DE10016424A1 - Liquid detergent with polyamide - Google Patents

Abstract

The use of polyamides, which are activated by structural activators, leads to an improvement of the rheological properties or, in addition, to an improved prevention of sedimentation of suspended particles in liquid washing and cleaning agents and other fluidic to highly viscous media such as cosmetics, adhesives, paints, varnishes, enamels, waxes, varnish removers, oil drilling fluids, lubricants, inks, polyester resins, epoxy resins, and sealants. To this end, the invention relates to activated polyamides and to a method for the production thereof. The invention particularly relates to liquid washing and cleaning agents containing such activated polyamides and to a method for producing said agents.

Description

The invention relates to the use of activated polyamide derivatives as a rheological additive, the provision of activated polyamide derivatives and a process for the production of activated Polyamides using structural activators. Furthermore, the invention relates to liquid washing or cleaning agents that contain activated polyamides, and a method for producing them such means.

The rheology of liquid systems is of great importance for many areas of technology. Around the viscosity behavior of fluid components, such as. B. gels and pastes, on the respective rheological additives, in particular, can set application-specific requirements Thixotropic agents can be incorporated into existing liquid systems. Known representatives These additives are layered silicates and castor oil derivatives, which are produced using certain processes activated and thus made usable as a thixotropic agent. The most important rheological behaviors of viscous materials are pseudoplastic, thixotropic, dilated and Newtonian flow. They result from the different dependencies the viscosity from the shear rate. With pseudoplastic flow, the Viscosity decreases with increasing shear rate. This is the case with thixotropic flow also the case, here the shear rate decreases with subsequent decrease Viscosity increases again, but this process is time-dependent and may be reached It was only much later that the values returned that were the same shear rates before shearing corresponded. Dilatant flow denotes the increase in viscosity with increasing Shear rate, while in Newtonian flow the viscosity is independent of the Shear rate remains constant. Especially pseudoplastic or thixotropic flow is Often desired for viscous materials, as they are used for storage and transport where low until low shear forces act, are more viscous and when used or processed where higher shear forces act, are less viscous and therefore easy to pour and process.  

The use of different thickening systems to build structured and thixotropic Liquid matrices are described in various patent applications.

WO 99/00483 describes the use of castor oil derivatives in non-aqueous Liquid detergents. The derivatives are activated by a high shear stress and are in activated form able to build up a structured gel phase, which in turn forms the basis for a stable dispersion of surfactants and incorporated solids.

WO 98/00518 describes non-aqueous liquid detergents which, in addition to polycarboxylates and Polyvinylpyrrolidones can also contain polyamide resins as a thickening system. Leave it to produce stable detergent suspensions containing solids.

The use of polyamides and polyamide derivatives as rheological additives is also described.

European patent application EP 582 363 A2 discloses polyamide esters which are known as rheological Additives can be used in paints and varnishes. The additives prevent this Decrease in dye pigments and improve the rheological properties of the Paint dispersions. Without activators, however, the non-activated polyamide derivatives showed worsened rheological effect, lower viscosity and reduced control of the Sinking of dispersed particulate ingredients, also an undesirably high Consistency that adversely affects the originally desired rheological properties subsequent shear (e.g. casting).

An object of the invention was to activate activated polyamide derivatives as rheological To provide additives in liquid, fluid or highly viscous media improved rheological properties, desired pseudoplastic or thixotropic flow or reduced tendency to decrease the dispersed in the gel phase Cause solid particles.

An additional object of the invention was to provide a method for activating such To develop polyamide derivatives.

Another object of the invention was to provide an activated polyamide derivative containing liquid detergent or cleaning agent, the improved rheological Properties, desired pseudoplastic or thixotropic flow and good physical storage stability of solids customary in detergent formulations, such as  Bleaching agents, bleach activators, enzymes, optical brighteners, inorganic and organic builders, etc.

Another object of the invention was to provide a method for producing such to develop liquid detergents or cleaning agents.

It has been found that by activating polyamide derivatives with structural activators, rheological additives are created which can be used in a wide variety of media Build thixotropic or pseudoplastic fluid systems that lead to increasing Shear shows a decrease in viscosity.

The invention therefore relates to the use of Polyamide derivatives that are activated by at least one structural activator as rheological Additive in liquid washing or cleaning agents and other fluid to highly viscous Media such as cosmetics, adhesives, enamel, waxes, paint removers, oil drilling fluids, greases, Inks.

In another embodiment, the invention relates to the use of Polyamide derivatives which are selected by at least one structural activator from the group of Carboxylic acid derivatives and the organic carbonic acid ester and any mixtures of these with itself and other activators from the group of liquid alcohols and aromatics, are activated as a rheological additive in liquid to highly viscous polyester resins, Epoxy resins, sealants, paints and varnishes.

All natural and artificial polyamides can be used as polyamide derivatives, in particular polyamide ester compounds, as disclosed in EP 528 363 and on which is explicitly referred to in this application.

The preferred polyamide ester compounds originate from the reaction product Polycarboxylic acids, an active hydrogen compound, an alkoxylated compound with active hydrogen and a monocarboxylic acid.

The polycarboxylic acids have between 5 and 36 carbon atoms per carboxylic acid group. Preferred polycarboxylic acids are those in which the number of carboxylic acid groups is two. Due to the manufacturing process, however, mixtures are often used that also contain substances with only a carboxylic acid group and / or three or more carboxylic acid groups. Especially  those polycarboxylic acids are preferred, the dimeric and oligomeric units more natural Form fatty acids.

Compounds with active hydrogen follow the general formula: X _m -RY _n , in which R represents a group with 2 to 12 carbon atoms, which may also contain non-reactive groups such as ether, alkoxy or halogen. X and Y are independent of one another and can be primary and secondary amino and hydroxyl groups. The variables m and n are at least 1 and the sum (m + n) is at least 2.

The alkoxylated compound with active hydrogen is a polyether segment with at least 2 active hydrogen atoms. The active hydrogen alkoxylated compound must have an active amino or hydroxy group at each end of the polyether chain, and / or one end of the polyether chain is attached to a molecular fragment with at least one additional amino or hydroxy group and / or a linked polyether chain. This definition therefore includes not only polyalkylene glycols, polyalkylene diols or polyoxyethylenes with terminal amino groups, but also compounds of the following formula:

R ¹ : linear or branched alkyl chain with 6 to 30 carbon atoms
R: H, methyl or ethyl
q, r: at least 1 and the sum (q + r) is from 2 to 50.
s: 0 or 1

Alkoxylated substances with 3 or more active hydrogen atoms can also be present. An example of this is represented by the following formula:

R ³ , R ² : independently of one another linear or branched alkyl chain with 6 to 30 carbon atoms
p: 1 to 20
x, y, z: independently of one another 0 or greater than 0, the sum of x + y + z ranging from 1 to 50.

The monocarboxylic acid is used to make the reaction from the polycarboxylic acids with the active ones Hydrogen-bearing substances (alkoxylated and non-alkoxylated) to quit. The Monocarboxylic acids have between 2 and 22 carbon atoms and can both be saturated be unsaturated as well. You can also add other functional groups such as wear tert-amino, alkoxy, halo, keto, etc. However, preference is given to those monocarboxylic acids which carry hydroxyl groups and / or are unsaturated.

The polyamide esters are produced using known techniques, such as those used in the EP 528 363 A2 can be described. For example, the individual components in one Reaction vessel, which with a mechanical stirrer, a thermometer, a cooler and provided with a nitrogen inlet. The reaction vessel can be heated, the reaction mixture being stirred under a nitrogen atmosphere can be. The end of the reaction is based on the acid number (preferably less than 20) certainly. The polyamide ester is cooled and optionally ground. Preferably those that are commercially available, for example from Rheox, can be used Polyamide derivatives Thixatrol TSR, Thixatrol SR 100, Thixafrol SR and in particular thixafrol Plus.

To prevent the settling of dispersed solids and to regulate the viscosity Suitable polyamide derivatives should be selected depending on the polarity of the fluid system.

Structural activators generally improve the gel formation of the polyamide derivatives. In many cases, such a chemical activator is helpful to create a structured liquid matrix build up in which solid particles can be dispersed. Suitable as structure activators aromatics and aliphatic alcohols such as ethanol, propan-1-ol, Propan-2-ol, butan-1-ol, butan-2-ol, isobutanol, isoamyl alcohol, cyclohexanol, glycol, propane or butanediol, glycerol, diglycol, propyl or butyl diglycol, 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, dipropylene glycol monomethyl, or - ethyl ether, di-isopropylene glycol monomethyl or ethyl ether, methoxy, ethoxy or Butoxytriglycol, 1-butoxyethoxy-2-propanol, butoxypropoxy propanol (BPP), 3-methyl-3- methoxybutanol, propylene glycol t-butyl ether and mixtures thereof. Preferred Structure activators are liquid carboxylic acid and carbonic acid derivatives, in which the Ratio of oxygen to carbon per structural activator molecule in the range from 3: 1 to 1: 3, preferably from 3: 2 to 2: 5 and in particular from 1: 1 to 1: 2. Particularly preferred Liquid carboxylic acid derivatives are the carboxylic acid esters and anhydrides, in particular one or multi-acetylated compounds such as triethylacetyl citrate, triethyl citrate, Ethylene glycol diacetate and glycerol triacetate. Particularly preferred liquid carbonic acid derivatives are the linear and in particular cyclic carbonic acid esters, such as that Propylene carbonate and the glycerine carbonate.

The structure activators can of course also be mixed with themselves in any mixtures or other organic solvents, such as ketones, aldehydes, ethers, Polyethers, nitriles, aliphatics, halogenated hydrocarbons, amines, carboxylic acids and surfactants be used.

The structure activators are used in amounts so that the weight ratio of Structure activators for polyamide derivative from 500: 1 to 1: 500, preferably from 50: 1 to 1:50, is particularly preferably from 20: 1 to 1:20 and in particular from 10: 1 to 1:10.

A preferred area of application of the activated polyamide derivatives is liquid washing or Detergents, especially those that are non-aqueous. Under the term In the context of the present invention, “non-aqueous” means agents that are only minor Amounts of free water that is not bound as water of crystallization or otherwise bound contain. Since even non-aqueous solvents and raw materials (especially those technical Qualities) have certain water contents, are completely anhydrous agents in the industrial scale can only be produced with great effort and high costs. In the "Non-aqueous" agents of the present invention can thus contain small amounts of free Contain water that are below 5 wt .-%, preferably below 2 wt .-%, each based on the finished means.  

These agents can preferably contain solids, which are usually in washing or Cleaning agents are used, such as bleach, bleach activators, enzymes, optical Brighteners, UV absorbers, inorganic and organic builders, etc., through the use of activated polyamide derivatives are advantageously physically stabilized. The liquid Detergents or cleaning agents are explained in more detail below.

In a further embodiment, the invention relates to polyamide derivatives which pass through at least one structural activator selected from the group of carboxylic acid derivatives and organic carbonic acid esters and any mixtures of these with themselves and others Activators from the group of liquid alcohols and aromatics, are activated, the Weight ratio of structure activators to polyamide derivative advantageously from 500: 1 to 1: 500, preferably from 50: 1 to 1:50, particularly preferably from 20: 1 to 1:20 and in particular from 10: 1 to 1:10. The polyamide derivatives and structural activators and their respective preferred embodiments are described above.

In another embodiment, the invention relates to a method for the production of activated polyamide derivatives, the structure activators selected from the group of Carboxylic acid derivatives and the organic carbonic acid ester and any mixtures of these with itself and other activators from the group of liquid alcohols and aromatics and where the are optionally different from the structural activators Solvents or solvent mixtures and / or surfactants dispersed polyamide derivatives with the structural activators under shear, preferably in a highly dispersing device with strong shear, can be mixed.

The polyamide derivatives according to the invention and used according to the invention are mixed with the structure activators also described there, selected from the group of Carboxylic acid derivatives and the organic carbonic acid ester and any mixtures of these with itself and other activators from the group of liquid alcohols and aromatics, optionally in the presence of one or more surfactants and / or solvents, which of the structure activators are different, mixed. In a preferred embodiment these are liquid surfactants. In a particularly preferred embodiment are non-ionic surfactants, and possibly other solvents that do not Structure activators are anionic surfactants, cationic surfactants, amphoteric surfactants and / or other detergent ingredients used.  

Possible nonionic surfactants are preferably alkoxylated, advantageously ethoxylated and / or propoxylated, in particular primary alcohols with 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. Particularly preferred are 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, with a degree of ethoxylation 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 can preferably be linearly or particularly preferably methyl-branched in the 2-position or contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. In particular, however, alcohol ethoxylates with linear residues from alcohols of native origin with 12 to 18 carbon atoms, for. B. from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol preferred. The preferred ethoxylated alcohols include, for example, C _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 thereof, such as mixtures of C _12-14 alcohol with 3 EO and C _12-18 alcohol with 5 EO. The degrees of ethoxylation and propoxylation given represent statistical averages, which can be an integer or a fraction for a specific 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, especially primary and secondary amines with preferably 1 to 18 carbon atoms per alkyl chain and on average 1 to 12 moles of ethylene oxide (EO) and / or 1 to 10 moles Propylene oxide (PO) per mole of amine.

In addition, as further nonionic surfactants, alkyl glycosides of the general formula R ⁴ O (G) _x , e.g. B. as compounds, especially with anionic surfactants, in which R ^{4 is} a primary straight-chain or methyl-branched, in particular in the 2-position methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 C atoms and G is the symbol, which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.

Another class of preferred nonionic surfactants, either as the sole nonionic surfactant or used in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated Fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular Fatty acid methyl esters, as described, for example, in Japanese patent application JP 58/217598 are described or which are preferably according to the WO- in the international patent application A-90/13533 described processes can be produced.

Also nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N- dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the Fatty acid alkanolamides can be suitable.

So-called gemini surfactants can be considered as further surfactants. Below are in generally understood such compounds, the two hydrophilic groups and two have hydrophobic groups per molecule. These groups are usually by one so-called "spacers" separated from each other. This spacer is usually one Carbon chain, which should be long enough that the hydrophilic groups have a sufficient Have a distance so that they can act independently of each other. Draw such surfactants is characterized by an unusually low critical micelle concentration and the Ability to greatly reduce the surface tension of the water. In exceptional cases However, under the term Gemini surfactants, not only are dimers but also trimeric Understood 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 tris sulfates and ether sulfates according to international patent application WO-A-96/23768. End group capped dimeric and trimeric mixed ethers according to the German Patent application DE-A-195 13 391 are particularly characterized by their bi- and Multifunctionality. For example, the end group-closed surfactants mentioned have good ones Network properties and are low-foaming, so that they are particularly suitable for use in machine washing or cleaning processes.  

Gemini polyhydroxy fatty acid amides or poly Polyhydroxy fatty acid amides, as described in international patent applications WO-A-95/19953, WO-A-95/19954 and WO-A-95/19955 can be described.

Other suitable surfactants are polyhydroxy fatty acid amides of the following formula,

in which R ⁶ CO for an aliphatic acyl radical with 6 to 22 carbon atoms, R ⁵ for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups stands. 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.

The group of polyhydroxy fatty acid amides also includes compounds of the following formula

in which R ⁷ for a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ⁸ for a linear, branched or cyclic alkyl radical or an aryl radical with 2 to 8 carbon atoms and R ⁹ for a linear, branched or cyclic alkyl radical or Aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, C _1-4 alkyl or phenyl radicals being preferred and [Z ¹ ] representing 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 ¹ ] 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 converted, for example according to the teaching of international application WO-A-95/07331, into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.

Anionic surfactants used are, for example, those of the sulfonate and sulfate type. The surfactants of the sulfonate type are preferably C _9-13 -alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates such as are obtained, for example, from C _12-18 monoolefins having an end or internal double bond by sulfonating with gaseous Sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products is considered. Also suitable are alkanesulfonates obtained from C _12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. Likewise, the esters of α-sulfofatty acids (ester sulfonates), e.g. B. the α-sulfonated methyl ester of hydrogenated coconut, palm kernel or tallow fatty acids.

Other suitable anionic surfactants are sulfonated fatty acid glycerol esters. Under Fatty acid glycerol esters are to be understood as the mono-, di- and triesters and their mixtures, as in the preparation by esterification of a monoglycerol with 1 to 3 mol Obtained fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol become. Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated ten fatty acids with 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) yl sulfates are the alkali and in particular the sodium salts of the sulfuric acid half esters of C ₁₂ -C ₁₈ fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁₀ -C ₂₀ oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical prepared on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials. The C ₁₂ -C ₁₆ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates as well as C ₁₄ -C ₁₅ alkyl sulfates are preferred from the point of view of washing technology. 2,3-Alkyl sulfates, which are produced, for example, according to US Pat. Nos. 3,234,258 or 5,075,041 and can be obtained as commercial products from the Shell Oil Company under the name DAN®, are also suitable anionic surfactants.

The sulfuric acid monoesters of the straight-chain or branched C _7-21 alcohols ethoxylated with 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C _9-11 alcohols with an average of 3.5 mol of ethylene oxide (EO) or C _12-18 - Fatty alcohols with 1 to 4 EO are suitable. Because of their high foaming behavior, they are used in cleaning agents only in relatively small amounts, for example in amounts of 1 to 5% by weight.

Other suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contain C _8-18 fatty alcohol residues or mixtures thereof. Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which are nonionic surfactants in themselves. Again, sulfosuccinates, the fatty alcohol residues of which are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are particularly preferred. It is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.

Soaps are particularly suitable as further anionic surfactants. Are suitable saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearin säuxe, hydrogenated erucic acid and behenic acid and in particular from natural fatty acids, e.g. B. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.

The anionic surfactants including the soaps can 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 in the form of their sodium or potassium salts, especially in the form of the sodium salts.  

Another class of anionic surfactants is the class of ether carboxylic acids and their salts, which are accessible by reacting 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 sensitive and have excellent properties Surfactant properties. Production and application are, for example, in soaps, oils, fats, waxes 101, 37 (1975); 115, 235 (1989) and Tenside Deterg. 25, 308 (1988).

Cationic surfactants contain the high molecular weight hydrophobic residue that causes surface activity when dissociated in aqueous solution in the cation. The most important representatives of the cationic surfactants are the quaternary ammonium compounds of the general formula: (R ¹ R ² R ³ R ⁴ N ⁺ ) X ^- . R ₁ stands for C ₁ -C ₈ -alk (en) yl, R ² to R ⁴ independently of one another for C _n H _{2n + 1-px} {Y ¹ (CO) R ⁵ } _p (Y ² H) _x , where n stands for integers without 0 and p and x stand for integers or 0. Y ¹ and Y ² are independently O, N or NH. R ⁵ denotes a C ₃ -C ₂₃ alk (en) yl chain. X is a counter ion, which is preferably selected from the group of halides, alkyl sulfates and alkyl carbonates. Cationic surfactants in which the nitrogen group is substituted by two long acyl and two short alk (en) yl radicals are particularly preferred.

Amphoteric or ampholytic surfactants have several functional groups which can ionize in aqueous solution and - depending on the conditions of the medium - give the compounds anionic or cationic character (cf. DIN 53900, July 1972). In the vicinity of the isoelectric point (around pH 4) the amphoteric surfactants form internal salts, which make them difficult or insoluble in water. Amphoteric surfactants are divided into ampholytes and betaines, the latter being in solution as zwitterions. Ampholytes are amphoteric electrolytes, ie compounds that have both acidic and basic hydrophilic groups and therefore behave acidic or basic depending on the condition. Betaines are compounds with the atomic grouping R ₃ N ⁺ -CH ₂ -COO ^- that show typical properties of zwitterions.

The amounts of surfactants are up to 99% by weight, preferably up to 98% by weight, particularly preferably from 0.1% by weight to 98% by weight and in particular from 30% by weight to 98% by weight, each based on the entire mixture.

The other organic solvents that have no structural activators and no liquid Surfactants include, for example, solvents such as ketones, aldehydes, ethers, polyethers,  Nitriles, aliphatics, halogenated hydrocarbons, amines, carboxylic acids and mixtures thereof Solvent.

The amounts of other solvents that have no structural activators and no liquid ones Surfactants are up to 90% by weight, preferably up to 50% by weight and in particular up to 20% by weight, based in each case on the entire mixture.

The mixture of polyamide derivative, structural activator, selected from the group of Carboxylic acid derivatives and the organic carbonic acid ester and any mixtures of these with itself and other activators from the group of liquid alcohols and aromatics, and optionally surfactant and / or other solvents are carried out under shear, preferably in a highly dispersing device with strong shear (20 min at 4000 up to 15000 rpm). The mixture is quickly, for example, by at least one rotating, perforated dispersing disk, whereby a fine dispersion of the Polyamide derivatives in the structural activator or, where appropriate, in the structural activator surfactant and / or solvent mixture is formed. In a preferred embodiment, the Components of the mixture are mixed in a stirred container, and the mixture is mixed with a or several toothed disk stirrers, so-called dissolver disks, or with one or several rotor-stator stirrers (e.g. Ultra-Turrax®) strongly sheared and / or in one Dispersing machine (e.g. a Cavitron) or a ball mill severely sheared.

After activation by means of the structure activator under dispersion and shear you get the so-called stock paste, the activated and optionally in a surfactant and / or other solvent present polyamide derivative, depending on the medium in which it as a rheological additive or structuring agent or to prevent the sinking of others dispersed substances to be used, further process steps are supplied can.

In a further embodiment, the invention relates to a liquid washing or Cleaning agents containing activated polyamide derivative, in particular such polyamide derivatives, which were activated according to the invention.

The liquid detergent or cleaning agent contains activated ingredient (s) as an essential component Polyamide derivative (s) preferably in amounts of 0.01 to 20 wt .-%, particularly preferably 0.05 to less than 10% by weight, in particular 0.05 to 5% by weight, based on the total agent.  

The liquid detergent or cleaning agent is in a preferred embodiment non-aqueous. More preferred agents can be organic solvents that do not Structural activators are included, and wash-active substances.

The organic solvents used in the washing or cleaning agents according to the invention can be used include the structural activators as described above, and also ethers and polyethers. You can in amounts up to 90 wt .-%, preferably 70% by weight, particularly preferably from 0.1% by weight to 70% by weight and in particular from 5 to 60 wt .-%, each based on the total agent, are used.

Anionic surfactants, cationic surfactants, amphoteric surfactants can be used as washing-active substances and / or nonionic surfactants, as described above, and their mixtures, be used. The amounts of surfactant, based on the total average, are from 0.1% by weight to 98% by weight, preferably from 0.1% by weight to 90% by weight, particularly preferably from 5% by weight to 85% by weight and in particular from 15% by weight to 80% by weight.

If necessary, non-aqueous agents can preferably contain bleaching agents. Among the compounds which serve as bleaching agents and supply H ₂ O ₂ in water, sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Further usable bleaching agents are, for example, peroxopyro phosphates, citrate perhydrates and H ₂ O ₂ -supplying peracidic salts or peracids, such as persulphates or persulfuric acid. The urea peroxohydrate percarbamide can also be used, which can be described by the formula H ₂ N-CO-NH ₂ .H ₂ O ₂ . In particular, when using the agents for cleaning hard surfaces, for example in automatic dishwashing, they can, if desired, also contain bleaching agents from the group of organic bleaching agents, although their use is in principle also possible for agents for textile washing. Typical organic bleaching agents are the diacyl peroxides, such as dibenzoyl peroxide. Other typical organic bleaching agents are peroxy acids, examples of which include alkyl peroxy acids and aryl peroxy acids. 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, phamidimidoxycarboxy acid, phamidimoxoxycarboxyacid oxyacid oxybenzoic acid, , N-nonenylamido operadipic acid and N-nonenylamidopersuccinate, and aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperoxysebacic acid, diperoxybrassyl acid, the diperoxyphthalic acids, 2-decanedoybutoyl terexidoybutoyl acid-2-decyldiperoxy-tereoxybutanoic acid, 2-decyldiperoxy-tereoxybutoyl acid-2-decyldiperoxy-tereoxybutoyl acid, 2-decyldiperoxy-tereoxybutoyl acid, 2-decyldiperoxy-tereoxybutoyl acid, 2-decyldiperoxy-tereoxybutoyl acid, 2-decyldiperoxy acid, 2-decyldiperoxyacid, -di (6-aminopercaproic acid) can be used. The amount of bleaching agent in the agents according to the invention is usually between 0.5% by weight and 70% by weight, preferably between 0.5 and 30% by weight and in particular between 5 and 25% by weight, in each case based on the entire mean.

In preferred embodiments, the agents according to the invention can furthermore contain bleach activators. Bleach activators which can be used are compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic 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 number of carbon atoms mentioned and / or optionally substituted benzoyl groups. Multi-acylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, more particularly n- nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, more particularly phthalic anhydride, acylated polyhydric alcohols, especially triacetin, triethyl (TEAC), ethylene glycol diacetate, 2 , 5-diacetoxy-2,5-dihydrofuran and the enol esters known from German patent applications DE 196 16 693 and DE 196 16 767 as well as acetylated sorbitol and mannitol or their mixtures described in European patent application EP 0 525 239 (SORMAN), acylated sugar derivatives , in particular pentaacetylglucose (PAG), pentaacetylfructose, tetraacetylxylose and octaacetyllactose and acetylated tes, optionally N-alkylated glucamine and gluconolactone, and / or N-acylated lactams, for example N-benzoylcaprolactam, which are known from international patent applications WO 94/27970, WO 94/28102, WO 94/28103, WO 95/00626, WO 95 / 14759 and WO 95/17498 are known. The hydrophilically substituted acylacetals known from German patent application DE 196 16 769 and the acyl lactams described in German patent application DE 196 16 770 and international patent application WO 95/14075 are also preferably used. The combinations of conventional bleach activators known from German patent application DE 44 43 177 can also be used. Another class of preferred liquid bleach activators are the liquid imide bleach activators of the formula below.

where R ¹¹ = C ₇ -C ₁₃ linear or branched, saturated or unsaturated alkyl, preferably R ¹ = C ₇ -C ₉ linear alkyl; R ¹² = C ₁ -C ₂ alkyl, preferably methyl and R ¹³ = C ₁ -C ₂ alkyl, preferably methyl.

Such bleach activators are in the usual range of amounts, preferably in amounts of 1% by weight to 50% by weight, in particular 2% by weight to 15% by weight, based on the total average, contain.

In addition to the conventional bleach activators listed above or in their place can also be those from European patents EP 0 446 982 and EP 0 453 003 knew sulfonimines and / or bleach-enhancing transition metal salts respectively Transition metal complexes can be included as so-called bleaching catalysts. To the one in question coming transition metal compounds include in particular those from the German Pa tentanmeldung DE 195 29 905 known manganese, iron, cobalt, ruthenium or Mo lybdenum-salt complexes and those known from German patent application DE 196 20 267 N-analogue compounds known from German patent application DE 195 36 082 Gan, iron, cobalt, ruthenium or molybdenum carbonyl complexes, which in the German Patent application DE 196 05 688 manganese, iron, cobalt, ruthenium, Molybdenum, titanium, vanadium and copper complexes with nitrogenous tripod ligands, the cobalt, iron, copper and from the German patent application DE 196 20 411 Ruthenium-amine complexes, which are described in German patent application DE 44 16 438 Manganese, copper and cobalt complexes described in the European patent Report EP 0 272 030 described cobalt complexes, which from the European Patentan Message EP 0 693 550 known manganese complexes, which are from the European patent EP 0 392 592 known manganese, iron, cobalt and copper complexes, which from the international patent applications WO 96/23859, WO 96/23860 and WO 96/23861 known  Cobalt complexes and / or those in European Patent EP 0 443 651 or European patent applications EP 0 458 397, EP 0 458 398, EP 0 549 271, EP 0 549 272, Manganese complexes described in EP 0 544 490 and EP 0 544 519. According to the European patent application EP 0 832 969 available bleach boosting Active ingredient combination can be used in the agents. Combinations of Bleach activators and transition metal bleach catalysts are for example from the German patent application DE 196 13 103 and the international patent application WO 95/27775 known. Bleach-enhancing transition metal complexes, especially with the Central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru are used in usual quantities preferably in an amount of up to 1% by weight, in particular from 0.0025% by weight to 0.25% by weight and particularly preferably from 0.01% by weight to 0.1% by weight, in each case based on the total Means used.

In addition to the substances mentioned, the agents according to the invention can contain further ingredients detergents or cleaning agents, for example from the group of builders, Enzymes, electrolytes, pH adjusting agents, complexing agents, fragrances, perfume carriers, Fluorescent agents, dyes, foam inhibitors, graying inhibitors, anti-crease agents, antimicrobial agents, germicides, fungicides, antioxidants, antistatic agents, ironing aids, UV absorbers, optical brighteners, anti-redeposition agents, color transfer inhibitors, Anti-shrink agents, corrosion inhibitors, waterproofing and impregnating agents, hydrotropes, Silicone oils as well as swelling and sliding resistant agents.

The agents according to the invention can contain builders. Everyone can do it Builders usually used in washing or cleaning agents in the agents according to the invention are introduced, in particular thus 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 are 2, 3 or 4. Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514. Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3. In particular, both β- and δ-sodium disilicates are Na ₂ Si ₂ O ₅ . yH ₂ O is preferred, wherein β-sodium disilicate can be obtained, for example, by the process described in international patent application WO-A-91/08171.

Amorphous sodium silicates with a modulus Na ₂ O: SiO ₂ of 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, can also be used are delayed in dissolving and have secondary washing properties. The delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compression 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 in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle. However, it can very well lead to particularly good builder properties if the silicate particles deliver washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred. Such so-called X-ray amorphous silicates, which also have a delay in dissolution compared to conventional water glasses, are described, for example, in German patent application DE-A-44 00 024. Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.

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. However, zeolite X and mixtures of A, X and / or P are also suitable. Commercially available and can preferably be used in the context of the present invention, for example a co-crystallizate of zeolite X and zeolite A (about 80% by weight of zeolite X) ), developed by CONDEA Augusta S. p. A. is sold under the brand name VEGOBOND AX® and through the formula

n Na 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 µm (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water. The zeolites can can also be used and are suitable as over-dried zeolites with lower water contents then due to their hygroscopicity to remove unwanted traces of free Water.

It goes without saying that the generally known phosphates are also used as Builder substances possible, provided that such use is not for ecological reasons should be avoided. The sodium salts of orthophosphates are particularly suitable Pyrophosphates and especially the tripolyphosphates.

Organic builders that can be used as cobuilders Viscosity regulation serve, for example, are those that can be used in the form of their sodium salts Polycarboxylic acids, where polycarboxylic acids are understood to mean those carboxylic acids which carry more than one acid function. For example, these are 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 of this. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, Succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these.

The acids themselves can also be used. The acids have besides theirs Builder effect typically also the property of an acidifying component and serve thus also for setting a lower and milder pH of washing or Detergents. In particular, citric acid, succinic acid, glutaric acid, Adipic acid, gluconic acid and any mixtures of these. More usable Acidifiers are known pH regulators such as sodium bicarbonate and Sodium bisulfate.

Polymeric polycarboxylates are also suitable as builders, for example those Alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a molecular weight of 500 to 70,000 g / mol.  

For the purposes of this document, the molecular weights given for polymeric polycarboxylates are weight-average molecular weights M _{w of} the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), using a UV detector. The measurement was made against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship to the polymers investigated. This information differs significantly from the molecular weight information for which polystyrene sulfonic acids are used as standard. The molecular weights measured against polystyrene sulfonic acids are generally significantly higher than the molecular weights given in this document.

Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of Have 2000 to 20,000 g / mol. Because of their superior solubility, this can Group in turn the short-chain polyacrylates, the molar masses from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, may be preferred.

Suitable polymers can also include substances that are partially or completely composed Units consist of vinyl alcohol or its derivatives.

Also suitable are copolymeric polycarboxylates, especially those of acrylic acid Methacrylic acid and acrylic acid or methacrylic acid with maleic acid. As special copolymers of acrylic acid with maleic acid have proven suitable, the 50 to Contain 90 wt .-% acrylic acid and 50 to 10 wt .-% maleic acid. Your relative Molecular weight, based on free acids, is generally 2,000 to 70,000 g / mol, preferably 20,000 to 50,000 g / mol and in particular 30,000 to 40,000 g / mol. The (Co) polymeric polycarboxylates can either as an aqueous solution or preferably as Powder can be used.

To improve water solubility, the polymers can also allylsulfonic acids, such as for example in EP-B-0 727 448 allyloxybenzenesulfonic acid and methallylsulfonic acid, as Contain monomer.

Biodegradable polymers of more than two are also particularly preferred various monomer units, for example those which according to DE-A-43 00 772 as Monomeric salts of acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol Derivatives or according to DE-C-42 21 381 as monomers salts of acrylic acid and 2- Contain alkylallylsulfonic acid and sugar derivatives.  

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

Likewise, other preferred builder substances are polymeric aminodicarboxylic acids, their To name salts or their precursors. Polyaspartic acids are particularly preferred or their salts and derivatives, of which in the German patent application DE-A-195 40 086 it is disclosed that, in addition to cobuilder properties, it also has a bleach-stabilizing effect exhibit. Polyvinylpyrrolidones, castor oil derivatives and polyamine derivatives such as quaternized and / or ethoxylated hexamethylene diamines.

Other suitable builder substances are polyacetals, which are obtained by converting Dialdehydes with polyol carboxylic acids, which have 5 to 7 carbon atoms and at least 3 have hydroxyl groups, for example as in European patent application EP-A- 0 280 223 can be obtained. Preferred polyacetals are made from Dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from Obtained polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.

Dextrins, for example oligomers, are also suitable as organic builder substances or polymers of carbohydrates obtained by partial hydrolysis of starches can. The hydrolysis can be carried out according to customary methods, for example acid-catalyzed or enzyme-catalyzed Procedures are carried out. They are preferably hydrolysis products with average molar masses in the range from 400 to 500000 g / mol. A polysaccharide is included a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30 preferred, DE being a common measure of the reducing effect of a poly saccharids compared to dextrose, which has a DE of 100. Both are usable Maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins with higher ones Molar masses in the range from 2000 to 30000 g / mol. 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 processes for their preparation are known, for example, from European patent applications EP-A-0 232 202, EP-A-0 427 349, EP-A-0 472 042 and EP-A-0 542 496 as well as international patent applications WO- A-92/18542, WO-A-93/08251, WO-A-93/16110, WO-A-94/28030, WO-A-95/07303, WO-A-95/12619 and WO-A- 95/20608 known. An oxidized oligosaccharide according to German patent application DE-A-196 00 018 is also suitable. A product oxidized at C _{6 of} the saccharide ring can be particularly advantageous.

Oxydisuccinates and other derivatives of disuccinates are also preferred Ethylene diamine disuccinate are other suitable cobuilders. Here, ethylenediamine-N, N'- disuccinate (EDDS), the synthesis of which is described, for example, in US Pat. No. 3,158,615, preferably used in the form of its sodium or magnesium salts. Are also preferred in this context also glycerol disuccinates and glycerol trisuccinates such as for example in US Pat. Nos. 4,524,009, 4,639,325, in European patent application EP-A-0 150 930 and Japanese patent application JP-A- 93/339 896. Suitable amounts are in zeolite and / or formulations containing silicate at 3 to 15% by weight.

Other useful organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may also be in lactone form and which at least 4 carbon atoms and at least one hydroxyl group and a maximum of two Acid groups included. Such cobuilders are used, for example, in the international Patent application WO 95/20029 described.

The amount of builders in the agents according to the invention is usually 1 to 50% by weight. %, preferably 10 to 25% by weight. Preferred non-aqueous liquid detergents contain as Builders water-soluble builders, preferably from the group of oligo- and Polycarboxylates, the carbonates and the crystalline and / or amorphous silicates. Under these Compounds, the salts of citric acid have proven to be particularly suitable, the Alkali and among them in particular the sodium salts are preferred.

Enzymes include, in particular, those from the classes of hydrolases such as proteases, Esterases, lipases or lipolytic enzymes, amylases, cellulases or others Glycosyl hydrolases and mixtures of the enzymes mentioned in question. All of these hydrolases wear in the laundry to remove stains such as protein, fat or starchy Stains and graying. Cellulases and other glycosyl hydrolases can furthermore by removing pilling and microfibrils for color preservation and Contribute to increasing the softness of the textile. To bleach or inhibit the Color transfer can also use oxireductases. Are particularly well suited  Bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus and Humicola insolens obtained enzymatic agents. Preferably be Proteases of the subtilisin type and in particular proteases obtained from Bacillus lentus be used. There are enzyme mixtures, for example of protease and amylase or protease and lipase or lipolytic enzymes or protease and cellulase or from cellulase and lipase or lipolytically active enzymes or from protease, amylase and Lipase or lipolytic enzymes or protease, lipase or lipolytic Enzymes and cellulase, but especially protease and / or lipase-containing mixtures or Mixtures with lipolytically active enzymes of particular interest. examples for Such lipolytic enzymes are the well-known cutinases. Peroxidases or Oxidases have been found to be suitable in some cases. To the suitable amylases include in particular α-amylases, iso-amylases, pullulanases and pectinases. As cellulases are preferably cellobiohydrolases, endoglucanases and β-glucosidases, which also Cellobiases are called, or mixtures of these are used. Because there are different Can distinguish cellulase types by their CMCase and avicelase activities targeted mixtures of the cellulases the desired activities can be set.

The enzymes can be adsorbed or coated as supports on carrier substances, to protect them against premature decomposition. The proportion of enzymes, enzyme mixtures or enzyme granules can, for example, about 0.1 to 5% by weight, preferably 0.12 to about 2% by weight be.

As stabilizers especially for per-compounds and enzymes that are sensitive to Are heavy metal ions, the salts come from polyphosphonic acids, in particular 1-hydroxyethane-1,1-diphosphonic acid (HEDP), diethylenetriaminepentamethylenephosphonic acid (DETPMP) or ethylenediaminetetramethylenephosphonic acid.

A wide number of different salts can be used as electrolytes from the group of inorganic salts. 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 agents according to the invention is usually 0.1 to 5% by weight.

In order to bring the pH of the agents according to the invention into the desired range the use of pH adjusting agents should be indicated. All known acids can be used here or lyes, unless their use is based on application technology or ecological Prohibited reasons or for reasons of consumer protection. Usually exceeds that The amount of these adjusting agents is not 2% by weight of the total formulation.

To make the decomposition of certain ingredients catalyzed by heavy metals more wash-active To avoid formulations, substances that are heavy metals can be used complex. The alkali metal salts, for example, fall into the group of complexing agents Nitrilotriacetic acid (NTA) and its derivatives and alkali metal salts of anionic Polyelectrolytes such as polyacrylates, polymaleates and polysulfonates. Furthermore are low molecular weight hydroxycarboxylic acids such as citric acid, tartaric acid, malic acid or Gluconic acid and its salts are suitable. A preferred class of complexing agents are Phosphonates in preferred liquid detergent formulations in amounts of 0.01 up to 1.5% by weight, preferably 0.02 to 1% by weight and in particular from 0.03 to 0.5% by weight are included. These preferred compounds include in particular organophosphonates such as 1-hydroxyethane-1,1-diphosphonic acid (HEDP), aminotri (methylene phosphonic acid) (ATMP), diethylenetriamine-penta (methylenephosphonic acid) (DTPMP or DETPMP) and 2-phosphonobutane-1,2,4-tricarboxylic acid (PBS-AM), mostly in the form of their Ammonium or alkali metal salts are used.

Dyes and fragrances are added to the agents according to the invention in order to improve the aesthetics Improve impression of the products and the consumer in addition to the washing or Cleaning performance a visually and sensory "typical and distinctive" product for To make available. As perfume oils or fragrances, individual fragrance compounds, e.g. B. the synthetic products of the type of esters, ethers, aldehydes, ketones, alcohols and Hydrocarbons are used. Fragrance compounds of the ester type are e.g. B. Benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, Dimethylbenzyl-carbinyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, Ethyl methylphenyl glycinate, allyl cyclohexyl propionate, styrallyl propionate and benzyl salicylate. The ethers include, for example, benzyl ethyl ether, the aldehydes z. B. the linear Alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde,  Hydroxycitronellal, Lilial and Bourgeonal, to the ketones z. B. the Jonone, α-isomethyl ionone and methyl cedryl ketone, to the alcohols anethole, citronellol, eugenol, geraniol, linalool, Phenylethyl alcohol and terpineol, the hydrocarbons mainly include Terpenes like limes and pinene. However, mixtures of different are preferred Fragrances are used, which together produce an appealing fragrance. Such perfume oils can also contain natural fragrance mixtures, such as those from plant sources are accessible, e.g. B. pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Likewise suitable are muscatel, sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, Linden blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well Orange blossom oil, neroliol, orange peel oil and sandalwood oil.

The fragrances can be incorporated directly into the agents according to the invention, it can but it may also be advantageous to apply the fragrances to carriers, which increase the adhesion of the perfume reinforce on the laundry and by a slower fragrance release for long-lasting fragrance of textiles. Cyclodextrins, for example, have become such carrier materials proven, the cyclodextrin-perfume complexes additionally with other auxiliaries can be coated.

In order to improve the aesthetic impression of the agent according to the invention, you can use suitable dyes are colored. Preferred dyes, the selection of which Expert has no difficulty, have a high storage stability and Insensitivity to the other ingredients of the agents and to light and none pronounced substantivity towards textile fibers so as not to stain them.

Examples of foam inhibitors that can be used in the compositions are Soaps, paraffins or silicone oils, which may be based on carrier materials can be upset.

Graying inhibitors have the task of removing the dirt detached from the fibers in the liquor to keep suspended and thus prevent the dirt from re-opening. For this are Suitable water-soluble colloids mostly organic, for example glue, gelatin, salts of ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters cellulose or starch. Water-soluble polyamides containing acidic groups are also  suitable for this purpose. Soluble starch preparations and others other than that can also be used Use the above starch products, e.g. B. degraded starch, aldehyde starches, etc. Also Polyvinyl pyrrolidone is useful. However, cellulose ethers such as Carboxymethyl cellulose (Na salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as Methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and their mixtures in amounts of 0.1 to 5% by weight, based on the total agent, used

Since textile fabrics, in particular from rayon, wool, cotton and their mixtures, can tend to crease because the individual fibers prevent bending, kinking, pressing and Squeezing across the grain is sensitive, the agents can be synthetic Anti-crease included. These include, for example, synthetic products based on of fatty acids, fatty acid esters, fatty acid amides, alkylol esters, alkylolamides or Fatty alcohols, which are mostly reacted with ethylene oxide, or products based on Lecithin or modified phosphoric acid ester.

To combat microorganisms, detergents or cleaning agents can be antimicrobial Contain active ingredients. A distinction is made depending on the antimicrobial spectrum and Mechanism of action between bacteriostatics and bactericides, fungistatics and fungicides etc. Important substances from these groups are, for example, benzalkonium chlorides, Alkylarylsulfonates, halophenols and phenol mercuric acetate. The terms antimicrobial Effect and antimicrobial agent have in the context of the teaching of the invention professional meaning, for example, by K. H. Wallhäußer in "Practice of Sterilization, Disinfection - Preservation: Germ Identification - Industrial Hygiene "(5th ed. - Stuttgart; New York: Thieme, 1995) is reproduced, with all substances described there with antimicrobial effect can be used. Suitable antimicrobial agents are preferably selected from the groups of alcohols, amines, aldehydes, antimicrobial Acids or their salts, carboxylic acid esters, acid amides, phenols, phenol derivatives, diphenyls, Diphenylalkanes, urea derivatives, oxygen, nitrogen acetals and formals, benzamidines, Isothiazolines, phthalimide derivatives, pyridine derivatives, antimicrobial surfactants Compounds, guanidines, antimicrobial amphoteric compounds, quinolines, 1,2-dibromo 2,4-dicyanobutane, iodo-2-propyl-butyl-carbamate, iodine, iodophores, peroxo compounds, Halogen compounds and any mixtures of the above.  

The antimicrobial active ingredient can be selected from ethanol, n-propanol, i-propanol, 1,3-butanediol, phenoxyethanol, 1,2-propylene glycol, glycerin, undecylenic acid, benzoic acid, salicylic acid, dihydracetic acid, o-phenylphenol, N-methylmorpholine acetonitrile (MMA), 2-benzyl-4-chlorophenol, 2,2'-methylene-bis- (6-bromo-4-chlorophenol), 4,4'-dichloro-2'-hydroxydiphenyl ether (dichlosan), 2.4 , 4'-trichloro-2'-hydroxydiphenyl ether (trichlosan), chlorhexidine, N- (4-chlorophenyl) -N- (3,4-dichlorophenyl) urea, N, N '- (1,10-decane-diyldi- 1-pyridinyl-4-ylidene) bis (1-octanamine) dihydrochloride, N, N'-bis (4-chlorophenyl) -3,12-diimino-2,4,11,13-tetraaza-tetradecanediimidamide, Glucoprotamines, antimicrobial surface-active quaternary compounds, guanidines including the bi- and polyguanidines, such as 1,6-bis- (2-ethylhexyl-biguanido-hexane) dihydrochloride, 1,6-di- (N ₁ , N ₁ '- phenyldiguanido- N ₅ , N ₅ ') -hexane-tetrahydochloride, 1,6-di- (N ₁ , N ₁ ' -phenyl-N ₁ , N ₁ ^' -methyldiguanido- N ₅ , N ₅ ') -hexane dihydrochloride, 1,6-di- (N ₁ , N ₁ ' -o-chlorophenyldiguanido-N ₅ , N ₅ ') -hexane dihydrochloride, 1,6-di- (N ₁ , N ₁ '-2,6-dichlorophenyldiguanido-N ₅ , N ₅ ') hexane dihydrochloride, 1,6-di- [N ₁ , N ₁ '-beta- (p methoxyphenyl) diguanido-N ₅ , N ₅ ' ] -hexane-dihydrochloride, 1,6-di- (N ₁ , N ₁ '-alpha-methyl-.beta.- phenyldiguanido-N ₅ , N ₅ ') -hexane-dihydrochloride, 1,6-di- (N ₁ , N ₁ '-p-nitrophenyldiguanido-N ₅ , N ₅ ') hexane-dihydrochloride, omega: omega-di- (N ₁ , N ₁ '-phenyldiguanido-N ₅ , N ₅ ') -di-n propylether- dihydrochloride, omega: omega'-di- (N ₁ , N ₁ '-p-chlorophenyldiguanido-N ₅ , N ₅ ') -di-n-propylether-tetrahydrochloride, 1,6-di- (N ₁ , N ₁ ' -2,4-dichlorophenyldiguanido-N ₅ , N ₅ ') hexane tetrahydrochloride, 1,6-di- (N ₁ , N ₁ ' -p-methylphenyldiguanido-N ₅ , N ₅ ') hexane dihydrochloride, 1,6- Di- (N ₁ , N ₁ '-2,4,5-trichlorophenyldiguanido-N ₅ , N ₅ ') hexane-tetrahydrochloride, 1,6-di- [N ₁ , N ₁ '- alpha- (p-chlorophenyl) ethyldiguanido-N ₅ , N ₅ '] hexane dihydrochloride, omega: omega-di- (N ₁ , N ₁ ' - p-chlorophenyldiguanido-N ₅ , N ₅ ') m-xylene-dihydrochloride, 1,12-di- (N ₁ , N ₁ ' -p-chlorophenyldiguanido-N ₅ , N ₅ ') dodecane-dihydrochloride, 1.10- Di- (N ₁ , N ₁ '-phenyldiguanido-N ₅ , N ₅ ') -decane-tetrochydrid, 1,12-di- (N ₁ , N ₁ '-phenyldiguanido-N ₅ , N ₅ ') dodecane tetrahydrochloride, 1,6-di- (N ₁ , N ₁ '-o-chlorophenyldiguanido-N ₅ , N ₅ ') hexane-dihydrochloride, 1,6-di- (N ₁ , N ₁ '-o-chlorophenyldiguanido-N ₅ , N ₅ ') hexane-tetrahydrochloride, ethylene bis (1-tolyl biguanide), ethylene bis (p-tolyl biguanide), ethylene bis (3,5-dimethylphenyl biguanide), ethylene bis (p-tert- amylphenyl biguanide), ethylene bis (nonylphenyl biguanide), ethylene bis (phenyl biguanide), ethylene bis (N-butylphenyl biguanide), ethylene bis (2,5-diethoxyphenyl biguanide), ethylene bis (2,4-dimethylphenyl biguanide) ), Ethylene bis (o diphenyl biguanide), ethylene bis (mixed amyl naphthyl biguanide), N-butyl ethylene bis (phenyl biguanide), trimethylene bis (o-tolyl biguanide), N-butyl trimethyl bis (phenyl biguanide) ) and the corresponding Sa salts such as acetates, gluconates, hydrochlorides, hydrobromides, citrates, bisulfites, fluorides, polymaleates, N-cocoalkylsarcosinates, phosphites, hypophosphites, perfluorooctanoates, silicates, sorbates, salicylates, maleates, tartrates, fumarates, ethylenediamine tetraacetate, arylate, arylateate, arateate, arateate, arateate, arateate, arateate, arateate, arateate, arateate, arateate, arateate, arateate Pyromellitates, tetracarboxybutyrates, benzoates, glutarates, monofluorophosphates, perfluoropropionates and any mixtures thereof. Halogenated xylene and cresol derivatives, such as p-chlorometacresol or p-chloro-meta-xylene, as well as natural antimicrobial active ingredients of vegetable origin (e.g. from spices or herbs), animal and microbial origin are also suitable. Preferably antimicrobial surface-active quaternary compounds, a natural antimicrobial active ingredient of plant origin and / or a natural antimicrobial active ingredient of animal origin, extremely preferably at least one natural antimicrobial active ingredient of plant origin from the group comprising caffeine, theobromine and theophylline and essential oils such as eugenol, thymol and geraniol, and / or at least one natural antimicrobial active ingredient of animal origin from the group comprising enzymes such as protein from milk, lysozyme and lactoperoxidase, and / or at least one antimicrobial surface-active quaternary compound with an ammonium, sulfonium, phosphonium, iodonium - Or arsonium group, peroxo compounds and chlorine compounds are used. Substances of microbial origin, so-called bacteriocins, can also be used.

The quaternary ammonium compounds (QAV) suitable as antimicrobial active ingredients have the general formula (R ¹ ) (R ² ) (R ³ ) (R ⁴ ) N ⁺ X ^- , in which R ¹ to R ^{4 are} identical or different C ₁ -C ₂₂ -alkyl radicals, C ₇ -C ₂₈ aralkyl radicals or heterocyclic radicals, two or, in the case of an aromatic integration, as in pyridine, even three radicals together with the nitrogen atom, the heterocycle, for. B. a pyridinium or imidazolinium compound form, represent and X ^- halide ions, sulfate ions, hydroxide ions or similar anions. For an optimal antimicrobial effect, at least one of the residues preferably has a chain length of 8 to 18, in particular 12 to 16, carbon atoms.

QAV are by reacting tertiary amines with alkylating agents, such as. B. methyl chloride, Benzyl chloride, dimethyl sulfate, dodecyl bromide, but also ethylene oxide can be produced. The alkylie Tension of tertiary amines with a long alkyl residue and two methyl groups succeeds particularly easy, also the quaternization of tertiary nurses with two long residues and one  Methyl group can be carried out with the help of methyl chloride under mild conditions become. Amines which have three long alkyl residues or hydroxy-substituted alkyl residues gene, are not very reactive and are preferably quaternized with dimethyl sulfate.

Suitable QAC are, for example, benzalkonium chloride (N-alkyl-N, N-dimethyl-benzyl-ammonium chloride, CAS No. 8001-54-5), benzalkon B (m, p-dichlorobenzyl-dimethyl-C12-alkyl ammonium chloride, CAS No. 58390-78-6), benzoxonium chloride (benzyl-dodecyl-bis- (2-hy droxyethyl) ammonium chloride), cetrimonium bromide (N-hexadecyl-N, N-trimethyl-ammonium bromide, CAS No. 57-09- 0), Benzetoniunchlorid (N, N-Dimethyl-N- [2- [2- [p- (1,1,3,3-tetrame thylbutyl) -pheno-xy] ethoxy] ethyl] -benzylammonium chloride, CAS No. 121 -54-0), dialkyldime thylammonium chloride such as di-n-decyl-dimethyl-ammonium chloride (CAS No. 7173-51-5-5), didecyldi-methylammonium bromide (CAS No. 2390-68-3), dioctyl-dimethyl -ammoniumchloric, 1-cetylpyridinium chloride (CAS No. 123-03-5) and thiazoline iodide (CAS No. 15764-48-1) and their mixtures. Particularly preferred QAV are the benzalkonium chlorides with C ₈ -C ₁₈ alkyl radicals, in particular C ₁₂ -C ₁₄ alkyl-benzyl-dimethyl-ammonium chloride.

Benzalkonium halides and / or substituted benzalkonium halides are for example commercially available as Barquat® ex Lonza, Marquat® ex Mason, Variquat® ex Witco / Sherex and Hyamine® ex Lonza, as well as Bardac® ex Lonza. More commercially available antimicrobial agents are N- (3-chloroallyl) hexaminium chloride such as Dowicide® and Dowicil® ex Dow, benzethonium chloride such as Hyamine® 1622 ex Rohm & Haas, Methylbenzethonium chloride such as Hyamine® 10X ex Rohm & Haas, cetylpyridinium chloride such as Cepacol chloride ex Merrell Labs.

The antimicrobial active ingredients are used in amounts of 0.0001% by weight to 1% by weight, preferably from 0.001% by weight to 0.8% by weight, particularly preferably from 0.005% by weight to 0.3 wt .-% and in particular from 0.01 to 0.2 wt .-% used.

In order to prevent undesirable changes in the formulations and / or the treated textiles caused by the action of oxygen and other oxidative processes, the formulations can contain antioxidants. Phenols, bisphenols and thiobisphenols substituted by sterically hindered groups can be used as antioxidants. Other substance classes are aromatic amines, preferably secondary aromatic amines and substituted p-phenylenediamines, phosphorus compounds with trivalent phosphorus such as phosphines, phosphites and phosphonites, compounds containing endiol groups, so-called reductones, such as ascorbic acid and its derivatives, organosulfur compounds, such as the esters of 3 , 3'-Thiodipropionic acid with C _1-18 alkanols, especially C _10-18 alkanols, metal ion deactivators, which are able to catalyze the auto-oxidation metal ions, such as. As copper, to complex, such as EDTA, nitrilotriacetic acid, etc. and their mixtures. A large number of examples of such antioxidants is summarized in DE 196 16 570 (BASF AG) - the antioxidants mentioned there can be used in the context of the present invention.

An increased wearing comfort can result from the additional use of antistatic agents, which are added to the funds. Antistatic agents increase the surface conductivity and thus enable an improved drainage of charges formed. External antistatic agents are usually substances with at least one hydrophilic molecular ligand and give up on the Surfaces a more or less hygroscopic film. These are mostly surface-active Antistatic agents can be broken down into nitrogen-containing (amines, amides, quaternary ammonium compounds), phosphorus-containing (phosphoric acid esters) and sulfur-containing (alkyl sulfonates, alkyl sulfates) Divide antistatic agents. External antistatic agents are described, for example, in patent applications FR 1,156,513, GB 873 214 and GB 839 407. The Lauryl (or Stearyl-) dimethylbenzylammoniumchloride are suitable as antistatic agents for textiles or as Addition to the non-aqueous liquid detergents according to the invention, with an additional Finishing effect is achieved.

For example, silicone derivatives can be used in the formulations to improve the water absorption capacity, the rewettability of the treated textiles and to facilitate ironing of the treated textiles. These additionally improve the rinsing behavior of the wash-active formulations due to their foam-inhibiting properties. Preferred silicone derivatives are, for example, polydialkyl or alkylarylsiloxanes in which the alkyl groups have one to five carbon atoms and are completely or partially fluorinated. Preferred silicones are polydimethyl siloxanes which may be optionally derivatized, and are then aminofunctional or quaternized or Si-OH ^-, Si-H and / or Si-Cl bonds. The viscosities of the preferred silicones at 25 ° C. are in the range between 100 and 100,000 mPas, it being possible for the silicones to be used in amounts between 0.2 and 5% by weight, based on the total agent.

The agents can contain UV absorbers, which absorb onto the treated textiles and which Lightfastness of the fibers and / or the lightfastness of the other recipe components improve. UV absorbers are understood to mean organic substances (light protection filters) that are able to absorb ultraviolet rays and the absorbed energy in the form longer-wave radiation, e.g. B. to release heat again. Connections that you want Have properties are, for example, those due to radiationless deactivation active compounds and derivatives of benzophenone with substituents in 2- and / or 4- Position. Substituted benzotriazoles, such as, for example, the water-soluble one, are also present Benzenesulfonic acid 3- (2H-benzotriazol-2-yl) -4-hydroxy-5- (methylpropyl) monosodium salt (Cibafast® H), in the 3-position phenyl substituted acrylates (cinnamic acid derivatives), if necessary with cyano groups in the 2-position, salicylates, organic Ni complexes and natural products such as Umbelliferon and the body's own urocanoic acid are suitable. Have special meaning Biphenyl and especially stilbene derivatives as described for example in EP 0728749 A. and are commercially available as Tinosorb® FD or Tinosorb® FR ex Ciba. As UV B-absorbers are to be mentioned 3-benzylidene camphor or 3-benzylidene norcampher and its Derivatives, e.g. B. 3- (4-methylbenzylidene) camphor, as described in EP 0693471 B1; 4- Aminobenzoic acid derivatives, preferably 4- (dimethylamino) 2-ethylhexyl benzoate, 4- 2-octyl (dimethylamino) benzoate and amyl 4- (dimethylamino) benzoate; Esters cinnamic acid, preferably 2-ethylhexyl 4-methoxycinnamate, 4-methoxycinnamate pro pyl ester, 4-methoxycinnamic acid isamyl ester, 2-cyano-3,3-phenylcinnamic acid 2-ethylhexyl ester (Octocrylene); Esters of salicylic acid, preferably 2-ethylhexyl salicylic acid, salicylic acid 4-isopropylbenzyl ester, salicylic acid homomethyl ester; 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. B. 2,4,6- Trianilino- (p-carbo-2'-ethyl-1'-hexyloxy) -1,3,5-triazine and octyl triazone, as in EP 0818450 A1 described or dioctyl butamido triazone (Uvasorb® HEB); Propane-1,3-dione, such as B. 1- (4-tert-butylphenyl) -3- (4'methoxyphenyl) propane-1,3-dione; Ketotricyclo (5.2.1.0) decane derivatives, as described in EP 0694521 B1. Also suitable are 2-phenylbenzimidazole-5-sulfonic acid and its alkali, alkaline earth, ammonium,  Alkyl ammonium, alkanol ammonium and glucammonium salts; Sulfonic acid derivatives of Benzophenones, preferably 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and their Salts; Sulfonic acid derivatives of 3-benzylidene camphor, such as. B. 4- (2-Oxo-3-bornylidenme thyl) benzenesulfonic acid and 2-methyl-5- (2-oxo-3-bornylidene) sulfonic acid and their salts. Derivatives of benzoylmethane are particularly suitable as typical UV-A filters, such as for example 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 DE 197 12 033 A1 (BASF). The UV-A and UV-B filters can of course also be used in mixtures. In addition to the the soluble substances mentioned also come with insoluble light protection pigments for this purpose, namely finely dispersed, preferably nanoized metal oxides or salts in question. examples for Suitable metal oxides are in particular zinc oxide and titanium dioxide and also oxides of Iron, zirconium, silicon, manganese, aluminum and cerium as well as their mixtures. As Salts can be silicates (talc), barium sulfate or zinc stearate. The oxides and Salts in the form of pigments are already used for skin-care and skin-protecting emulsions and used 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 exhibit. They can have a spherical shape, but they can also Particles are used that are ellipsoidal or otherwise spherical Have a different shape. The pigments can also be surface treated, i.e. H. are hydrophilized or hydrophobized. Typical examples are coated titanium dioxides, such as B. Titanium dioxide T 805 (Degussa) or Eusolex® T2000 (Merck). As a hydrophobic Coating agents come primarily from silicones and especially trialkoxyoctylsilanes or Simethicone in question. Micronized zinc oxide is preferably used. More suitable UV light protection filters can be found in P. Finkel's overview in SÖFW-Journal 122, 543 (1996) remove.

The UV absorbers are usually used in amounts of 0.01% by weight to 5% by weight, preferably from 0.03% by weight to 1% by weight.

Optical brighteners (so-called "whiteners") can be added to the agents according to the invention to remove graying and yellowing of the treated textiles. This Fabrics pull on the fiber and cause a lightening and pretended bleaching effect, by converting invisible ultraviolet radiation into visible longer-wave light, whereby  the ultraviolet light absorbed from the sunlight as a slightly bluish fluorescence is emitted and with the yellow tone of the grayed or yellowed laundry pure white results. Are suitable for. B. 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) style salts ben-2,2'-disulfonic acid or compounds of a similar structure which instead of the morpholino A diethanolamino group, a methylamino group, an anilino group or a 2- Wear methoxyethylamino group. Brighteners of the substituted di phenylstyryle may be present, e.g. B. the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'- Bis (4-chloro-3-sulfostyryl) diphenyl, or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl) diphenyl. Other suitable compounds come, for example, from the substance classes of 4,4'- Diamino-2,2'-stilbene disulfonic acids (flavonic acids), 4,4'-distyryl biphenyls, methylumbelli ferones, coumarins, dihydroquinolinones, 1,3-diarylpyrazolines, naphthalic imides, benzoxazole, Benzisoxazole and benzimidazole systems and those substituted by heterocycles Pyrene derivatives. Mixtures of the aforementioned brighteners can also be used. The optical brighteners are usually used in amounts between 0.01 and 0.5% by weight,

Suitable antiredeposition agents, which are also referred to as soil repellents, are for example nonionic cellulose ethers such as methyl cellulose and Methyl hydroxypropyl cellulose with a proportion of methoxy groups of 15 to 30 wt .-% and of hydroxypropyl groups from 1 to 15% by weight, based in each case on the nonionic Cellulose ethers and the polymers of phthalic acid known from the prior art and / or terephthalic acid or its derivatives, in particular polymers Ethylene terephthalates and / or polyethylene glycol terephthalates or anionic and / or nonionically modified derivatives of these. Of these, the are particularly preferred sulfonated derivatives of phthalic and terephthalic polymers.

In a preferred embodiment, the agent can also be more commonly used Contain thickeners and anti-settling agents as well as viscosity regulators.

Preferred liquid detergents are shear thinning, i.e. H. they show as a rheological property pseudoplastic or thixotropic flow described at the beginning.

The viscosity of the liquid agent can be adapted to the special requirements of different areas of application. In this way it is possible to formulate viscous and easily movable agents, but also viscous to pasty agents for washing or cleaning, which are known in the market as gels, can be produced. Agents which do not flow under the influence of gravity, that is to say are no longer pourable and have a consistency which can be spread or cut, can also be produced without problems in the context of the present invention. The viscosity of the agents for a large number of application areas is usually between 500 and 50,000 mPas, values between 1000 and 10,000 mPas being preferred and values between 3000 and 5000 mPas being particularly preferred (T = 20 ° C., shear rate: 50 s ^{- 1} ) . For areas of application in which a non-pourable consistency is desired (e.g. detergent pastes for automatic dispensers in commercial washing machines), a significantly higher viscosity may be indicated - this can lead to dimensionally stable compositions in which a viscosity in the above sense is no longer indicated can be.

In a further embodiment, the invention relates to a process for the production of liquid washing or cleaning agents containing activated polyamide derivative (s), in which

• a) in a first process step polyamide derivative (s) by at least one Structure activator, can be activated, and if necessary in one of the Structure activators of various solutions 05670 00070 552 001000280000000200012000285910555900040 0002010016424 00004 05551 agent or solvent mixture and / or Surfactant (s) dispersed polyamide derivative (s) mixed with the structural activators become,
• b) the mixture obtained in process step (a) with further detergent components is mixed and optionally ground,
• c) optionally further substances, preferably sensitive to process step (b) or to Process step (b) unwanted substances are added.

Step (a) has already been described above as a method for activating the polyamide derivatives described in detail. The polyamide derivatives in step (a) are preferably in one part of the solvent or solvent mixture different from the structural activators and / or surfactant (s) and, if appropriate, dispersing the dispersion after activation further addition of the solvent other than the structural activators or Solvent mixture and / or surfactant changed in its consistency.

As further detergent ingredients and added in process steps (b) and (c) Substances can include all substances listed above such as surfactants, builders,  Cobuilders, bleaches, bleach activators, enzymes, solvents, soil repellents, alkaline Salts, foam inhibitors, complexing agents, enzyme stabilizers, graying inhibitors, optical brighteners, UV absorbers, thickeners, perfumes, dyes and others common detergent ingredients are used.

Substances sensitive to process step (b) are, for example, enzymes which can be denatured, bleaching agents, bleach activators and optionally coated Materials like percarbonate that can decompose. Unwanted in process step (b) Substances are, for example, dyes, brighteners, fragrances, etc. B. to an increased Give cause for effort in cleaning the system in the event of a product change.

In a preferred embodiment, a milling and / or Comminution process, preferably in an annular gap ball mill or a roller mill, carried out. In a further preferred embodiment, step (a) and step (b), preferably steps (a) to (c) are carried out simultaneously as a one-step process.

The particles obtained advantageously have after grinding and / or Comminution process a size of 1 to 200 microns, preferably 5 to 50 microns, in particular 10 to 30 µm (volume distribution; measurement method: Coulter counter).

Agents which contain polyamide derivative (s) which have been activated by this process, have improved rheological properties, preferably desired pseudoplastic or thixotropic flow and reduced tendency to sink in the gel phase dispersed solid particles.  

Examples

Two steps are essential for the preparation of the recipes: the activation of the polyamide and the mixing, optionally grinding process of the solids.

In the first process step, the polyamide derivative with part of the surfactant and one Structural activator (compositions E1 to E9 in Example 1; Tables 1 and 2) mixed, see above that a suspension was obtained. For comparison, two mixtures V1 and V2 indicated that did not contain a structure activator.

example 1 Premix compositions Table 1

The quantities are given in parts by weight, the viscosity values are in mPas specified.

Table 2

Quantities in percent by weight, based on the entire mixture

The suspensions were activated by strong shear (20 min; 8000 rpm) swelling in an Ultra Turrax and cooling by means of a thermostat (2 ° C). As Polyamide derivative was used Thixatrol® Plus ex Rheox. The viscosity values in Table 1 were using a Brookfield RTV, 20 ° C, spindle No. 2 with the shear rates given there measured. The compositions E1 to E6 according to the invention (Table 1) show a significantly more pronounced thixotropy behavior than the comparative examples V1 and V2 without Structure activator.

Example 2 Non-aqueous liquid detergents

The non-aqueous liquid detergents E10 to E12 were prepared as follows. Suspensions of surfactant, structure activator and polyamide derivative, such as the Mixtures E7 to E9 from Table 2 were activated by strong shear. In a second Process step was the stock paste with further recipe components and, if necessary mixed with other surfactant.

In a third step, enzymes and bleach activator were finally stirred in.

The funds obtained by this process (Table 3) were distinguished by the Stabilization by the activated polyamide derivative through excellent physical Properties such as storage stability of the bleaching agents, bleach activators and enzymes and reduced tendency for the solid particles dispersed in the gel phase to sink on.  

Table 3 Recipes for non-aqueous liquid detergents

All information is given in percent by weight and relates to the entire mixture.

Claims (29)

1. Use of polyamide derivatives which are activated by one or more structure activators, are activated as a rheological additive in liquid washing or cleaning agents and other fluid to highly viscous media such as cosmetics, adhesives, enamel, waxes, Paint removers, oil drilling fluids, greases and inks to improve rheological Properties of the medium or to prevent it from sinking into the medium dispersed solid particles. 2. Use of polyamide derivatives which are activated by one or more structure activators, selected from the group of carboxylic acid derivatives and organic carbonic acid esters and any mixtures of these with themselves and other activators from the group of liquid alcohols and aromatics, are activated as a rheological additive in liquid to highly viscous polyester resins, epoxy resins, sealants, paints and varnishes. 3. Use of polyamide derivatives according to claim 1 or 2, characterized in that that the polyamide derivatives by liquid carboxylic acid and carbonic acid derivatives, in which the ratio of oxygen to carbon per structural activator molecule in the range of 3: 1 to 1: 3, preferably from 3: 2 to 2: 5 and in particular from 1: 1 to 1: 2 become. 4. Use of polyamide derivatives according to claim 3, characterized in that the Polyamide derivatives by triethylacetyl citrate, triethyl citrate, ethylene glycol diacetate, Glycerol triacetate, propylene carbonate and glycerol carbonate, as well as any mixtures of these, be activated. 5. Use of polyamide derivatives according to one of claims 1 to 4, characterized characterized in that the weight ratio of structural activators to polyamide derivative from 500: 1 to 1: 500, preferably from 50: 1 to 1:50, particularly preferably from 20: 1 to 1:20 and in particular from 10: 1 to 1:10. 6. Use of polyamide derivatives according to one of claims 1 to 5, characterized characterized in that the activated polyamide derivatives in non-aqueous liquid washing or cleaning agents are used. 7. Activated polyamide derivatives, characterized in that the polyamide derivatives by Structural activators selected from the group of carboxylic acid derivatives and organic carbonic acid esters and any mixtures of these with themselves and  further activators from the group of liquid alcohols and aromatics, activated become. 8. Activated polyamide derivatives according to claim 7, characterized in that the Polyamide derivatives through liquid carboxylic acid and carbonic acid derivatives, in which the Ratio of oxygen to carbon per structural activator molecule in the range of 3: 1 to 1: 3, preferably from 3: 2 to 2: 5 and in particular from 1: 1 to 1: 2. 9. Activated polyamide derivatives according to claim 8, characterized in that the Polyamide derivatives by triethylacetyl citrate, triethyl citrate, ethylene glycol diacetate, Glycerol triacetate, propylene carbonate and glycerol carbonate, as well as any mixtures of these, be activated. 10. Activated polyamide derivatives according to claim 7 to 9, characterized in that the Weight ratio of structure activators to polyamide derivative from 500: 1 to 1: 500, preferably from 50: 1 to 1:50, particularly preferably from 20: 1 to 1:20 and in particular from 10: 1 to 1:10. 11. A process for the preparation of activated polyamide derivatives, characterized in that that the polyamide derivatives by structural activators selected from the group of Carboxylic acid derivatives and the organic carbonic acid ester as well as any mixtures this with itself and other activators from the group of liquid alcohols and Aromatics, are activated, which may be in one of the structural activators dispersed various solvents or solvent mixtures and / or surfactants Polyamide derivatives with the structural activators under shear, preferably in one highly dispersing device with strong shear, can be mixed. 12. The method according to claim 11, characterized in that the weight ratio of Structure activators for polyamide derivative from 500: 1 to 1: 500, preferably from 50: 1 to 1:50, is particularly preferably from 20: 1 to 1:20 and in particular from 10: 1 to 1:10. 13. The method according to any one of claims 11 or 12, characterized in that as of the structure activators different solvents or solvent mixtures nonionic surfactants, especially ethoxylated and / or propoxylated alcohols, and / or organic solvents and optionally anionic surfactants, cationic surfactants, Amphoteric surfactants and / or other detergent ingredients are used.   14. The method according to any one of claims 11 to 13, characterized in that as nonionic surfactants C ₈ -C ₁₆ alcohol alkoxylates, preferably ethoxylated and / or propoxylated C ₁₀ -C ₁₅ alcohol alkoxylates, in particular C ₁₂ -C ₁₄ alcohol alkoxylates, with a degree of ethoxylation between 1 and 12, preferably between 2 and 10, in particular between 3 and 8, and / or a degree of propoxylation between 1 and 10, preferably between 1 and 6, in particular between 1, 5 and 5, can be used. 15. The method according to any one of claims 11 to 14, characterized in that the added surfactants in amounts of up to 99% by weight, preferably up to 98% by weight, particularly preferably from 0.1% by weight to 98% by weight and in particular from 50% by weight to 98% by weight, each based on the entire mixture. 16. The method according to any one of claims 11 to 15, characterized in that the added other solvents that do not contain structural activators and no liquid Surfactants are, in amounts up to 90% by weight, preferably up to 50% by weight and in particular up to 20% by weight, based in each case on the entire mixture, are present. 17. The method according to any one of claims 11 to 16, characterized in that

• a) the components of the mixture are mixed in a stirred tank and
• b) the mixture is strongly sheared with one or more toothed disk stirrers or with one or more rotor-stator stirrers and / or
• c) the mixture is strongly sheared in a dispersing machine or a ball mill.

18. Liquid detergent or cleaning agent containing activated polyamide derivatives. 19. Composition according to claim 18, containing activated polyamide derivatives according to one of the claims 7 to 10. 20. Agent according to one of claims 18 or 19, characterized in that the agent Polyamide derivatives in amounts of preferably 0.01 to 20% by weight, particularly preferably 0.05 wt .-% to 10 wt .-%, in particular 0.05 wt .-% to 5 wt .-%, based on the ge all means.   21. Composition according to one of claims 18 or 20, characterized in that the means are not aqueous. 22. Agent according to one of claims 18 to 21, characterized in that the agent contain organic solvents, in amounts up to 90 wt .-%, preferably up 70% by weight, particularly preferably from 0.1% by weight to 70% by weight and in particular from 5 to 60 wt .-%, each based on the total agent. 23. Agent according to one of claims 18 to 22, characterized in that the agent Surfactants, preferably anionic surfactants, cationic surfactants, amphoteric surfactants and / or nonionic surfactants, especially ethoxylated and / or propoxylated alcohols, in Amounts from 0.1% by weight to 98% by weight, preferably from 0.1% by weight to 90% by weight, particularly preferably from 5% by weight to 85% by weight and in particular from 15% by weight to Contain 80 wt .-%, based on the total agent. 24. Agent according to one of claims 18 to 23, characterized in that the agent Bleach and optionally other detergent ingredients such as. B. bleaching stock contain vators and enzymes. 25. Agent according to one of claims 18 to 24, characterized in that the agent show thixotropic or pseudoplastic flow behavior. 26. A method for producing liquid detergents or cleaning agents according to one of claims 18 to 25, characterized in that

• a) in a first process step, polyamide derivatives are activated according to a process according to one of claims 11 to 17,
• b) the mixture obtained in process step (a) is mixed with further detergent constituents and optionally ground,
• c) optionally further substances, preferably substances that are sensitive to process step (b) or undesirable for process step (b), are added.

27. The method according to claim 26, characterized in that step (a) and step (b), preferably steps (a) to (c) are carried out simultaneously as a one-step process.   28. The method according to claim 26 or 27, characterized in that the polyamide derivatives in step (a) in part of the solvent other than the structural activators or solvent mixture and / or surfactant and the dispersion after activation by further addition of the structure activators Solvent or solvent mixture and / or surfactant in its consistency is changed. 29. The method according to any one of claims 26 to 28, characterized in that in Step (b) a grinding and / or grinding process, preferably in a ring slotted ball mill or a roller mill, and the particles obtained after the grinding and / or grinding process, preferably a size of 1 to 200 μm, particularly preferably 5 to 50 μm, in particular 10 to 30 μm.