphatischer Alkylrest mit 12 bis 22 Kohlenstoffatomen mit 0, 1, 2 oder 3 Doppelbindungen sein. s kann Werte zwischen 0 und 5 annehmen. R¹⁸ und R¹⁹ stehen unabhängig voneinander jeweils für H, C_1-4-Alkyl oder Hydroxyalkyl. Bevorzugte Verbindungen sind Fettsäureamidoamine wie das unter der Bezeichnung Tego Amid^®S 18 erhältliche Stearylamidopropyldimethylamin oder das unter der Bezeichnung Stepantex^® X 9124 erhältliche 3-Talgamidopropyl-trimethylammonium-methosulfat, die sich neben einer guten konditionierenden Wirkung auch durch farbübertragungsinhibierende Wirkung sowie speziell durch ihre gute biologische Abbaubarkeit auszeichnen. Besonders bevorzugt sind alkylierte quaternäre Ammoniumverbindungen, von denen mindestens eine Alkylkette durch eine Estergruppe und/oder Amidogruppe unterbrochen ist, insbesondere N-Methyl-N(2-hydroxyethyl)-N,N-(ditalgacyloxyethyl)ammonium-methosulfat und/oder N-Methyl-N(2-hydroxyethyl)-N,N-(palmitoyloxyethyl)ammonium-methosulfat.Also usable are compounds of the formula (VI)

the alkylamidoamines may be in their unquaternized or their quaternized form as shown. R ¹⁷ may be an aliphatic alkyl radical having 12 to 22 carbon atoms with 0, 1, 2 or 3 double bonds. s can take values between 0 and 5. R ¹⁸ and R ¹⁹ are each independently H, C _1-4 alkyl or hydroxyalkyl. Preferred compounds are fatty acid amidoamines such as Stearylamidopropyldimethylamin available under the name Tego Amid ^® S 18 or 3-Talgamidopropyl-trimethylammonium methosulfate available under the name Stepantex ^® X 9124, which in addition to a good conditioning effect by color transfer inhibiting effect and especially by their good distinguish biodegradability. Particularly preferred are alkylated quaternary ammonium compounds, of which at least one alkyl chain is interrupted by an ester group and / or amido group, in particular N-methyl-N (2-hydroxyethyl) -N, N- (ditalgacyloxyethyl) ammonium methosulfate and / or N-methyl -N (2-hydroxyethyl) -N, N- (palmitoyloxyethyl) ammonium methosulfate.

As nonionic plasticizers are especially Polyoxyalkylenglycerolalkanoate, as described in British Patent GB 2,202,244 , Polybutylenes, as described in the British patent specification GB 2,199,855 , long-chain fatty acids, as in the EP 13 780 , ethoxylated fatty acid ethanolamides as described in the EP 43 647 , Alkylpolyglycoside, in particular sorbitan mono-, di- and triester, as described in the EP 698,140 and fatty acid esters of polycarboxylic acids, as described in the German patent DE 2,822,891 to be discribed.

In a preferred embodiment, the fine detergents according to the invention contain cationic surfactants, preferably alkylated quaternary ammonium compounds, of which at least one alkyl chain is interrupted by an ester group and / or amido group.

The use of esterquats of the abovementioned formula II has proved to be particularly advantageous and effective. In particular, esterquats of the formula [(CH ₃ ) ₂ N ⁺ (CH ₂ CH ₂ OC (O) -R) ₂ ] X ^- or [(HOCH ₂ CH ₂ ) (CH ₃ ) N ⁺ (CH ₂ CH ₂ OC ( O) -R) ₂ ] X ^- with R = linear saturated or unsaturated alkyl radical having 11 to 19, preferably 13 to 17 carbon atoms. In a particularly preferred embodiment, the fatty acid residues are tallow fatty acid residues. X ^- is either a halide, for example chloride or bromide, methophosphate or phosphate ion, preferably from methosulfate, and mixtures of these.

Furthermore, preference is given to the quaternary ammonium compounds of the abovementioned formula V.

In particular in combination with the esterquats and / or the abovementioned ammonium compounds of the formula V, the lint-reducing and wrinkle-reducing as well as the pill-reducing action have proven to be particularly intensive, in particular when microcrystalline cellulose, as described above, is used as the lint reduction component.

In particular, N-methyl-N (2-hydroxyethyl) -N, N- (ditallowacyloxyethyl) ammonium methosulfate or N-methyl-N (2-hydroxyethyl) -N, N- (dipalmitoylethyl) ammonium methosulfate are preferred.

In a further preferred embodiment, the mild detergent according to the invention contain plasticizer component in an amount of up to 15 wt .-%, preferably from 0.1 to 10 wt .-%, particularly preferably from 0.5 to 7 wt .-% and in particular from 1 to 3 wt .-%, each based on the total agent.

In addition to the foregoing components, the liquid laundry detergents or mild detergents or liquid laundry detergents or nonaqueous liquid laundry detergents of the invention may contain pearlizing agents. Pearlescing agents give the textiles an extra gloss and are therefore preferably used in the fine detergents according to the invention.

Examples of suitable pearlescing agents are: alkylene glycol esters, fatty acid alkanolamides; partial glycerides; Esters of polybasic, optionally hydroxy-substituted carboxylic acids with fatty alcohols having 6 to 22 carbon atoms; Fatty substances, such as, for example, fatty alcohols, fatty ketones, fatty aldehydes, fatty ethers and fatty carbonates, which in total have at least 24 carbon atoms; Ring opening products of olefin epoxides having 12 to 22 carbon atoms with fatty alcohols having 12 to 22 carbon atoms, fatty acids and / or polyols having 2 to 15 carbon atoms and 2 to 10 hydroxyl groups and mixtures thereof.

Furthermore, the liquid textile cleaners or mild detergents or liquid detergents or nonaqueous liquid detergents according to the invention may additionally contain thickeners. The use of thickeners in the liquid detergent according to the invention has proved to be particularly advantageous. To increase consumer acceptance, the use of thickening agents has proven particularly useful in gel-type liquid detergents. The Thickened consistency of the agent simplifies the application of the agent directly to the spots to be treated. A run, as usual with thin liquids, is thereby prevented.

Natural-derived polymers used as thickening agents include agar-agar, carrageenan, tragacanth, gum arabic, alginates, pectins, polyoses, guar flour, locust bean gum, starch, dextrins, gelatin and casein.

Modified natural products come mainly from the group of modified starches and celluloses, examples being carboxymethyl cellulose and cellulose ethers, hydroxyethyl and - propyl cellulose and Kemmehlether called.

A large group of thickeners, which find wide use in a variety of applications, are the fully synthetic polymers such as polyacrylic and polymethacrylic compounds, vinyl polymers, polycarboxylic acids, polyethers, polyimines, polyamides and polyurethanes.

Thickeners from said substance classes are widely available commercially and are sold for example under the trade name Acusol ^® -820 (methacrylic acid (stearyl alcohol 20 EO) ester-acrylic acid copolymer, 30% in water, Rohm & Haas), Dapral ^® -GT -282-S (alkyl polyglycol ethers, Akzo), DEUTEROL ^® polymer-11 (dicarboxylic acid copolymer, Schoner GmbH) deuteron ^® -xg (anionic heteropolysaccharide based on β-D-glucose, D-mannose, D-glucuronic acid, Beautiful GmbH), -XN deuteron ^® (non-ionic polysaccharide, Schoner GmbH), DICRYLAN ^® -Verdicker-O (ethylene oxide adduct, 50% solution in water / isopropanol, Pfersse Chemie), EMA ^® -81 and EMA ^® -91 (ethylene maleic anhydride copolymer, Monsanto) (polyurethane emulsion, 19 to 21% strength in water / diglyme, Rohm & Haas), Mirox ^® -AM (anionic acrylic acid-acrylate copolymer dispersion, 25% in thickener QR-1001 water, Stockhausen), SER-AD FX 1100 (hydrophobic urethane polymer, servo Delden), Shellflo ^® -S (hoc hmolekulares polysaccharide, stabilized with formaldehyde, Shell), and Shellflo XA ^® (xanthan biopolymer, stabilized with formaldehyde, Shell).

A preferred polymeric polysaccharide thickener is xanthan gum, a microbial anionic heteropolysaccharide produced by Xanthomonas campestris and some other species under aerobic conditions and having a molecular weight of from 2 to 15 million g / mole. Xanthan is formed from a chain of β-1,4-linked glucose (cellulose) with side chains. The structure of the subgroups consists of glucose, mannose, glucuronic acid, acetate and pyruvate, the number of pyruvate units determining the viscosity of the xanthan gum.

It is particularly advantageous to use xanthans and modified xanthans because of their high acid stability and oxidation stability.

Xanthan can be described by the following formula:

In a preferred embodiment, the liquid detergents according to the invention additionally comprise thickeners, preferably in amounts of up to 10% by weight, more preferably up to 5% by weight, in particular from 0.1 to 1% by weight, in each case based on the total Medium.

Furthermore, the liquid laundry detergents or mild detergents or liquid laundry detergents according to the invention can be used or non-aqueous liquid detergents additionally contain odor absorbers and / or color transfer inhibitors. In particular, for the fine and liquid detergents according to the invention, the use of Farbübertragungsinhibtoren has proven. The use of odor absorbers has proven to be very useful for deodorizing foul-smelling constituents of formulations, for example amine-containing components, but also for sustainable deodorization of the laundered textiles.

In a preferred embodiment, the compositions according to the invention optionally contain 0.1% by weight to 2% by weight, preferably 0.2% by weight to 1% by weight, of color transfer inhibitor, which in a preferred embodiment of the invention comprises a polymer of vinylpyrrolidone , Vinylimidazole, vinylpyridine N-oxide or a copolymer of these. Useful are both the example of the European patent application EP 0 262 897 known Polyvinylpyrrolidone with molecular weights of 15,000 to 50,000 as well as those of the international patent application WO 95/06098 known polyvinylpyrrolidones having molecular weights above 1 000 000, in particular from 1 500 000 to 4 000 000, which are known from the German patent applications DE 28 14 287 or DE 38 03 630 or the international patent applications WO 94/10281 . WO 94/26796 , WO 95/03388 and WO 95/03382 known N-vinylimidazole / N-vinylpyrrolidone copolymers, which are known from the German patent application DE 28 14 329 Polyvinyloxazolidone known from the European patent application EP 610 846 known copolymers based on vinyl monomers and carboxamides, from the international patent application WO 95/09194 known Pyrrolidongnrppenhaltigen polyester and polyamides, from the international patent application WO 94/29422 known grafted polyamidoamines and polyethyleneimines, from the German patent application DE 43 28 254 known polymers with amide groups from secondary amines, which are from the international Patent Application WO 94/02679 or the European patent application EP 0135 217 known polyamine N-oxide polymers, from the European patent application EP 0 584 738 known polyvinyl alcohols and those of the European patent application EP 0 584 709 known copolymers based on acrylamidoalkenylsulfonic acids. However, it is also possible to use enzymatic systems comprising a peroxidase and hydrogen peroxide or a substance which gives hydrogen peroxide in water, as described, for example, in the international patent applications WO 92/18687 and WO 91/05839 are known. The addition of a mediator compound for the peroxidase, for example one from the international patent application WO 96/10079 known acetosyringone, one from the international patent application WO 96/12845 known phenol derivative or one from the international patent application WO 96/12846 known phenotiazine or phenoxazine, is preferred in this case, whereby also above-mentioned polymeric Farbübertragungsinhibitorwirkstoffe can be used. Polyvinylpyrrolidone preferably has an average molecular weight in the range from 10 000 to 60 000, in particular in the range from 25 000 to 50 000, for use in compositions according to the invention. Among the copolymers, those of vinylpyrrolidone and vinylimidazole in a molar ratio of 5: 1 to 1: 1 having an average molecular weight in the range of 5,000 to 50,000, especially 10,000 to 20,000 are preferred.

Preferred deodorizing substances in the context of the invention are one or more metal salts of an unbranched or branched, unsaturated or saturated, mono- or polyhydroxylated fatty acid having at least 16 carbon atoms and / or a rosin acid with the exception of the alkali metal salts and any desired mixtures thereof.

A particularly preferred unbranched or branched, unsaturated or saturated, mono- or polyhydroxylated fatty acid having at least 16 carbon atoms is ricinoleic acid. A particularly preferred rosin acid is abietic acid.

Preferred metals are the transition metals and the lanthanides, in particular the transition metals of Groups VIIIa, Ib and IIb of the Periodic Table and lanthanum, cerium and

Neodymium, more preferably cobalt, nickel, copper and zinc, most preferably zinc. The cobalt, nickel and copper salts and the zinc salts are similarly effective, but for toxicological reasons, the zinc salts are to be preferred.

It is advantageous and therefore particularly preferred to use as deodorizing substances one or more metal salts of ricinoleic acid and / or abietic acid, preferably zinc ricinoleate and / or zinc abietate, in particular zinc ricinoleate.

Cyclodextrins, as well as any desired mixtures of the abovementioned metal salts with cyclodextrins, preferably in a weight ratio of from 1:10 to 10: 1, particularly preferably from 1: 5 to 5: 1 and in particular from 1, also prove to be suitable further deodorizing substances : 3 to 3: 1. The term "cyclocodextrin" includes all known cyclodextrins, i. both unsubstituted cyclodextrins having 6 to 12 glucose units, in particular alpha-, beta- and gamma-cyclodextrins and mixtures thereof and / or their derivatives and / or mixtures thereof.

The liquid textile cleaners or mild detergents or liquid detergents or nonaqueous liquid detergents according to the invention may additionally contain further surfactants, for example amphoteric surfactants.

The amphoteric surfactants (zwitterionic surfactants) which can be used according to the invention include betaines, amine oxides, alkylamidoalkylamines, alkyl-substituted amino acids, acylated amino acids or biosurfactants, of which the betaines are particularly preferred within the scope of the teaching according to the invention.

R¹

ein gesättigter oder ungesättigter C_6-22-Alkylrest, vorzugsweise C_8-18-Alkylrest, insbesondere ein gesättigter C_10-16-Alkylrest, beispielsweise ein gesättigter C_12-14-Alkylrest,

X

NH, NR⁴ mit dem C_1-4-Alkylrest R⁴, O oder S,

n

eine Zahl von 1 bis 10, vorzugsweise 2 bis 5, insbesondere 3,

x

0 oder 1, vorzugsweise 1,

R², R³

unabhängig voneinander ein C_1-4-Alkylrest, ggf. hydroxysubstituiert wie z.B. ein Hydroxyethylrest, insbesondere aber ein Methylrest,

m

eine Zahl von 1 bis 4, insbesondere 1, 2 oder 3,

y

0 oder 1 und

Y

COO, SO₃, OPO(OR⁵)O oder P(O)(OR⁵)O, wobei R⁵ ein Wasserstoffatom H oder ein C_1-4-Alkylrest ist.

Suitable betaines are the alkylbetaines, the alkylamidobetaines, the imidazolinium betaines, the sulfobetaines ( INCI Sultaines) and the phosphobetaines and preferably satisfy formula I,

R ¹ - [CO-X- (CH ₂ ) _n ] _x -N ⁺ (R ² ) (R ³ ) - (CH ₂ ) _m - [CH (OH) -CH ₂ ] _y -Y ^- (I)

in the

R ¹

a saturated or unsaturated C _6-22 alkyl, preferably C _8-18 alkyl group, preferably a saturated C _10-16 alkyl group, for example a saturated C _12-14 alkyl group,

X

NH, NR ⁴ with the C _1-4 -alkyl radical R ⁴ , O or S,

n

a number from 1 to 10, preferably 2 to 5, in particular 3,

x

0 or 1, preferably 1,

R ² , R ³

independently of one another represent a C _1-4 -alkyl radical, if appropriate hydroxy-substituted, for example a hydroxyethyl radical, but in particular a methyl radical,

m

a number from 1 to 4, in particular 1, 2 or 3,

y

0 or 1 and

Y

COO, SO ₃ , OPO (OR ⁵ ) O or P (O) (OR ⁵ ) O, wherein R ^{5 is} hydrogen H or C _1-4 alkyl.

The alkyl and alkylamido betaines, betaines of the formula I having a carboxylate group (Y ^- = COO ^- ) are also called carbobetaines.

Preferred amphoteric surfactants are the alkylbetaines of the formula (Ia), the alkylamidobetaines of the formula (Ib), the sulfobetaines of the formula (Ic) and the amidosulfobetaines of the formula (Id),

R ¹ -N ⁺ (CH ₃ ) ₂ -CH ₂ COO ^- (Ia)

R ¹ -CO-NH- (CH ₂ ) ₃ -N ⁺ (CH ₃ ) ₂ -CH ₂ COO ^- (Ib)

R ^{1 is} -N ⁺ (CH ₃ ) ₂ -CH ₂ CH (OH) CH ₂ SO ₃ ^- (Ic)

R ¹ -CO-NH- (CH ₂ ) ₃ -N ⁺ (CH ₃ ) ₂ -CH ₂ CH (OH) CH ₂ SO ₃ ^- (Id)

in which R ^{1 has} the same meaning as in formula I.

Particularly preferred amphoteric surfactants are the carbo-betaines, in particular the carbo-betaines of the formula (Ia) and (Ib), most preferably the alkylamido-betaines of the formula (Ib).

Examples of suitable betaines and sulfobetaines are the following compounds designated as INCI : almondamidopropyl betaines, apricotamidopropyl betaines, avocadamidopropyl betaines, babassuamidopropyl betaines, behenamidopropyl betaines, behenyl betaines, betaines, canolamidopropyl betaines, caprylic / capramidopropyl betaines, carnitines, cetyl betaines, cocamidoethyl betaines, cocamidopropyl Betaines, cocamidopropyl hydroxysultaines, coco-betaines, coco-hydroxysultaines, coco / oleamidopropyl betaines, coco-sultaines, decyl betaines, dihydroxyethyl oleyl glycinates, dihydroxyethyl soy glycinates, dihydroxyethyl stearyl glycinates, dihydroxyethyl tallow glycinates, dimethicones, propyl PG-betaines, erucamidopropyl hydroxysultaines, Hydrogenated Tallow Betaine, Isastearamidapropyl Betaine, Lauramidopropyl Betaine, Lauryl Betaine, Lauryl Hydroxysultaine, Lauryl Sultaine, Milkamidopropyl Betaine, Minkamidopropyl Betaine, Myristamidopropyl Betaine, Myristyl Betaine, Oleamidopropyl Betaine, Oleamidopropyl Hydroxysult aine, oleylbetaines, olivamidopropyl betaines, palmamidopropyl betaines, palmitamidopropyl betaines, palmitoyl carnitines, palm ketamidopropyl betaines, polytetrafluoroethylene acetoxypropyl betaines, ricinoleamidopropyl betaines, sesamidopropyl betaines, soyamidopropyl betaines, stearamidopropyl betaines, stearyl betaines, tallowamidopropyl betaines, tallowamidopropyl hydroxysultaines, tallow betaines, tallow Dihydroxyethyl betaines, undecylenamidopropyl betaines and wheat germamidopropyl betaines.

R⁶

ein gesättigter oder ungesättigter C_6-22-Alkylrest, vorzugsweise C_8-18-Alkylrest, insbesondere ein gesättigter C_10-18-Alkylrest, beispielsweise ein gesättigter C_12-14-Alkylrest, der in den Alkylamidoaminoxiden über eine Carbonylami- doalkylengruppe -CO-NH-(CH₂)_z- und in den Alkoxyalkylaminoxiden über eine Oxaalkylengruppe -O-(CH₂)_z- an das Stickstoffatom N gebunden ist, wo- bei z jeweils für eine Zahl von 1 bis 10, vorzugsweise 2 bis 5, insbesondere 3,

R⁷, R⁸

unabhängig voneinander ein C_1-4-Alkylrest, ggf. hydroxysubstituiert wie z.B. ein Hydroxyethylrest, insbesondere ein Methylrest, ist.

The amine oxides suitable in accordance with the invention include alkylamine oxides, in particular alkyldimethylamine oxides, alkylamidoamine oxides and alkoxyalkylamine oxides. Preferred amine oxides satisfy formula II,

R ⁶ R ⁷ R ⁸ N ⁺ -O ^- (II)

R ⁸ - [CO-NH- (CH ₂ ) _w ] _z -N ⁺ (R ⁷ ) (R ⁸ ) -O ^- (II)

in the

R ⁶

a saturated or unsaturated C _6-22 alkyl radical, preferably C _8-18 alkyl radical, in particular a saturated one C _10-18 -alkyl radical, for example a saturated C _12-14 -alkyl radical which in the alkylamidoamine oxides via a carbonylami- doalkylengruppe -CO-NH- (CH ₂ ) _z - and in the Alkoxyalkylaminoxiden via an oxaalkylene group -O- (CH ₂ ) _z - is bonded to the nitrogen atom N, where z is in each case a number from 1 to 10, preferably 2 to 5, in particular 3,

R ⁷ , R ⁸

independently of one another a C _1-4 -alkyl radical, if appropriate hydroxy-substituted, for example a hydroxyethyl radical, in particular a methyl radical.

Examples of suitable amine oxides are the following compounds designated as INCI : Almondamidopropylamine oxides, Babassuamidopropylamine oxides, Behenamine oxides, Cocamidopropyl Amine oxides, Cocamidopropylamine oxides, Cocamine oxides, Coco-Morpholine oxides, Decylamine oxides, Decyltetradecylamine oxides, Diaminopyrimidine oxides, Dihydroxyethyl C8-10 alkoxypropylamines oxides , Dihydroxyethyl C9-11 alkoxypropylamines oxides, dihydroxyethyl C12-15 alkoxypropylamines oxides, dihydroxyethyl cocamine oxides, dihydroxyethyl lauramine oxides, dihydroxyethyl stearamines oxides, dihydroxyethyl tallowamine oxides, hydrogenated palm kernel, amine oxides, hydrogenated tallowamine oxides, hydroxyethyl hydroxypropyl, C12-15 alkoxypropylamines oxides, isostearamidopropylamines Oxides, Isostearamidopropyl Morpholine Oxide, Lauramidopropylamine Oxide, Lauramine Oxide, Methyl Morpholine Oxide, Milkamidopropyl Amine Oxide, Minkamidopropylamine Oxide, Myristamidopropylamine Oxide, Myristamine Oxide, Myristyl / Cetyl Amine Oxide e, Oleamidopropylamine Oxide, Oleamine Oxide, Olivamidopropylamine Oxide, Palmitamidopropylamine Oxide, Palmitamine Oxide, PEG-3 Lauramine Oxide, Potassium Dihydroxyethyl Cocamine Oxide Phosphate, Potassium Trisphosphonomethylamine Oxide, Sesamidopropylamine Oxide, Soyamidopropylamine Oxide, Stearamidopropylamine Oxide, Stearamine Oxide, Tallowamidopropylamine Oxide, Tallowamine Oxide , Undecylenamidopropylamine oxides and wheat germamidopropylamine oxides.

R⁹

ein gesättigter oder ungesättigter C_8-22-Alkylrest, vorzugsweise C_9-18-Alkylrest, insbesondere ein gesättigter C_10-18-Alkylrest, beispielsweise ein gesättigter C_12-14-Alkylrest,

R¹⁰

ein Wasserstoffatom H oder ein C_1-4-Alkylrest, vorzugsweise H,

i

eine Zahl von 1 bis 10, vorzugsweise 2 bis 5, insbesondere 2 oder 3,

R¹¹

ein Wasserstoffatom H oder CH₂COOM (zu M s.u.),

j

eine Zahl von 1 bis 4, vorzugsweise 1 oder 2, insbesondere 1,

k

eine Zahl von 0 bis 4, vorzugsweise 0 oder 1,

I

0 oder 1, wobei k = 1 ist, wenn I = 1 ist,

Z

CO, SO₂, OPO(OR¹²) oder P(O)(OR¹²), wobei R¹² ein C_1-4-Alkylrest oder M (s.u.) ist, und

M

ein Wasserstoff, ein Alkalimetall, ein Erdalkalimetall oder ein protoniertes Alkanolamin, z.B. protoniertes Mono-, Di- oder Triethanolamin, ist.

The alkylamidoalkylamines ( INCI alkylamido alkylamines) are amphoteric surfactants of the formula (III)

R ⁹ -CO-NR ¹⁰ - (CH ₂ ) _i -N (R ¹¹ ) - (CH ₂ CH ₂ O) _j - (CH ₂ ) _k - (CH (OH)] _i -CH ₂ -Z-OM ( III)

in the

R ⁹

a saturated or unsaturated C _8-22 -alkyl radical, preferably C _9-18 -alkyl radical, preferably a saturated C _10-18 alkyl group, for example a saturated C _12-14 alkyl group,

R ¹⁰

a hydrogen atom H or a C _1-4 -alkyl radical, preferably H,

i

a number from 1 to 10, preferably 2 to 5, in particular 2 or 3,

R ¹¹

a hydrogen atom H or CH ₂ COOM (to M su),

j

a number from 1 to 4, preferably 1 or 2, in particular 1,

k

a number from 0 to 4, preferably 0 or 1,

I

0 or 1, where k = 1, if I = 1,

Z

CO, SO ₂ , OPO (OR ¹² ) or P (O) (OR ¹² ), wherein R ^{12 is} a C _1-4 alkyl radical or M (su), and

M

a hydrogen, an alkali metal, an alkaline earth metal or a protonated alkanolamine, for example protonated mono-, di- or triethanolamine.

Preferred representatives satisfy the formulas IIIa to IIId,

R ⁹ -CO-NH- (CH ₂ ) ₂ -N (R ¹¹ ) -CH ₂ CH ₂ O-CH ₂ -COOM (IIIa)

R ⁹ -CO-NH- (CH ₂ ) ₂ -N (R ¹¹ ) -CH ₂ CH ₂ O-CH ₂ CH ₂ -COOM (IIIb)

R ⁹ -CO-NH- (CH ₂ ) ₂ -N (R ¹¹ ) -CH ₂ CH ₂ O-CH ₂ CH (OH) CH ₂ -SO ₃ M (IIIc)

R ⁹ -CO-NH- (CH ₂ ) ₂ -N (R ¹¹ ) -CH ₂ CH ₂ O-CH ₂ CH (OH) CH ₂ -OPO ₃ HM (IIId)

in which R ¹¹ and M have the same meaning as in formula (III).

Exemplary alkylamidoalkylamines are the following named according to INCI compounds: Cocoamphodipropionic Acid, Cocobetainamido amphopropionates, DEA-Cocoamphodipropionate, Disodium Caproamphodiacetate, Disodium Caproamphodipropionate, Disodium Capryloamphodiacetate, Disodium Capryloamphodipropionate, Disodium Cocoamphocarboxyethylhydroxypropylsulfonate, Disodium Cocoamphodiacetate, Disodium Cocoamphodipropionate, Disodium Isostearoamphodiacetate, Disodium Isostearoamphodipropionate, Disodium laureth 5 Carboxyamphodiacetates, Disodium Lauroamphodiacetate, Disodium Lauroamphodipropionate, Disodium Oleoamphodipropionate, Disodium PPG-2-Isodeceth-7 Carboxyamphodiacetate, Disodium Stearoamphodiacetate, Disodium Tallowamphodiacetate, Disodium Wheatgermamphodiacetate, Lauroamphodipropionic Acid, Quaternium-85, Sodium Caproamphoacetate, Sodium Caproamphohydroxypropylsulfonate, Sodium Caproamphopropionate, Sodium Capryloamphoacetate, Sodium Capryloamphohydroxypropylsulfonate, Sodium Capryloamphopropionate, Sodium Cocoamphoacetate, Sodium Cocoamphohydroxypropylsulfonate, Sodium Cocoamphopropionate, Sodium Comamphopropionate, Sodium Isostearoamphoacetate, Sodium Isostearoamphopropionate, Sodium lauroamphoacetate, sodium Lauroamphohydroxypropylsulfonate, Sodium Lauroampho PG-Acetate Phosphate, Sodium Lauroamphopropionate, Sodium Myristoamphoacetate, Sodium Oleoamphoacetate, Sodium Oleoamphohydroxypropylsulfonate, Sodium Oleoamphopropionate, Sodium Ricinoleoamphoacetate, Sodium Stearoamphoacetate, Sodium Stearoamphohydroxypropylsulfonate, Sodium Stearoamphopropionate, Sodium Tallamphopropionate, Sodium Tallowamphoacetate, Sodium Undecylenoamphoacetate, Sodium Undecylenoamphopropionate, Sodium Wheat Germamphoacetate and Trisodium Lauroampho PG-Acetate Chloride phosphate.

R¹³

ein gesättigter oder ungesättigter C_6-22-Alkylrest, vorzugsweise C_8-18-Alkylrest, insbesondere ein gesättigter C_10-16-Alkylrest, beispielsweise ein gesättigter C_12-14-Alkylrest,

R¹⁴

ein Wasserstoffatom H oder ein C_1-4-Alkylrest, vorzugsweise H,

u

eine Zahl von 0 bis 4, vorzugsweise 0 oder 1, insbesondere 1, und

M'

ein Wasserstoff, ein Alkalimetall, ein Erdalkalimetall oder ein protoniertes Alka- nolamin, z.B. protoniertes Mono-, Di- oder Triethanolamin, ist,

alkylsubstituierte Iminosäuren gemäß Formel (V),

        R¹⁵-N-[(CH₂)_v-COOMM"]₂     (V)

in der

R¹⁵

ein gesättigter oder ungesättigter C_6-22-Alkylrest, vorzugsweise C_6-18-Alkylrest, insbesondere ein gesättigter C_10-18-Alkylrest, beispielsweise ein gesättigter C_12-14-Alkylrest,

v

eine Zahl von 1 bis 5, vorzugsweise 2 oder 3, insbesondere 2, und

M"

ein Wasserstoff, ein Alkalimetall, ein Erdalkalimetall oder ein protoniertes Alka- nolamin, z.B. protoniertes Mono-, Di- oder Triethanolamin, wobei M" in den bei- den Carboxygruppen die gleiche oder zwei verschiedene Bedeutungen haben kann, z.B. Wasserstoff und Natrium oder zweimal Natrium sein kann, ist,

und mono- oder dialkylsubstituierte natürliche Aminosäuren gemäß Formel (VI),

        R¹⁶-N(R¹⁷)-CH(R¹⁸)-COOM"'     (VI)

in der

R¹⁶

ein gesättigter oder ungesättigter C_6-22-Alkylrest, vorzugsweise C_8-18-Alkylrest, insbesondere ein gesättigter C_10-16-Alkylrest, beispielsweise ein gesättigter C_12-14-Alkylrest,

R¹⁷

ein Wasserstoffatom oder ein C_1-4-Alkylrest, ggf. hydroxy- oder aminsubstitu- iert, z.B. ein Methyl-, Ethyl-, Hydroxyethyl- oder Aminpropylrest,

R¹⁸

den Rest einer der 20 natürlichen α-Aminosäuren H₂NCH(R¹⁸)COOH, und

M"'

ein Wasserstoff, ein Alkalimetall, ein Erdalkalimetall oder ein protoniertes Al- kanolamin, z.B. protoniertes Mono-, Di- oder Triethanolamin, ist.

Preferred alkyl-substituted amino acids ( INCI alkyl-substituted amino acids) according to the invention are monoalkyl-substituted amino acids according to formula (IV),

R ¹³ -NH-CH (R ¹⁴ HCH ₂ ) _u -COOM '(IV)

in the

R ¹³

a saturated or unsaturated C _6-22 alkyl, preferably C _8-18 alkyl group, preferably a saturated C _10-16 alkyl group, for example a saturated C _12-14 alkyl group,

R ¹⁴

a hydrogen atom H or a C _1-4 -alkyl radical, preferably H,

u

a number from 0 to 4, preferably 0 or 1, in particular 1, and

M '

is a hydrogen, an alkali metal, an alkaline earth metal or a protonated alkanolamine, for example protonated mono-, di- or triethanolamine,

alkyl-substituted imino acids according to formula (V),

R ¹⁵ -N - [(CH ₂ ) _v -COOMM "] ₂ (V)

in the

R ¹⁵

a saturated or unsaturated C _6-22 -alkyl radical, preferably C _6-18 -alkyl radical, in particular a saturated C _10-18 -alkyl radical, for example a saturated C _12-14 -alkyl radical,

v

a number from 1 to 5, preferably 2 or 3, in particular 2, and

M "

a hydrogen, an alkali metal, an alkaline earth metal or a protonated alkanolamine, for example protonated mono-, di- or triethanolamine, where M "in the two carboxy groups may have the same or two different meanings, for example hydrogen and sodium or twice sodium can be, is

and mono- or dialkyl-substituted natural amino acids according to formula (VI),

R ¹⁶ -N (R ¹⁷ ) -CH (R ¹⁸ ) -COOM "'(VI)

in the

R ¹⁶

a saturated or unsaturated C _6-22 alkyl, preferably C _8-18 alkyl group, preferably a saturated C _10-16 alkyl group, for example a saturated C _12-14 alkyl group,

R ¹⁷

is a hydrogen atom or a C _1-4 -alkyl radical, optionally hydroxyl- or amine-substituted, eg a methyl, ethyl, hydroxyethyl or aminopropyl radical,

R ¹⁸

the remainder of one of the 20 natural α-amino acids H ₂ NCH (R ¹⁸ ) COOH, and

M ''

is a hydrogen, an alkali metal, an alkaline earth metal or a protonated alkanolamine, for example protonated mono-, di- or triethanolamine.

Particularly preferred alkyl-substituted amino acids are the aminopropionates according to formula (IVa),

R ¹³ -NH-CH ₂ CH ₂ COOM '(IVa)

in which R ¹³ and M 'have the same meaning as in formula (IV).

Exemplary alkyl-substituted amino acids are the following compounds designated as INCI : aminopropyl laurylglutamine, cocaminobutyric acid, cocaminopropionic acid, DEA-lauraminopropionate, disodium Cocaminopropyl iminodiacetates, disodium dicarboxyethyl Cocopropylenediamine, Disodium Lauriminodipropionate, Disodium Steariminodipropionate, Disodium Tallowiminodipropionate, Lauraminopropionic Acid, Lauryl Aminopropylglycine, lauryl Diethylenediaminoglycine, Myristaminopropionic Acid, Sodium C12-15 alkoxypropyl iminodipropionates, Sodium Cocamincpropionate, Sodium Lauraminopropionate, Sodium Lauriminodipropionate, Sodium Lauroyl Methylaminopropionate, TEA Lauraminopropionate and TEA myristaminopropionate.

Acylated amino acids are amino acids, in particular the 20 natural α-amino acids which carry on the amino nitrogen the acyl radical R ¹⁹ CO of a saturated or unsaturated fatty acid R ¹⁹ COOH, where R ^{19 is} a saturated or unsaturated C _6-22 alkyl radical, preferably C _8-18 alkyl radical, preferably a saturated C _10-16 alkyl group, for example a saturated C _12-14 alkyl group is acylated, the amino acids can also be used as alkali metal salt, alkaline earth metal or alkanolammonium, for example mono-, di- or triethanolammonium. Exemplary acylated amino acids are the acyl derivatives summarized in accordance with INCI under Amino Acids, for example sodium cocoyl glutamate, lauroyl glutamic acid, capryloyl glycine or myristoyl methylalanine.

In a preferred embodiment, the total surfactant content, without the amount of fatty acid soap, is below 55% by weight, preferably below 50% by weight, particularly preferably between 38 and 48% by weight, in each case based on the total agent.

The liquid laundry detergents or mild detergents or liquid laundry detergents or nonaqueous liquid laundry detergents according to the invention may additionally contain further laundry detergent additives. for example from the group of builders, bleaches, bleach activators, electrolytes, pH adjusters, fragrances, perfume carriers, fluorescers, dyes, foam inhibitors, grayness inhibitors, wrinkle inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, antistatic agents, ironing aids, UV absorbers, optical brighteners , Anti-redeposition agents, viscosity regulators, anti-shrinkage agents, corrosion inhibitors, preservatives, repellents and impregnating agents.

The agents according to the invention may contain builders.
All builders conventionally used in detergents and cleaning agents can be incorporated into the compositions according to the invention, in particular zeolites, silicates, carbonates, organic cobuilders and, where there are no ecological prejudices against their use, also the phosphates.

Suitable crystalline layered sodium silicates have the general formula NaMSi _x O _{2x + 1} • H ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2, 3 or 4 are. Such crystalline sheet silicates are described, for example, in the European patent application EP-A-0 164 514 described. Preferred crystalline layered silicates of the formula given are those in which M is sodium and x 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-Natnumdisilikat can be obtained for example by the method described in the international patent application WO-A-91/08171 is described.

It is also possible to use amorphous sodium silicates with a Na ₂ O: SiO ₂ modulus of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which Delayed and have secondary washing properties. The dissolution delay compared with conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compaction / densification or by overdrying. In the context of this invention, the term "amorphous" is also understood to mean "X-ray amorphous". This means that the silicates do not yield sharp X-ray reflections typical of crystalline substances in X-ray diffraction experiments, but at most one or more maxima of the scattered X-rays having a width of several degrees of diffraction angle. However, it may well even lead to particularly good builder properties if the silicate particles provide blurred or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline regions of size 10 to a few hundred nm, values of up to max. 50 nm and in particular up to max. 20 nm are preferred. Such so-called X-ray amorphous silicates, which likewise have a dissolution delay compared with the conventional water glasses, are described, for example, in US Pat German patent application DE-A-44 00 024 described. Particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates.

The finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P. As zeolite P, zeolite ^MAP® (commercial product from Crosfield) is particularly preferred. Also suitable, however, are zeolite X and mixtures of A, X and / or P. Commercially available and preferably usable in the context of the present invention is, for example, a cocrystal of zeolite X and zeolite A (about 80% by weight of zeolite X) ), which is sold by the company CONDEA Augusta SpA under the brand name VEGOBOND AX ^® and by the formula

nNa ₂ O • (1-n) K ₂ O • Al ₂ O ₃ • (2 - 2.5) SiO ₂ • (3.5-5.5) H ₂ O

can be described. Suitable zeolites have an average particle size of less than 10 microns (Volume distribution, measuring method: Coulter Counter) and preferably contain 18 to 22 wt .-%, in particular 20 to 22 wt .-% of bound water. The zeolites can also be used as overdried zeolites with lower water contents and then, due to their hygroscopicity, are suitable for removing unwanted residual traces of free water.
Of course, a use of the well-known phosphates as builders is possible, unless such use should not be avoided for environmental reasons. Particularly suitable are the sodium salts of orthophosphates, pyrophosphates and in particular tripolyphosphates.

Suitable organic builders useful as co-builders, which of course also serve to regulate the viscosity, are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. These are, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA) and their derivatives and mixtures thereof. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures thereof.

The acids themselves can also be used. In addition to their builder effect, the acids also typically have the property of an acidifying component and thus also serve to set a lower and milder pH of detergents or cleaners. In particular, citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here. Further useable acidulants are known pH regulators, such as sodium bicarbonate and sodium hydrogen sulfate. Other suitable builders are polymeric polycarboxylates, for example the alkali metal salts of polyacrylic acid or of polymethacrylic acid, for example those having a relative molecular weight of 500 to 70,000 g / mol.

For the purposes of this document, the molecular weights stated for polymeric polycarboxylates are weight-average molar masses M _{w of} the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship with the polymers investigated. These data differ significantly from the molecular weight data, in which polystyrene sulfonic acids are used as standard. The molar masses measured against polystyrenesulfonic acids are generally significantly higher than the molecular weights specified in this document.

Suitable polymers are in particular polyacrilates, which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molecular weights of from 2,000 to 10,000 g / mol, and particularly preferably from 3,000 to 5,000 g / mol, may again be preferred from this group.

Suitable polymers may also include substances consisting partly or wholly of units of vinyl alcohol or its derivatives.

Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable. Their relative molecular weight, based on free acids, is generally from 2,000 to 70,000 g / mol, preferably from 20,000 to 50,000 g / mol and in particular from 30,000 to 40,000 g / mol. The (co) polymeric polycarboxylates can be used either as an aqueous solution or, preferably, as a powder.

To improve the water solubility, the polymers may also allylsulfonic acids, such as in the EP-B-0 727 448 Allyloxybenzenesulfonic acid and methallylsulfonic acid, as a monomer.

Also particularly preferred are biodegradable polymers of more than two different monomer units, for example, those according to the DE-A-43 00 772 as monomers, salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or according to the DE-C-42 21 381 as monomers, salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives.

Further preferred copolymers are those described in the German patent applications DE-A-43 03 320 and DE-A-44 17 734 be described and as monomers preferably acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.

Also to be mentioned as further preferred builders polymeric aminodicarboxylic acids, their salts or their precursors. Particularly preferred are polyaspartic acids or their salts and derivatives, of which in the German patent application DE-A-195 40 086 is disclosed that they also have a bleach-stabilizing effect in addition to Cobuilder properties. Also suitable are polyvinylpyrrolidones, polyamine derivatives such as quaternized and / or ethoxylated hexamethylenediamines.

Further suitable builder substances are polyacetals which are prepared by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 C atoms and at least 3 hydroxyl groups, for example as in the European patent application EP-A-0 280 223 described, can be obtained. Preferred polyacetals are selected from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.

Also suitable as organic builders are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches. The hydrolysis can be carried out by customary, for example acid or enzyme catalyzed processes. Preferably, it is hydrolysis products having average molecular weights in the range of 400 to 500 000 g / mol. In this case, a polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30 is preferred, DE being a common measure of the reducing action of a polysaccharide compared to dextrose, which has a DE of 100 , is. Both maltodextrins with a DE of between 3 and 20 and dry glucose syrups with a DE of between 20 and 37 and also yellow dextrins and white dextrins with relatively high molecular weights in the range from 2 000 to 30 000 g / mol are useful. A preferred dextrin is in the British patent application 94 19 091 described.

The oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function. Such oxidized dextrins and methods of their preparation are, for example, from the European patent applications EP-A-0 232 202 . EP-A-0 427 349 . EP-A-0 472 042 and EP-A-0 642 496 as well as the international patent applications WO-A-92/18542 . WO-A-93/08261 . WO-A-93/16110 . WO 94/28030 . WO-A-95/07303 . WO 95/12619 and WO 95/20608 known. Also suitable is an oxidized oligosaccharide according to the German patent application DE-A-196 00 018 , A product oxidized to C _{6 of} the saccharide may be particularly advantageous.

Oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate, are other suitable co-builders. In this case, ethylenediamine-N, N'-disuccinate (EDDS), the synthesis of which, for example, in US 3,158,615 is described, preferably used in the form of its sodium or magnesium salts. Also preferred in this context are glycerol disuccinates and glycerol trisuccinates, as described, for example, in US Pat US 4,524,009 . US 4,639,325 In the European patent application EP-A-0 150 930 and Japanese Patent Application JP-A-931339 896 to be discribed. Suitable amounts are in zeolithhaltigen and / or silicate-containing formulations at 3 to 15 wt .-%.

Other useful organic cobuilders are, for example, acetylated hydroxycarboxylic acids or salts thereof, which may optionally also be present in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups. Such co-builders are used, for example, in the international Patent Application WO 95/20029 described.

The agents according to the invention may optionally be builders in amounts of from 1 to 30% by weight, preferably from 10 to 25% by weight. The nonaqueous liquid detergents according to the invention advantageously contain as builders water-soluble builders, preferably from the group of the oligo- and polycarboxylates, the carbonates and the crystalline and / or amorphous silicates. Among these compounds, the salts of citric acid have been found to be particularly suitable, with the alkali metal and, in particular, the sodium salts are preferred.

The compositions according to the invention, in particular the nonaqueous liquid detergents according to the invention, may contain bleaching agents.

Among the compounds serving as bleaches in water H ₂ O ₂ , sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Other useful bleaching agents are, for example, peroxopyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracidic salts or peracids, such as persulfates or persulfuric acid. Also useful is the urea peroxohydrate percarbamide, which can be described by the formula H ₂ N-CO-NH ₂ .H ₂ O ₂ . In particular, when using the means for cleaning hard surfaces, for example in automatic dishwashing, they may, if desired, also contain bleaching agents from the group of organic bleaches, although their use is also possible in principle for laundry detergents. Typical organic bleaches are the diacyl peroxides, such as dibenzoyl peroxide. Other typical organic bleaches are the peroxyacids, examples of which include the alkyl peroxyacids and the aryl peroxyacids. Preferred representatives are the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy-α-naphthoic acid and magnesium monoperphthalate, the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ε-phthalimidoperoxycaproic acid (phthalimidoperoxyhexanoic acid, PAP), o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonylamidopersuccinates, and aliphatic and araliphatic peroxydicarboxylic acids such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperoxysebacic acid, diperoxybrassic acid, the diperoxyphthalic acids, 2-decyldiperoxybutane-1,4-diacid, N, N-terephthaloyl di (6-aminopercaproic acid) can be used. The agents according to the invention can particularly preferably contain phthalimidoperoxyhexanoic acid (PAP).

The bleaching agents may be coated to protect against premature degradation.

The agents of the invention may contain bleach activators.
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, especially triacetin, triethyl acetyl citrate (TEAC), 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 96/14769 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. Another class of preferred liquid bleach activators are the liquid imide bleach activators of the formula below,

The agents according to the invention may contain electrolytes.
As electrolytes from the group of inorganic salts, a wide number of different salts can be used. Preferred cations are the alkali and alkaline earth metals, preferred anions are the halides and sulfates. From a production point of view, the use of NaCl or MgCl ₂ in the agents according to the invention is preferred. The proportion of electrolytes in the inventive compositions is usually 0.5 to 5 wt .-%.

The agents according to the invention may contain pH adjusting agents.
To bring the pH of the inventive agent in the desired range, the use of pH adjusting agents may be indicated. Can be used here are all known acids or alkalis, unless their use is not for technical application or environmental reasons or for reasons of consumer protection prohibited. Usually, the amount of these adjusting agents does not exceed 2% by weight of the total formulation.

The compositions of the invention may contain dyes and perfumes.
Dyes and fragrances are added to the compositions according to the invention in order to improve the aesthetics of the products and to provide the consumer with a visually and sensory "typical and unmistakable" product in addition to the washing or cleaning performance. As perfume oils or fragrances, individual perfume compounds, for example the synthetic products of the ester type, ethers, aldehydes, ketones, alcohols and hydrocarbons can be used. Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalyl benzoate, benzylformate, ethylmethylphenylglycinate, allylcyclohexylpropionate, styrallylpropionate and benzylsalicylate. The ethers include, for example, benzyl ethyl ether, to the aldehydes, for example, the linear alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, lilial and bourgeonal, to the ketones such as the ionone, α-isomethylionone and methyl cedrylketone , the alcohols include anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons mainly include the terpenes such as limonene and pinene. Preferably, however, mixtures of different fragrances are used, which together produce an attractive fragrance. Such perfume oils may also contain natural fragrance mixtures as are available from vegetable sources, eg pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage, chamomile, clove, lemon balm, mint, cinnamon, lime, juniper, vetiver, olibanum, galbanum and labdanum, and orange blossom, neroliol, orange peel and sandalwood.

The agents according to the invention may contain UV absorbers.
The agents may contain UV absorbers which are applied to the treated fabrics and improve the light fastness of the fibers and / or the lightfastness of the other ingredients of the formulation. Under UV absorber are organic substances (sunscreen) to understand, which are able to absorb ultraviolet rays and the absorbed energy in the form of longer-wave radiation, eg heat to give back. Compounds having these desired properties include, for example, the non-radiative deactivating compounds and derivatives of benzophenone having substituents in the 2- and / or 4-position. In addition, substituted benzotriazoles, such as the water-soluble benzenesulfonic acid-3- (2H-benzotriazol-2-yl) -4-hydroxy-5- (methylpropyl) monosodium salt (Ciba ^® Fast H), phenyl-substituted in the 3-position acrylates (cinnamic acid derivatives) , optionally with cyano groups in the 2-position, salicylates, organic Ni complex and natural substances such as umbelliferone and the body's own urocanic acid suitable. Of particular importance are biphenyl and especially Stilbenderivate as described for example in the EP 0728749 A are described and commercially available as Tinosorb FD ^® or Tinosorb FR ^® are available ex Ciba. As IJV-B absorber are 3-Benzylidencampher or 3-Benzylidennorcampher and its derivatives, for example, 3- (4-methylbenzylidene) camphor, as in EP 0693471 B1 described; 4-aminobenzoic acid derivatives, preferably 2-ethylhexyl 4- (dimethylamino) benzoate, 2-octyl 4- (dimethylamino) benzoate and 4- (dimethylamino) benzoesäureamylester; Esters of cinnamic acid, preferably 4-methoxycinnamic acid 2-ethylhexyl ester, 4-methoxycinnamic acid propyl ester, 4-methoxycinnamic acid isoamyl ester, 2-cyano-3,3-phenylcinnamic acid 2-ethylhexyl ester (octocrylene); Esters of salicylic acid, preferably 2-ethylhexyl salicylate, 4-isopropylbenzyl salicylate, homomenthyl salicylate; Derivatives of benzophenone, preferably 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone; Esters of benzalmalonic acid, preferably di-2-ethylhexyl 4-methoxybenzmalonate, triazine derivatives such as 2,4,6-trianilino (p-carbo-2'-ethyl-1'-hexyloxy) -1,3,5-triazine and octyl Triazone, as in the EP 0818450 A1 or dioctyl butamido triazone (Uvasorb® HEB); Propane-1,3-diones such as 1- (4-tert-butylphenyl) -3- (4'-methoxyphenyl) propane-1,3-dione; Ketotricyclo (5.2.1.0) decane derivatives as described in U.S.P. EP 0694521 B1 described. Also suitable are 2-phenylbenzimidazole-5-sulfonic acid and its alkali metal, alkaline earth metal, ammonium, alkylammonium, alkanolammonium and glucammonium salts; Sulfonic acid derivatives of benzophenones, preferably 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its salts; Sulfonic acid derivatives of 3-Benzylidencamphers, such as 4- (2-oxo-3-bomylidenemethyl) benzenesulfonic acid and 2-methyl-5- (2-oxo-3-bomylidene) sulfonic acid and salts thereof. As a typical UV-A filter in particular derivatives of benzoylmethane are suitable, such as 1- (4'-tert-butylphenyl) -3- (4'-methoxyphenyl) propane-1,3-dione, 4-tert-butyl 4'-methoxydibenzoylmethane (Parsol 1789), 1-phenyl-3- (4'-isopropylphenyl) -propane-1,3-dione, and enamine compounds as described in U.S.P. DE 19712033 A1 (BASF). Of course, the UV-A and UV-B filters can also be used in mixtures. In addition to the soluble substances mentioned, insoluble photoprotective pigments, namely finely dispersed, preferably nano-metal oxides or salts, are also suitable for this purpose. Examples of suitable metal oxides are in particular zinc oxide and titanium dioxide and, in addition, oxides of iron, zirconium, silicon, manganese, aluminum and cerium and mixtures thereof. As salts silicates (talc), barium sulfate or zinc stearate can be used. The oxides and salts are already used in the form of the pigments for skin-care and skin-protecting emulsions and decorative cosmetics. The particles should have an average diameter of less than 100 nm, preferably between 5 and 50 nm and in particular between 15 and 30 nm. They may have a spherical shape, but it is also possible to use those particles which have an ellipsoidal or otherwise deviating shape from the spherical shape. The pigments can also be surface-treated, ie hydrophilized or hydrophobized. Typical examples are coated titanium dioxides, such as titanium dioxide T 805 (Degussa) or Eusolex® T2000 (Merck). Suitable hydrophobic coating agents are in particular silicones and in particular trialkoxyoctylsilanes or simethicones. Preferably, micronized zinc oxide is used. Further suitable UV light protection filters can be found in the review by P. Finkel in SÖFW Journal 122, 543 (1996).
The UV absorbers are usually used in amounts of from 0.01% by weight to 5% by weight, preferably from 0.03% by weight to 1% by weight.

The compositions of the invention may contain wrinkle inhibitors.
Since fabrics, in particular of rayon, wool, cotton and their blends, may tend to wrinkle because the individual fibers are susceptible to flexing, buckling, squeezing and squeezing across the grain, the compositions may contain synthetic crease inhibitors. These include, for example, synthetic products based on fatty acids, fatty acid esters, fatty acid amides, -alkylolestem, -alkylolamiden or fatty alcohols, which are usually reacted with ethylene oxide, or products based on lecithin or modified phosphoric acid ester.

The agents according to the invention may contain grayness inhibitors.
Grayness inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the dirt from being rebuilt. Water-soluble colloids of mostly organic nature are suitable for this purpose, for example glue, gelatine, salts of ether sulfonic acids or cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Also, water-soluble polyamides containing acidic groups are suitable for this purpose. It is also possible to use soluble starch preparations and starch products other than those mentioned above, for example degraded starch, aldehyde starches etc. Polyvinylpyrrolidone is also useful. However, preferred are cellulose ethers such as carboxymethyl cellulose (Na salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as methylhydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose.

In a particularly preferred embodiment, the nonaqueous liquid detergents according to the invention are present as a portion in a completely or partially water-soluble coating. The non-aqueous liquid detergent granules facilitate the dosability of the consumer.

The nonaqueous liquid detergents can be packed in foil bags, for example. Film bags made of water-soluble film make it unnecessary for the consumer to tear open the packaging. In this way, a convenient dosing of a single, sized for a wash portion by inserting the bag directly into the washing machine or by inserting the bag into a certain amount of water, for example in a bucket, a bowl or in Handwasch- or -spülbecken, possible. The film bag surrounding the washing portion dissolves without residue when it reaches a certain temperature. Laundry detergents also packaged in bags of water-soluble film are described in large numbers in the prior art. Thus, the older patent application discloses DE 198 31 703 a portioned detergent or cleaner composition in a bag of water-soluble film, in particular in a bag of (optionally acetalized) polyvinyl alcohol (PVAL), wherein at least 70 % By weight of the particles of the detergent or cleaner preparation have particle sizes> 800 μm.

Numerous processes for the preparation of water-soluble detergent portions which are included in the context of this application already exist in the prior art. The best known methods are the tubular film processes with horizontal and vertical sealing seams. Further suitable for the production of film bags or dimensionally stable detergent portions is the Thermoformverrfahren, as for example in the WO-A1 00/55068 is described. The water-soluble sheathings need not necessarily consist of a film material, but can also represent dimensionally stable containers that can be obtained for example by means of an injection molding process.

A known method for producing water-soluble Spritzgußhohlkörpem containing detergents and / or cleaning agents is, for example, in the WO-A1 01/36290 described.

Furthermore, the prior art discloses processes for preparing water-soluble capsules of polyvinyl alcohol or gelatin, which in principle offer the possibility of providing capsules with a high degree of filling. The methods are based on introducing the water-soluble polymer into a shaping cavity. The filling and sealing of the capsules takes place either synchronously or in successive steps, in which case the filling takes place through a small opening in the latter case. Processes in which the filling and sealing is parallel, for example, in WO 97/35537 described. The filling of the capsules is carried out by a Befkekeif, which is above two mutually rotating drums having on their surface Kugeihaibschalen arranged. The drums carry polymer bands that cover the ball half-shell cavities. At the positions where the polymer band of one drum coincides with the polymer tape of the opposite drum, a seal takes place. In parallel, the filling material is injected into the forming capsule, wherein the injection pressure of the filling liquid presses the polymer bands in the Kugelhalbschalenkavitäten.

A process for producing water-soluble capsules in which first the filling and then the sealing is carried out in the WO 01/64421 disclosed. The manufacturing process is based on the so-called Bottle-Pack ^® method, as for example in the German Offenlegungsschrift DE 14 114 69 is described. In this case, a tubular preform is guided into a two-part cavity. The cavity is closed, the lower tube portion is sealed, then the tube is inflated to form the capsule shape in the cavity, filled and finally sealed.

The shell material used for the preparation of the water-soluble portion is preferably a water-soluble polymeric thermoplastic, more preferably selected from the group (optionally partially acetalized) polyvinyl alcohol, polyvinyl alcohol copolymers. Polyvinylpyrrolidone, polyethylene oxide, gelatin, cellulose and derivatives thereof, starch and derivatives thereof, blends and composites, inorganic salts and mixtures of said materials, preferably hydroxypropylmethylcellulose and / or polyvinylalcohol blends.

The polyvinyl alcohols described above are commercially available, for example under the trademark Mowiol® ^® (Clariant). In the present invention, particularly suitable polyvinyl alcohols are, for example, Mowiol ^® 3-83, Mowiol ^® 4-88, Mowiol ^® 5-88, Mowiol ^® 8-88 and Clariant L648.

Further polyvinyl alcohols which are particularly suitable as material for the hollow bodies are shown in the following table: description Degree of hydrolysis [%] Molecular weight [kDa] Melting point [° C] Airvol ^® 205 88 15-27 230 Vinex ^® 2019 88 15-27 170 Vinex ^® 2144 88 44 - 65 205 Vinex ^® 1025 99 15-27 170 Vinex ^® 2025 88 25 - 45 192 Gohsefimer ^® 5407 30 - 28 23,600 100 Gohsefimer ^® LL02 41 - 51 17,700 100

Other suitable as a material for the sheath are polyvinyl alcohols ^® ELVANOL 51-05, 52-22, 50-42, 85-82, 75-15, T-25, T-66, 90-50 (trademark of Du Pont), ALCOTEX ^® 72.5, 78, B72, F80 / 40, F88 / 4, F88 / 26, F88 / 40, F88 / 47 (trademark of Harlow Chemical Co.), Gohsenol ^® NK-05, A-300, AH-22, C -500, GH-20, GL-03, GM-14L, KA-20, KA-500, KH-20, KP-06, N-300, NH-26, NM11Q, KZ-06 (Trademark of Nippon Gohsei KK ).

The water-soluble thermoplastic used to prepare the portion according to the invention may additionally comprise polymers selected from the group comprising acrylic acid-containing polymers, polyacrylamides, oxazoline polymers, polystyrene sulfonates, polyurethanes, polyesters, polyethers and / or mixtures of the above polymers.

It is preferred if the water-soluble thermoplastic used comprises a polyvinyl alcohol whose degree of hydrolysis makes up 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol%.

More preferably, the water-soluble thermoplastic used comprises a polyvinyl alcohol whose molecular weight is in the range of 10,000 to 100,000 gmol ^-1 , preferably 11,000 to 90,000 gmol ^-1 , more preferably 12,000 to 80,000 gmol ^-1 and especially 13,000 to 70,000 gmol ^-1 lies.

Further preferred is when the thermoplastics in amounts of at least 50 wt .-%, preferably of at least 70 wt .-%, more preferably of at least 80 wt .-% and in particular of at least 90 wt .-%, each based on the weight the water-soluble polymeric thermoplastic.

The polymeric thermoplastics may be plasticized to improve their machinability, i. Plasticizer, included. This may be advantageous in particular if polyvinyl alcohol or partially hydrolyzed polyvinyl acetate has been chosen as the polymer material for the portion. Glycerol, triethanolamine, ethylene glycol, propylene glycol, diethylene or dipropylene glycol, diethanolamine and methyldiethylamine have proved particularly suitable as plasticizing auxiliaries.

Another object of the invention is the use according to claim 31.

Another object of the invention is the use of a liquid textile cleaning agent or a mild detergent or a liquid detergent according to the invention or a non-aqueous liquid detergent according to the invention to reduce linting and / or reduce the pilling of textile fabrics.

Another object of the invention is a method for reducing the linting of textile fabrics by contacting textile sheets with a liquid laundry detergent or a fine detergent or a liquid detergent according to the invention or a nonaqueous liquid detergent according to the invention in a textile cleaning process.

The compositions of the invention are prepared by simple, familiar to the expert, mixing together and stirring of the individual components.

Examples

Liquid detergents according to the invention are, for example, E1 whose compositions are reproduced in Table 1. <b> Table 1 </ b> raw material E1 E2 E3 APG 600 ^[a] 1.5 --- --- Defoamers ^[b] 0.03 0.03 0.03 glycerin 5.0 --- --- diethylene glycol 0.5 --- --- Propylene-1,2-glycol --- 5 5 ethanol --- 2.5 2.3 Texapon N70 ^[c] 5 5 5 Dehydrol LT7 ^[d] 12 13 12 boric acid 0.25 1 1 sodium 1.5 --- --- Sodium Citrate x 2 H ₂ O --- 2 4 sodium hydroxide 0.85 0.85 1.5 lauric acid 3 3 6 oleic acid 1.5 1.5 2.4 ricinoleate 0.5 0.5 --- Acusol 820 ^[e] 0.2 --- --- Dequest 2066 ^[f] 0.5 0.5 0.03 polyvinylpyrrolidone 0.1 0.1 0.4 protease 0.4 0.4 0.4 amylase --- 0.1 0.1 Perfume 0.7 0.7 0.7 Arbocel ^® BE 600-10 ^[g] 5.0 3.5 1.5 water ad 100 ad 100 ad 100 ^[a] C _12-16 fatty alcohol-1,4-glucoside
^[b] dimethylpolysiloxane-emulsifier mixture ex Dow
^[c] _12-14 C -Ethefsulfat with 2 EO ex Cognis
^[d] C _12-18 -Fottalkohol + 7 EO ex Cognis
^[e] methacrylic acid (stearyl alcohol-20-EO) ester-acrylic acid copolymer ex Cognis
^[f] Diethylenetriaminepentamethylenephosphonic acid Na salt ex Monsanto
^[g] microcrystalline cellulose (average fiber length: 18 μm) ex Rettenmaier

Table 2 shows the formulation of the mild detergent E4 according to the invention. <b> Table 2 </ b> raw material E4 APG 600 2.5 ethylene glycol 0.3 ethanol 0.37 Cetylstearylalkoholsulfat Na salt 0.47 Dehydrol LT7 14.0 Stepantex VA90 ^[h] 2.5 citric acid 0.05 cellulase 0.04 Perfume 0.7 Cellulon® ^[k] 0.5 water ad 100 ^[h] N-Methyl-N (2-hydroxyethyl) -N, N- (ditallowacyloxyethyl) -ammonium methosulfate ex Stepan
^[k] biotechnologically produced microcellulose ex Kelco

Table 3 shows a nonaqueous liquid detergent E5 according to the invention. <b> Table 3 </ b> raw material E5 glycerin 1 ethanol 3.3 C12-14 fatty alcohol + EO + PO 22.5 Dodecylbenzenesulfonic-isopropylamine salt 24.5 C _12-18 fatty acid 17.5 Dequest 2066 0.6 Monoethanolamine 4.9 protease 1 amylase 0.2 cellulase 0.06 water 6 Perfume 0.25 dye + Arbocel ^® BE 600-10 ^[9] 5.0 propylene glycol ad 100

The inventive compositions E1 to E5 showed a reduced linting and pilling compared to non-inventive agents that did not contain lint reduction component.

Claims (34)

1. A liquid textile cleaning agent, containing at least one lint-reducing component, which is a microcrystalline cellulose, preferably a microcrystalline cellulose resulting from a microbiological fermentation process, wherein the microcrystalline cellulose is chosen from the group consisting of microcrystalline celluloses, which could be obtained on 10 April 2002 under the references Arbocel® BE 600-10, Arbocel® BE 600-20 and Arbocel® BE 600-30 ex Rettenmaier and Cellulon® ex Kelco, and at least 90% of the particles of the lint-reducing component having a particle size smaller than 100 µm, and nonionic surfactants.
2. An agent according to claim 1, characterised in that at least 90% of the particles have a particle size smaller than 50 µm, particularly preferably smaller than 20 µm.
3. An agent according to claim 1 or claim 2, characterised in that the content of the lint-reducing component amounts to 0.005 to 15 wt.%, preferably 0.01 to 10 wt.%, particularly preferably 0.1 to 7 wt.% and in particular 0.5 to 5 wt.%, in each case relative to the total agent.
4. An agent according to any one of claims 1 to 3, characterised in that it contains as nonionic surfactants alkoxylated fatty alcohols, preferably ethoxylated and/or propoxylated fatty alcohols.
5. An agent according to any one of claims 1 to 4, characterised in that it contains anionic surfactants, preferably selected from the group of fatty alcohol sulfates and/or fatty alcohol ether sulfates and/or alkylbenzene sulfonates and/or soaps.
6. An agent according to any one of claims 1 to 5, characterised in that it contains complexing agents.
7. An agent according to any one of claims 1 to 6, characterised in that it contains enzymes, preferably selected from the group comprising proteases and/or amylases and/or cellulases.
8. An agent according to any one of claims 1 to 7, characterised in that it exhibits a viscosity of 50 to 5000 mPa·s, particularly preferably of 50 to 3000 mPa·s and in particular of 500 to 1500 mPa·s (measured at 20°C with a rotational viscometer (Brookfield RV, spindle 2) at 20 rpm).
9. A washing agent for delicate textiles according to any one of claims 1 to 8, characterised in that it additionally contains at least one softener component.
10. A washing agent for delicate textiles according to claim 9, characterised in that it contains as softener component cationic surfactants, preferably alkylated quaternary ammonium compounds, of which at least one alkyl chain is interrupted by an ester group and/or amido group, in particular N-methyl-N(2-hydroxyethyl)-N, N-(ditallowacyloxyethyl)ammonium methosulfate or N-methyl-N(2-hydroxyethyl)-N,N-(dipalmitoylethyl)-ammonium methosulfate.
11. A washing agent for delicate textiles according to either of claim 9 or claim 10, characterised in that it contains the softener component in a quantity of up to 15 wt.%, preferably of 0.1 to 10 wt.%, particularly preferably of 0.5 to 7 wt.% and in particular of 1 to 3 wt.%, in each case relative to the total agent.
12. A washing agent for delicate textiles according to any one claims 9 to 11, characterised in that it contains cellulase preferably in a quantity of 0.005 to 2 wt.%, particularly preferably of 0.01 to 1 wt.%, in particular of 0.02 to 0.5 wt.%, in each case relative to the total agent.
13. A washing agent for delicate textiles according to any one of claims 9 to 12, characterised in that it contains nonionic surfactants selected from the group comprising alkoxylated fatty alcohols and/or alkyl glycosides.
14. A washing agent for delicate textiles according to claim 13, characterised in that it contains the nonionic surfactants in quantities of up to 30 wt.%, preferably of 5 to 25 wt.%, particularly preferably of 10 to 20 wt.%, in each case relative to the total agent.
15. A washing agent for delicate textiles according to any one claims 9 to 14, characterised in that it contains anionic surfactants in quantities of below 10 wt.%, preferably of below 5 wt.% and in particular of below 1 wt.%, in each case relative to the total agent.
16. A washing agent for delicate textiles according to any one of claims 9 to 15, characterised in that it additionally contains a pearlescent agent.
17. A washing agent for delicate textiles according to any one of claims 9 to 16, characterised in that it contains up to 95 wt.%, particularly preferably 20 to 90 wt.% and in particular 50 to 80 wt.% of one or more solvents, preferably water-soluble solvents, and in particular water.
18. A liquid washing agent according to any one claims 1 to 8, characterised in that it contains anionic surfactants in quantities of up to 30 wt.%, preferably of up to 25 wt.%, particularly preferably of 5 to 20 wt.%, in particular of 8 to 15 wt.%, in each case relative to the total agent.
19. A liquid washing agent according to claim 18, characterised in that it contains the nonionic surfactants in quantities of up to 30 wt.%, preferably of 5 to 20 wt.%, in particular of 10 to 15 wt.%, in each case relative to the total agent.
20. A liquid washing agent according to either of claim 18 or claim 19, characterised in that it contains up to 90 wt.%, particularly preferably 20 to 85 wt.% and in particular 50 to 80 wt.% of one or more solvents, preferably water-soluble solvents, and in particular water.
21. A liquid washing agent according to any one claims 18 to 20, characterised in that it additionally contains thickeners, preferably in quantities of up to 10 wt.%, particularly preferably of up to 5 wt.%, in particular of 0.1 to 1 wt.%, in each case relative to the total agent.
22. A liquid washing agent according to any one of claims 18 to 21, characterised in that it contains enzyme, preferably protease and/or amylase.
23. A liquid washing agent according to any one of claims 18 to 22, characterised in that it contains additives selected from the group comprising odour absorbers and/or dye transfer inhibitors.
24. A non-aqueous liquid washing agent according to any one claims 1 to 8, characterised in that it comprises surfactants in a quantity of up to 35 wt.%, preferably of 15 wt.% to 25 wt.%, in each case relative to the total agent.
25. A non-aqueous liquid washing agent according to claim 24, characterised in that it contains anionic surfactants in quantities of up to 60 wt.%, preferably of 20 to 50 wt.%, in particular of 30 to 45 wt.%, in each case relative to the total agent.
26. A non-aqueous liquid washing agent according to either of claim 24 or claim 25, characterised in that the total surfactant content, without the quantity of fatty acid soap, is below 55 wt.%, preferably below 50 wt.%, in each case relative to the total agent.
27. A non-aqueous liquid washing agent according to any one claims 24 to 26, characterised in that it contains organic solvents in quantities of up to 50 wt.%, preferably of up to 45 wt.%, in particular of 20 to 40 wt.%, in each case relative to the total agent.
28. A non-aqueous liquid washing agent according to any one of claims 24 to 27, characterised in that it contains enzymes, preferably selected from the group comprising proteases and/or amylases and/or cellulases.
29. A non-aqueous liquid washing agent according to any one of claims 24 to 28, characterised in that it assumes the form of a portion in a wholly or partially water-soluble casing.
30. A non-aqueous liquid washing agent according to claim 29, characterised in that the wholly or partially water-soluble casing contains one or more materials selected from the group comprising (optionally partially acetalised) polyvinyl alcohol, polyvinyl alcohol copolymers, polyvinylpyrrolidone, polyethylene oxide, gelatine, cellulose and the derivatives thereof, starch and the derivatives thereof, blends and composites, inorganic salts and mixtures of the stated materials, preferably hydroxypropylmethylcellulose and/or polyvinyl alcohol blends.
31. Use of a microcrystalline cellulose, preferably a microcrystalline cellulose resulting from a microbiological fermentation process, wherein the microcrystalline celluloses are chosen according to claim 1, and at least 90% of the particles of the microcrystalline cellulose having a particle size smaller than 100 µm, in a liquid textile cleaning agent containing nonionic surfactants to reduce linting.
32. Use of a liquid textile cleaning agent according to any one of claims 1 to 8 or of a washing agent for delicate textiles according to any one of claims 9 to 17 or of a liquid washing agent according to any one of claims 18 to 23 or of a non-aqueous liquid washing agent according to any one of claims 24 to 30 to reduce the linting of textile fabric.
33. Use of a liquid textile cleaning agent according to any one of claims 1 to 8 or of a washing agent for delicate textiles according to any one of claims 9 to 17 or of a liquid washing agent according to any one of claims 18 to 23 or of a non-aqueous liquid washing agent according to any one of claims 24 to 30 to reduce the pilling of textile fabric.
34. A method of reducing the linting of textile fabric by bringing textile fabric into contact with a liquid textile cleaning agent according to any one of claims 1 to 8 or a washing agent for delicate textiles according to any one of claims 9 to 17 or a liquid washing agent according to any one of claims 18 to 23 or a non-aqueous liquid washing agent according to any one of claims 24 to 30 in a textile cleaning process.