DE10016423A1 - Liquid detergent with alkylene glycol carboxylic acid ester - Google Patents

Abstract

The use of liquid alkylene glycol carboxylic acid esters in washing or cleaning agents enables the production of agents, which can be poured with ease at low temperatures and which, in addition, have an excellent washing power. The invention relates to the use of liquid alkylene glycol carboxylic acid esters as a fluidic substitute medium for organic solvents and/or water in washing or cleaning agents.

Description

The present invention relates to liquid detergents, the liquid alkylene glycol carbon contain acid esters and good washing performance as well as excellent pourability exhibit at low temperatures.

Liquid detergents are due to their dust-free applicability, their simple do sierbarkeit and the generally better and faster solubility of the consumer asked. In addition, there is a strong need for liquid that is as concentrated as possible detergents to achieve a high washing performance with low dosage. Concentrated liquid detergents are characterized by the fact that they have a particularly high hen contain active detergent substances, so that parts of the water or or ganic solvent are replaced by surfactants. Show aqueous liquid detergent considerable deficits in the selection of detergent components to be used. So it is almost impossible to incorporate a bleach system into aqueous agents because the Bleach constantly lose activity due to signs of hydrolysis and the Means thus show reduced washing performance on bleachable stains. Because au also usual surfactant systems of liquid detergents, especially in the presence of anio niche surfactants, solid in the absence of water at temperatures below 10-15 ° C can be dispensed with water as a carrier medium only if instead orga nical solvent is used. However, these are not wash-active and lead often polluting the environment.  

In the prior art there are proposed solutions for the replacement of organic solutions medium by wash-active substances, but these are limited to the use of rivers siger fatty alcohol ethoxylates. For example, EP 691 018 describes concentrated non-aqueous rivers sigwaschmittel with 0.1 wt .-% to 10 wt .-% sodium metasilicate, the liquid Phase formed from liquid fatty alcohol ethoxylates and organic solvents the.

EP 225 654 describes concentrated liquid detergents in which the liquid phase is built up from non-ionic surfactants, which is formed by condensation of ethylene oxide (EO) and propylene oxide (PO) with alkylphenols, fatty alcohols or fatty amides. The molar ratio of PO / EO is in a range from 1:17 to 2: 1.

The use of fatty acid alkoxylates in detergents is also known, but who which they only use as solids for already liquid formulations. So be JP 57/05 17 99 writes an aqueous detergent composition in which 0.5 to 10.0 wt .-% solid fatty acid glycol ester with particle sizes of 5 to 30 microns is dispersed. JP 63/13 99 96 describes the production of a non-aqueous homogeneous dispersion from 1 to 35 wt .-% surfactant and solid fatty acid glycol esters at room temperature, which in Amounts of 0.1 to 35 wt .-% are contained in the dispersion.

SU 960 244 describes a concentrated paste containing bleach for cleaning Textiles containing both 7 to 17 wt .-% fatty acid polyethylene glycol ester and 10 to Contains 20 wt .-% ethylene glycol.

However, the concentrated detergents described in the prior art often show Problems with their pourability at low temperatures and their Washing performance.

The present invention was based on the object of a liquid washing or Rei Provide cleaning agents that are easy to pour at low temperatures is and also has an excellent washing performance.  

This problem is solved by using liquid alkylene glycol carboxylic acid esters in a detergent or cleaning agent formulation.

The invention thus relates to a liquid agent for washing or cleaning, wel ches liquid alkylene glycol carboxylic acid ester contains.

As an essential component, the agent according to the invention contains one or more liquids alkylene glycol carboxylic acid esters. Through the use of liquid alkylene glycol carboxylic acid reester in the agent according to the invention, can advantageously on the introduction other organic solvents or their use can be reduced. This not only has a positive ecological effect, but also increases washing performance, since the usual orga otherwise used in detergent or cleaning agent formulations African solvent replaced by wash-active liquid alkylene glycol carboxylic acid esters are.

Another object of the invention is therefore the use of liquid alkylene glycol colcarboxylic acid ester as a fluid replacement medium for organic solvents and / or what in detergents or cleaning agents.

The alkylene glycol carboxylic acid esters to be used according to the invention can be prepared industrially by alkoxylating carboxylic acids with ethylene oxide (EO) and / or propylene oxide (PO), as described, for example, in WO 98/25878 or EP 0 178 913 A1. Preferred alkylene glycol carboxylic acid esters are those described by the following formula I,

R ¹ CO (CH ₂ CH ₂ O) _n H (I)

in which R ^{1 is} a linear or branched, aliphatic, saturated or unsaturated alkyl radical having 6 to 22, preferably 6 to 18 and in particular 8 to 18 carbon atoms and n for numbers from 0.5 to 80, preferably 0.5 to 20, particularly preferably 0.5 to 5 and in particular 0.5 to 2.

According to formula I, the ethylene oxide units (EO) can advantageously be whole or partially replaced by propylene oxide units (PO). The specified Degrees of ethoxylation or degrees of propoxylation are statistical averages that can be an integer or a fraction for a specific product.

Typical examples are alkoxylation products, especially ethoxylation and pro poxylation products and their mixtures (simultaneous or subsequent alkoxy lation with EO and PO), benzoic acid and its derivatives, caproic acid, capryl acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid, Palmitic acid, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petro selinic acid, linoleic acid, linolenic acid, elaeostearic acid, arachic acid, gadoleic acid, Be hensic acid and erucic acid and their technical mixtures, the z. B. at the Druckspal treatment of natural fats and oils, in the reduction of aldehydes from the ro elen'schen oxosynthesis or the dimerization of unsaturated fatty acids. Alkylene glycol carboxylic acid esters which are below 25 ° C. preferably below 10 ° C, particularly preferably below 5 ° C and in particular which are liquid below 2 ° C.

Alkylene glycol carboxylic acid esters, particularly preferably ethylene glycol carboxylic acid esters, which are liquid below 25 ° C., preferably below 10 ° C., particularly preferably below 5 ° C. and in particular below half of 2 ° C., are preferably used in the agent according to the invention. In a preferred embodiment, C _6-14 carboxylic acids with 1 EO, in particular nonanoic acid with 1 EO or benzoic acid and their derivatives with 1 EO are used.

The alkylene glycol carboxylic acid esters are used in amounts of 0.1% by weight to 99% by weight, preferably from 5% by weight to 80% by weight, particularly preferably from 21% by weight to 70 wt .-% and in particular from 36 wt .-% to 50 wt .-%, each based on the ge all means used.

The quantities in percentages by weight are given and referenced below unless otherwise stated, on the entire average.  

The alkylene glycol carboxylic acid esters can be present as the sole surfactant. However, it can be advantageous if the agents according to the invention additionally contain one or more nonionic surfactant (s). Preferred nonionic surfactants are 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 methyl-branched linearly or particularly preferably in the 2-position or contain linear and methyl-branched radicals in the mixture, as is 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 to 9 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 containing 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C _12-14 alcohol with 3 EO and _C12-18 alcohol containing 5 EO. The degrees of ethoxylation and propoxylation given represent statistical mean values which, for a specific product, can be an integer or a fractional number. 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 pro poxylated, especially primary and secondary amines with preferably 1 to 18 C- Atoms per alkyl chain and an average of 1 to 12 moles of ethylene oxide (EO) and / or 1 to 10 moles of propylene oxide (PO) per mole of amine.  

In addition, alkyl glycosides of the general formula R ² O (G) _x can also be used as further nonionic surfactants, in which R is a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical with 8 to 22, preferably 12 to 18, carbon atoms. Atoms means 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, which are used either as allei some nonionic surfactant or in combination with other nonionic surfactants are used are alkoxylated, preferably ethoxylated or ethoxylated and pro poxylated fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl esters, as described, for example, in Japanese Pa tentanmeldung JP 58/217598 are described or which preferably according to the in ternational patent application WO-A-90/13533 who produced the.

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 alka nolamides may be suitable. The amount of these nonionic surfactants is before preferably not more than that of the ethoxylated fatty alcohols, especially not more than half of it.

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

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

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

in the R ⁵ for a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ⁶ for a linear, branched or cyclic alkyl radical or an aryl radical with 2 to 8 carbon atoms and R ⁷ for a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, C _1-4 -alkyl or phenyl radicals being preferred and [Z ² ] 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 radical.

[Z ² ] 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, by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst in the desired polyhydroxy fatty acid amides.

In the context of the present invention, liquid detergents are preferred which 0.01% by weight to 90% by weight, preferably 1% by weight to 80% by weight and in particular 5% by weight to 70% by weight of one or more nonionic surfactants, in particular of  the group of alkoxylated, preferably ethoxylated or ethoxylated and propoxy alcohols, preferably 10 to 20 and in particular 12 to 18 carbon atoms, contain.

The agents according to the invention can also contain amphoteric surfactants, in particular betaines. Betaines are known surfactants which are predominantly produced by carboxyalkylation, preferably carboxymethylation, of aminic compounds. The starting materials are preferably condensed with halocarboxylic acids or their salts, in particular with sodium chloroacetate, one mol of salt being formed per mole of betaine. Furthermore, the addition of unsaturated carboxylic acids, such as for example acrylic acid, is also possible. Regarding the nomenclature and in particular the distinction between betaines and "real" amphoteric surfactants, reference is made to the contribution by U. Ploog in Se fen-oils-fat waxes, 108, 373 (1982). Further overviews on this topic can be found, for example, by A. O'Lennick et al. in gAPPI, Nov. 70 (1986) S. Holzman et al. in tens. Surf. Det. 23, 309 (1986), R. Bibo et al. in Soap Cosm. Chem. Spec., Apr. 46 (1990) and P. Ellis et al. in Euro Cosm. 1, 14 (1994). Examples of suitable betaines are the carboxyalkylation products of secondary and in particular tertiary amines which follow the formula (I)

in the R ⁸ for alkyl and / or alkenyl radicals with 6 to 22 carbon atoms, R ⁹ for hydrogen or alkyl radicals with 1 to 4 carbon atoms, R ¹⁰ for alkyl radicals with 1 to 4 carbon atoms, n for numbers from 1 to 6 and X. represents an alkali and / or alkaline earth metal or ammonium. Typical examples are the carboxymethylation products of hexylmethylamine, hexyldimethylamine, octyldimethylamine, decyldimethylamine, Dode cylmethylamin, dodecyldimethylamine, Dodecylethylmethylamin, C methylamine _12/14 -Kokosalkyldi, myristyldimethylamine, cetyldimethylamine, stearyldimethylamine, Stearyle thylmethylamin, oleyldimethylamine, C _16/18 tallow alkyl dimethyl amine and technical mixtures thereof .

Carboxyalkylation products of amidoamines which follow the formula (II) are also suitable,

in which R ¹³ CO represents an aliphatic acyl radical having 6 to 22 carbon atoms and 0 or 1 to 3 double bonds, m represents numbers from 1 to 3 and R ^{11 represents} hydrogen or alkyl radicals having 1 to 4 carbon atoms, R ^{12 represents} alkyl radicals with 1 up to 4 carbon atoms, n represents numbers from 1 to 6 and X represents an alkali and / or alkaline earth metal or ammonium. Typical examples are reaction products of fatty acids with 6 to 22 carbon atoms, namely caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, arenachic acid, gadoleic acid, gadeleic acid, gadoleic acid, gadeleic acid, gadeleic acid, gadic acidic acid, galeic acidic acid, galeic acidic acid, galeic acidic acid, galeic acidic acid, galeic acidic acid, galeic acidic acid, galeic acidic acid, galeic acidic acid, galeic acidic acid, galeic acidic acid, galeic acidic acid, galeic acidic acid, gadic acidic acid, gaelic acidic acid, gadic acidic acid, gaelic acidic acid, gadic acidic acid, gaelic acidic acid, gaic acidic acid, gaic acidic acid gadic acidic acid and erucic acid and their technical mixtures, with N, N-dimethylaminoethylamine, N, N-dimethylaminopropylamine, N, N-diethylaminoethylamine and N, N-diethylaminopropylamine, which are condensed with sodium chloroacetate. It is preferred to use a condensation product of C _8/18 coconut fatty acid N, N-dimethylaminopropylamide with sodium chloroacetate.

The agents according to the invention can furthermore contain cationic surfactants. The most important representatives of the cationic surfactants are the quaternary ammonium compounds of the general formula: (R ¹⁴ R ¹⁵ R ¹⁶ R ¹⁷ N ⁺ ) X ^- . R ¹⁴ stands for C ₁ -C ₈ alk (en) yl, R ¹⁵ to R ¹⁷ independently of one another for C _n H _{2n + 1-px} {Y ¹ (CO) R ¹⁸ } _p (Y ² H) _x , where n stands for integers without ne 0 and p and x stand for integers or 0. Y ¹ and Y ² are independently of one another O, N or NH. R ¹⁸ 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.

The agents according to the invention can also contain anionic surfactants. 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 with a terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products. Also suitable are alkanesulfonates obtained from C _12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. The esters of α-sulfo fatty acids (ester sulfonates), e.g. B. the α-sulfonated Me methyl ester of hydrogenated coconut, palm kernel or tallow fatty acids.

Other suitable anionic surfactants are sulfonated fatty acid glycerol esters. Under fatty acid glyce The mono-, di- and triesters as well as their mixtures are to be understood as Rinestern, as in the production by esterification of a monoglycerin with 1 to 3 moles of fatty acid or obtained in the transesterification of triglycerides with 0.3 to 2 mol of glycerol. Before pulled sulfated fatty acid glycerol esters are the sulfonation products of saturated fat acids with 6 to 22 carbon atoms, for example caproic acid, caprylic acid, Ca. pric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.

The alk (en) yl sulfates are the alkali and especially 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, petrochemical-based straight-chain alkyl radical which have a degradation behavior similar to that of the adequate compounds based on oleochemical raw materials. From the washing, the C ₁₂ -C ₁₆ alkyl sulfates and C ₁₂ are - C ₁₅ alkyl sulfates and C ₁₄ -C ₁₅ alkyl sulfates of preferably. 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, Stearic acid, 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.

Preferred liquid detergents additionally contain anionic surfactants, preferably from the group of alkyl sulfates, alkanesulfonates, alkylbenzenesulfonates, sulfuric acid mo noester and fatty acid soaps.

In the context of the present invention, liquid detergents which are anionic are preferred Surfactants in amounts from 0.01% by weight to 80% by weight, preferably from 1% by weight to  60 wt .-%, particularly preferably from 5 wt .-% to 40 wt .-%, each based on the total funds included.

The agents according to the invention can also contain organic solvents such as ethanol, n- or i-propanol, butanols, glycol, propane or butanediol, glycerin, diglycol, pro pyl 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 me ethyl 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 butoxy triglycol, 1-butoxyethoxy-2-propanol, Bu toxypropoxy propanol (BPP), 3-methyl-3-methoxybutanol, propylene glycol t-butyl ether and mixtures of these solvents, preferably not in amounts above 20% by weight, but solvent-free agents are particularly preferred.

In the context of the present invention, the term “solvent-free” means understand the small amounts or traces of the solvents listed above contain. In the "solvent-free" agents of the present invention are thus ge small amounts of solvents tolerable, preferably below 2 wt .-%, in particular the less than 0.3 wt .-%, each based on the total agent.

The liquid detergents according to the invention can also contain water, preferably two in amounts not above 10% by weight, but non-aqueous are particularly preferred ge means.

The term “non-aqueous” means in the context of the present invention understand that only small amounts of free, so not as crystal water or in any other Way bound to contain water. Because even non-aqueous solvents and raw materials fe (in particular those technical qualities) have certain water contents completely water-free agents on an industrial scale only with great effort and high cost to manufacture. In the "non-aqueous" agents of the present invention So small amounts of free water tolerable, the less than 5 wt .-%, preferably un ter 2 wt .-%, each based on the finished agent.  

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 peracid salts or peracids, such as per sulfates. 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 bleaches from the group of organic bleaches, although their use is also possible in principle for agents for textile washing. Typical organic bleaching agents are the diacyl peroxides, such as dibenzoyl peroxide. Other typical organic bleaching agents are the peroxyacids, examples of which are alkyl peroxyacids and arylperoxyacids. Preferred representatives are the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy-α-naphthoic acid and magnesium monoper phthalate, the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ε-phthalimidanoic acid, o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinate, and aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperoxysebacinic acid, diperoxybrassoxydiacid-disiperic acid, 1,4-diperoxybrassoxydiacid, , N, N-terephthaloyl-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 50% by weight, preferably between 0.5 and 40% by weight and in particular between 2 and 30% 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. Preferred are multiply acylated alkylenediamines, in particular tetraacetylethylene diamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetyl glycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, especially n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, especially phthalic anhydride, acylated polyvalent alcohol triethyl triethyl triethyl, especially triac 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 pentaacetyl glucose (PAG), pentaacetyl fructose, tetraacetylxylose and octaacetyl lactose and acet y lated, optionally N-alkylated glucamine and gluconolactone, and / or N-acylated lactams, for example N-benzoylcaprolactam, which are derived 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 ¹⁹ = C ₇ -C ₁₃ linear or branched, saturated or unsaturated alkyl, preferably R ¹⁹ = C ₇ -C ₉ linear alkyl; R ²⁰ = C ₁ -C ₂ alkyl, preferably methyl and R ²¹ = C ₁ -C ₂ alkyl, preferably methyl.

Such bleach activators are in the usual range of amounts, preferably in amounts from 1% by weight to 15% by weight, in particular 2% by weight to 10% by weight, based on ge velvet means included.

In addition to the conventional bleach activators listed above or other The place from the European patents EP 0 446 982 and EP 0 453 003 known sulfonimines and / or bleach-enhancing transition metal salts or contain transition metal complexes as so-called bleaching catalysts his. The transition metal compounds in question include in particular known from the German patent application DE 195 29 905 manganese, iron, Cobalt, ruthenium or molybdenum salt complexes and those from the German Pa tentanmeldung DE 196 20 267 known N-analog compounds, which from the German Patent application DE 195 36 082 known manganese, iron, cobalt, ruthenium or Molybdenum carbonyl complexes, which be in the German patent application DE 196 05 688 wrote manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and Copper complexes with nitrogen-containing tripod ligands, which are derived from the German Pa Tent registration DE 196 20 411 known cobalt, iron, copper and ruthenium Ammine complexes described in German patent application DE 44 16 438 Manganese, copper and cobalt complexes described in the European patent application Cobalt complexes described in EP 0 272 030, which result from the European patent application EP 0 693 550 known manganese complexes, which from the European patent EP 0 392 592 known manganese, iron, cobalt and copper complexes, which from the in International patent applications WO 96/23859, WO 96/23860 and WO 96/23861 be knew 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, Manganese complexes described in EP 0 549 272, EP 0 544 490 and EP 0 544 519. Also the bleaching enhancer available according to European patent application EP 0 832 969 Active ingredient combination can be used in the agents. Combinations of bleach Activators and transition metal bleaching catalysts are for example from the German cal 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 amounts, preferably in an amount 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 all means.

In addition to the substances mentioned, the agents according to the invention can contain further substances Contain substances from detergents and cleaning agents, for example from the group of builders, enzymes, electrolytes, pH adjusting agents, complexing agents, fragrances, par film 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, Paint transfer inhibitors, anti-shrink agents, corrosion inhibitors, anti-settling agents, Phobing and impregnating agents, hydrotropes, silicone oils as well as swelling and anti-slip agents.

The agents according to the invention can contain builders. It can all übli chelating agents used in washing and cleaning agents in the invention appropriate agents are introduced, in particular thus zeolites, silicates, carbonates, orga niche 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 are preferred values for × 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 the 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 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, compaction / 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 in such a way that the products have microcrystalline ranges 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 release delay compared to the conventional water glass glasses, are described for example in German patent application DE-A-44 00 024. Particularly preferred are compressed / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates.

The finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P. As zeolite P, zeolite MAP® (commercial product from Crosfield) is particularly preferred. 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 (approx. 80% by weight zeolite X), which was 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 we less than 10 µm (volume distribution; measurement method: Coulter Counter) on and included preferably 18 to 22% by weight, in particular 20 to 22% by weight of bound water. The zeolites can also be used as over-dried zeolites with lower water contents  are and are then unsuitable for removal due to their hygroscopicity Desired traces of free water.

It goes without saying that the generally known phosphates are also used as buildersub punching possible, provided that such use is not avoided for ecological reasons should be. The sodium salts of orthophosphates, the py rophosphates and especially the tripolyphosphates.

Organic builders that can be used as cobuilders Viscosity regulation serve, for example, can be used in the form of their sodium salts ren polycarboxylic acids, polycarboxylic acids being understood to mean such carboxylic acids that have 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 right, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA) and their derivatives ge and mixtures of these. Preferred salts are the salts of the 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 their buil the 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. Another one settable acidifying agents are known pH regulators such as sodium hydrogen carbonate 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.

In the context of this document, the molecular weights given for polymeric polycarboxylates are weight-average molecular weights M _{w of} the respective acid form, which were determined in principle by means of gel permeation chromatography (GPC), using a UV detector. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship with the investigated polymers. 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, can this group in turn the short-chain polyacrylates, the molecular weights from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, before be moving.

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 with methacrylic acid and acrylic acid or methacrylic acid with maleic acid. As a special copolymers of acrylic acid with maleic acid, 50 to Contain 90 wt .-% acrylic acid and 50 to 10 wt .-% maleic acid. Your relative mole Cooling mass, based on free acids, is generally from 2000 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 can be used as powder.

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 right, contained as a monomer.

Biodegradable polymers of more than two ver. Are also particularly preferred different 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 monomer salts of acrylic acid and the 2-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 as monomers Have acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate. Likewise, further preferred builder substances are polymeric aminodicarboxylic acids, to name their salts or their precursors. Polyas are particularly preferred paraginic acids or their salts and derivatives, of which in the German patent application dung DE-A-195 40 086 discloses that, in addition to cobuilder properties, it also has a have a bleach-stabilizing effect. Polyvinylpyrrolidones are also suitable, Polyamine derivatives such as quaternized and / or ethoxylated hexamethylene diamines.

Other suitable builder substances are polyacetals, which are produced by the implementation of Dial dehyden with polyol carboxylic acids, which have 5 to 7 carbon atoms and at least 3 have hydroxyl groups, for example as in the 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 obtained from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.

Dextrins, for example oli, are also suitable as organic builder substances gomers or polymers of carbohydrates by partial hydrolysis of starches can be obtained. The hydrolysis can be carried out according to conventional methods, for example acid or enzyme-catalyzed processes are carried out. It is preferably Hy Drolysis products with average molecular weights in the range of 400 to 500000 g / mol. there is a polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40 ins particularly preferred from 2 to 30, DE being a common measure of the reducing Effect of a polysaccharide compared to dextrose, which has a DE of 100, is. Both maltodextrins with a DE between 3 and 20 and dry can be used glucose syrups with a DE between 20 and 37 as well as so-called yellow dextrins and White dextrins with higher molar masses in the range from 2000 to 30000 g / mol. A be preferred dextrin is described in British patent application 94 19 091.  

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 and 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.

Also oxydisuccinates and other derivatives of disuccinates, preferably ethylenedia mindisuccinate 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. Also preferred in this context are also glycerol disuccinates and glycerol trisuccinates as they are 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 those containing zeolite and / or formulations containing silicate at 3 to 15% by weight.

Other useful organic cobuilders are, for example, acetylated hydroxycarbon acids or their salts, which may optionally also be in lactone form, and which have at least 4 carbon atoms and at least one hydroxyl group and maxi contain two acid groups. Such cobuilders are used, for example, in the inter national patent application WO 95/20029.

The amount of builders in the agents according to the invention is usually 1 to 50% by weight, preferably 10 to 40% 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.  Among these compounds, the salts of citric acid have been found to be special proved to be suitable, the alkali and, in particular, the sodium salts before are moving.

Detergents or cleaning agents can be added by adding rheological additives sedimentation of solid particles can be prevented. Take over these anti-sedatives men often also function as builders or cobuilders and are therefore already at the top described. Layer silicates which are particularly suitable as anti-settling agents are such as bentonites and their organic modifications, polyacrylates, polycarboxylic acids, Po lysaccharides and their derivatives, activated polyamide derivatives, polyurethanes, polyvinylpyr rolidones, castor oil derivatives, polyamine derivatives such as quaternized and / or ethoxylated Hexamethylenediamines and any mixtures thereof.

The anti-settling agent content of the agents according to the invention is usually 1 to 50% by weight, preferably 10 to 40% by weight.

Enzymes in particular come from the hydrolase classes such as the protea sen, esterases, lipases or lipolytically active enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned in question. All this hy drolasen wear in the laundry to remove stains such as protein, fat or starchy stains and graying. Cellulases and other glycosyl hy drolasen can also be removed by removing pilling and microfibrils Color preservation and increase the softness of the textile. For bleaching or Color transfer inhibition can also be used oxireductases. Especially from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheni are well suited formis, Streptomyceus griseus and Humicola insolens enzymatic active ingredient fe. Proteases of the subtilisin type and in particular proteases which are preferred are obtained from Bacillus lentus. There are enzyme mixtures, at act from protease and amylase or protease and lipase or lipolytic the enzymes or protease and cellulase or from cellulase and lipase or lipolytically acting enzymes or from protease, amylase and lipase or lipolytically acting Enzymes or protease, lipase or lipolytically acting enzymes and cellulase, in particular  however, protease and / or lipase-containing mixtures or mixtures with lipo enzymes of particular interest. Examples of such lipolytic acting enzymes are the well-known cutinases. Also have peroxidases or oxidases proved to be suitable in some cases. Suitable amylases include in particular special α-amylases, iso-amylases, pullulanases and pectinases. As cellulases preferably cellobiohydrolases, endoglucanases and β-glucosidases, which are also cellobi asen are called, or mixtures of these are used. Since different Cel Differentiate lulase types by their CMCase and avicelase activities targeted mixtures of the cellulases the desired activities can be set.

The enzymes can be adsorbed onto carriers or embedded as shaped bodies to protect them against premature decomposition. The proportion of enzymes, Enzymmi Schungen or enzyme granules can, for example, about 0.1 to 5 wt .-%, preferably 0.12 to about 2 wt .-%.

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), diethylenetriaminepentamethylenephosphon acid (DETPMP), aminotri (methylenephosphonic acid) (ATMP) or ethylenediamine tetramethylenephosphonic acid into consideration.

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 manufacturing 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 0.5 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 may be indicated. All be can be used here knew acids or alkalis, provided that their use does not result from application technology or ecological reasons or for reasons of consumer protection. Usually  the amount of these adjusting agents exceeds 2% by weight of the total formulation Not.

About the decomposition of certain ingredients catalyzed by heavy metals waschakti ver formulations, substances can be used, the heavy metals complex. The alkali metal salts, for example, fall into the group of complexing agents Nitrilotriacetic acid (NTA) and allcalimetal salts of anionic polyelectrolytes such as Polyacrylates, polymaleates and polysulfonates. Low molecular weight hydroxy are also carboxylic acids such as citric acid, tartaric acid, malic acid or gluconic acid and their salts suitable. A preferred class of complexing agents are the phosphonates, which are described in preferred liquid detergent formulations in amounts of 0.01 to 3 wt .-%, before preferably 0.02 to 2 wt .-% and in particular from 0.03 to 1.5 wt .-% are included. These preferred compounds include, in particular, organophosphonates as in for example 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 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 to improve the impression of the products and the consumer in addition to the washing or Cleaning performance a visually and sensory "typical and distinctive" product to provide. As perfume oils or fragrances, individual fragrance ver ties, e.g. B. the synthetic products of the ester, ether, aldehyde, ketone type, Alcohols and hydrocarbons can be used. Fragrance compounds of the type the esters are e.g. B. benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, Linalyl acetate, dimethylbenzylcarbinylacetate, phenylethyl acetate, linalylbenzoate, benzyl formate, ethyl methylphenyl glycinate, allyl cyclohexyl propionate, styrallyl propionate and Benzyl salicylate. The ethers include, for example, benzyl ethyl ether and the aldehydes e.g. B. the linear alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetalde hyd, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal, to the ketones z. B. the Jonone, α-isomethyl ionone and methyl cedryl ketone, to the alcohols anethole, citro nellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, to the hydrocarbons  mainly include the terpenes like limes and pinene. To be favoured however, mixtures of different fragrances are used, which together address one Generate the appropriate fragrance. Such perfume oils can also contain natural fragrance mixtures contain as they are accessible from plant sources, e.g. B. pine, citrus, jasmine, Patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage oil, Chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper beer oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, Neroliol, orange peel oil and sandalwood oil.

The fragrances can be incorporated directly into the agents according to the invention but can also be advantageous to apply the fragrances to the carrier, which increase the liability of the perfume on the laundry and by a slower fragrance release for long-lasting fragrance of the textiles. As such carrier materials have been found for example, cyclodextrins have proven themselves, with the cyclodextrin-perfume complexes additionally can be coated with other auxiliaries.

In order to improve the aesthetic impression of the agents according to the invention, they can can be colored with suitable dyes. Preferred dyes, the selection of which Specialist poses no difficulty, has a high storage stability and is unstable sensitivity 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 such as soaps, paraffins or silicone oils, which may be on carrier material lien can be upset.

Graying inhibitors have the task of removing the dirt detached from the fiber in the Keep the liquor suspended and thus prevent the dirt from re-opening. Water-soluble colloids of mostly organic nature are suitable for this, for example Glue, gelatin, salts of ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Also water-soluble, acidic Group-containing polyamides are suitable for this purpose. Furthermore,  use soluble starch preparations and starch products other than the above, e.g. B. degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone can also be used. Before However, cellulose ethers such as carboxymethyl cellulose (sodium salt) and methyl cellulose are added se, hydroxyalkyl cellulose and mixed ethers such as methyl hydroxyethyl cellulose, methyl hy droxypropyl cellulose, methyl carboxymethyl cellulose and their mixtures in quantities of 0.1 to 5 wt .-%, based on the total agent used

Since textile fabrics, especially from rayon, wool, cotton and their Mi can tend to crease because the individual fibers prevent bending, knic The media can be sensitive to pressing and squeezing across the grain contain synthetic anti-crease agents. These include, for example, synthetic pro products based on fatty acids, fatty acid esters, fatty acid amides, alkylol esters, alkylolamides or fatty alcohols, which are mostly reacted with ethylene oxide, or Pro Products based on lecithin or modified phosphoric acid esters.

To combat microorganisms, detergents or cleaning agents can be antimicro bielle contain active ingredients. A distinction is made here 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 chloride, alkylarylsulfonates, halophenols and phenol mercuric acetate. The terms anti The microbial effect and antimicrobial agent have been invented teaching according to the technical meaning, for example by K.H. Wallhäußer in "Practice of Sterilization, Disinfection - Preservation: Germ Identification - Be drive hygiene "(5th ed. - Stuttgart; New York: Thieme, 1995) where be used for all substances described there with an antimicrobial effect can. Suitable antimicrobial agents are preferably selected from the Groups of alcohols, amines, aldehydes, antimicrobial acids or their salts, Car bonic acid esters, acid amides, phenols, phenol derivatives, diphenyls, diphenylalkanes, urine Substance derivatives, oxygen, nitrogen acetals and formals, benzamidines, isothiazolines, Phthalimide derivatives, pyridine derivatives, antimicrobial surface-active compounds, Guanidines, antimicrobial amphoteric compounds, quinolines, 1,2-dibromo-2,4-  dicyanobutane, iodo-2-propyl-butyl-carbamate, iodine, iodophores, peroxo compounds, halo gene compounds and any mixtures of the foregoing.

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-methyhnorpholine acetonitrile (MMA), 2-benzyl-4-chlorophenol, 2,2'-methylene-bis- (6-bromo-4-chlorophenol), 4,4'-di chloro-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- decan-diyldi-1-pyridinyl-4-ylidene) bis (1-octanamine) dihydrochloride, N, N'-bis (4-chlorophenyl) -3,12-diimino-2,4,11,13 -tetraaza-tetradecanediimidamide, glucoprotamines, anti-microbial 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 ' -methyldiguani do-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-dichlorophenyldi guanido-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- (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-propyl ether dihydro chloride, omega: omega-di- (N ₁ , N ₁ '-p-chlorophenyldiguanido-N ₅ , N ₅ ') -di-n-propyl ether-trahydrochloride, 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) ethyl diguanido-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 '-phenyldiguani do-N ₅ , N ₅ ') -decane-tetrahydrochloride, 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 (2nd , 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 ch end salts such as acetates, gluconates, hydrochlorides, hydrobromides, citrates, bisulfites, fluorides, polymaleates, N-cocoalkylsarcosinates, phosphites, hypophosphites, perfluoroocanoates, silicates, sorbates, salicylates, maleates, tartrates, fumarates, imate ethyanoateate ethylenediamine tetra , Arginates, pyromellitates, tetracarboxybuty rates, 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, including 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 lac toperoxidase, and / or at least one antimicrobial surface-active quaternary compound with an ammonium, sulfonium, Phosphonium, iodonium or arsonium group, peroxo compounds and chlorine compounds can be 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, where with two or in the case of an aromatic bond as in pyridine even three radicals together with the nitrogen atom, the heterocycle, for. B. a pyridinium or Imidazoli niumverbindung 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. Me thyl chloride, benzyl chloride, dimethyl sulfate, dodecyl bromide, but also ethylene oxide adjustable. The alkylation of tertiary amines with one long alkyl residue and two Methyl groups are particularly easy to achieve, including the quaternization of tertiary amines with two long residues and a methyl group can be taken with the help of methyl chloride mild conditions. Amines that have three long alkyl residues or Hydroxy-substituted alkyl radicals have little reactivity and are preferred with Quaternized 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-alkylammonium chloride, CAS No. 58390-78 -6), benzoxonium chloride (benzyl-dodecyl-bis (2-hydroxyethyl) ammonium chloride), cetrimonium bromide (N-hexadecyl-N, N-trimethyl ammonium bromide, CAS No. 57-09-0), benzetonium chloride (N, N-Dimethyl-N- [2- [2- [p- (1,1,3,3-tetramethylbutyl) phenoxy] ethoxy] ethyl] benzylammonium chloride, CAS No. 121-54-0), dialkyldimethylammonium- chlorides such as di-n-decyl-dimethyl-ammonium chloride (CAS No. 7173-51-5-5), didecyldimethylammonium 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 examples commercially available as Barquat® ex Lonza, Marquat® ex Mason, Variquat® ex Witco / Sherex and Hyamine® ex Lonza, as well as Bardac® ex Lonza. More commercial Available antimicrobial agents are N- (3-chloroallyl) hexaminium chloride such as Do. wicide® and Dowicil® ex Dow, benzethonium chloride such as Hyamine® 1622 ex Rohm & Haas, methylbenzethonium chloride such as Hyamine® 10X ex Rohm & Haas, cetylpyridini umchloride 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, endiol group-containing compounds, so-called reductones, such as ascorbic acid and its derivatives, organosulfur compounds, such as the esters the 3,3'-thiodipropionic acid with C _1-18 alkanols, in particular C _10-18 alkanols, metal ion deactivators which are able to catalyze the auto-oxidation metal ions, such as. B. copper to comple x, such as EDTA, nitrilotriacetic acid, etc. and their mixtures. A large number of games for 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.

Increased comfort can result from the additional use of antistatic agents that are additionally added to the funds. Antistatic agents enlarge the surfaces conductivity and thus enable an improved drainage of charges formed. Ou External antistatic agents are generally substances with at least one hydrophilic molecule ligands and give a more or less hygroscopic film on the surfaces. These mostly surface-active antistatic agents can be broken down into nitrogen-containing (amines, Amides, quaternary ammonium compounds), phosphorus-containing (phosphoric acid esters) and Subdivide sulfur-containing (alkyl sulfonates, alkyl sulfates) antistatic agents. External antistatic agents are, for example, in patent applications FR 1,156,513, GB 873 214 and GB 839 407 described. The lauryl (or stearyl) dimethylbenzylammoniumchlo disclosed here Ride are suitable as antistatic agents for textiles or as an additive to those according to the invention non-aqueous liquid detergents, with an additional finishing effect.  

To improve the water absorption capacity, the rewettability of the behan Delten textiles and to facilitate ironing of the treated textiles can in the formulations, for example silicone derivatives. Improve this in addition, the rinsing behavior of the wash-active formulations thanks to their foam properties. Preferred silicone derivatives are, for example, polydialkyl or Alkylarylsiloxanes in which the alkyl groups have one to five carbon atoms and all or partially fluorinated. Preferred silicones are polydimethylsiloxanes may be derivatized and then amino functional or quaternized or Si Have OH, Si-H and / or Si-Cl bonds. The viscosities of the preferred sili Cones are between 25 and 100,000 mPas at 25 ° C, the silicones in Amounts between 0.2 and 5 wt .-%, based on the total agent can.

The agents can contain UV absorbers, which are applied to the treated textiles and the lightfastness of the fibers and / or the lightfastness of the other formulation improve ingredients. Organic substances (light protection film ter) to understand who are able to absorb ultraviolet rays and the up energy taken in the form of longer-wave radiation, e.g. B. to release heat again. Ver Bonds that have these desired properties are, for example, those by radiation-free deactivation of active compounds and derivatives of benzophenone with substituents in the 2- and / or 4-position. Substituted benzotria are also available zoles, such as the water-soluble benzenesulfonic acid-3- (2H-benzotriazol-2-yl) -4- hydroxy-5- (methylpropyl) monosodium salt (Cibafast® H), in the 3-position phenyl substituent ated acrylates (cinnamic acid derivatives), optionally with cyano groups in the 2-position, Sa licylates, organic Ni complexes as well as natural substances such as umbelliferone and the body's own ne urocanoic acid suitable. Biphenyl and especially style ends are particularly important Derivatives as described for example in EP 0728749 A and commercially are available as Tinosorb® FD or Tinosorb® FR ex Ciba. As UV-B absorbers are too call 3-benzylidene camphor or 3-benzylidene norcampher and its derivatives, e.g. B. 3- (4-methylbenzylidene) camphor, as described in EP 0693471 B1; 4-aminobenzoe acid derivatives, preferably 2-ethylhexyl 4- (dimethylamino) benzoate, 2-octyl 4- (dimethylamino) benzoate  and 4- (dimethylamino) benzoic acid amyl ester; Esters of cinnamic acid, preferably 2-ethylhexyl 4-methoxycinnamate, 4-methoxy cinnamic acid propyl ester, 4-methoxycinnamic acid isamyl ester, 2-cyano-3,3-phenylcinnamic acid-2- ethylhexyl ester (octocrylene); Esters of salicylic acid, preferably salicylic acid 2- ethylhexyl ester, salicylic acid 4-isopropylbenzyl ester, salicylic acid homomethyl ester; Deri vate of benzophenone, preferably 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4- methoxy-4'-methylbenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone; Ester of ben zalmalonic acid, preferably di-2-ethylhexyl 4-methoxybenzmalonate; Triazinderi vate, such as B. 2,4,6-Trianilino- (p-carbo-2'-ethyl-1'-hexyloxy) -1,3,5-triazine and octyl tria zon, as described in EP 0818450 A1 or dioctyl butamido triazone (Uvasorb® HEB); Propane-1,3-diones such as e.g. B. 1- (4-tert-butylphenyl) -3- (4'methoxyphenyl) propane-1,3- dion; Ketotricyclo (5.2.1.0) decane derivatives, as described in EP 0694521 B1. Wei 2-phenylbenzimidazole-5-sulfonic acid and its alkali metal, alkaline earth metal, Ammonium, alkylammonium, alkanolammonium and glucanimonium salts; Sulfone acid derivatives of benzophenones, preferably 2-hydroxy-4-methoxybenzophenone-5- sulfonic acid and its salts; Sulfonic acid derivatives of 3-benzylidene camphor, such as. B. 4- (2- Oxo-3-bornylidene methyl) benzenesulfonic acid and 2-methyl-5- (2-oxo-3-bornylidene) sulfone acid and its salts.

Derivatives of benzoylmethane are particularly suitable as typical UV-A filters. such as 1- (4'-tert-butylphenyl) -3- (4'-methoxyphenyl) propane-1,3-dione, 4-tert.- Butyl-4'-methoxydibenzoylmethane (Parsol 1789), 1-phenyl-3- (4'-isopropylphenyl) -pro pan-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 be set. In addition to the soluble substances mentioned, un come for this purpose soluble light protection pigments, namely finely dispersed, preferably nanoised metal oxides or salts in question. Examples of suitable metal oxides are, in particular, zinc oxide and Titanium dioxide and also oxides of iron, zirconium, silicon, manganese, aluminum and cer and their mixtures. Silicates (talc), barium sulfate or Zinc stearate can be used. The oxides and salts are already in the form of the pigments used for skin-care and skin-protecting emulsions and decorative cosmetics. The particles should have an average diameter of less than 100 nm, preferably  have between 5 and 50 nm and in particular between 15 and 30 nm. she can have a spherical shape, but such particles can also be used sentence come that is an ellipsoidal or otherwise dependent on the spherical shape have softening shape. The pigments can also be surface treated, i.e. H. hydro philized or hydrophobic. 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. Vastness Suitable UV light protection filters are in the overview by P. Finkel in SÖFW-Journal 122, 543 (1996).

The UV absorbers are usually present in amounts of from 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 used in the agents according to the invention can be added to cause graying and yellowing of the treated textiles sided. These substances absorb on the fiber and bring about a lightening and pre deceived bleaching effect by turning invisible ultraviolet radiation into visible longer convert wavy light, the ultraviolet light absorbed from sunlight is emitted as a slightly bluish fluorescence and with the yellow tone of the grayed or yellowed laundry results in pure white. Are suitable for. B. 4,4'-bis (2- anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or the like built-up compounds that instead of the morpholino group a diethanolamino group pe, a methylamino group, an anilino group or a 2-methoxyethylamino group wear. Brighteners of the substituted diphenylstyryl type may also be present be, e.g. B. the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfo styryl) diphenyl, or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl) diphenyl.

Other suitable compounds originate, for example, from the substance classes of 4,4'-diamino-2,2'-stilbene disulfonic acids (flavonic acids), 4,4'-distyryl biphenylene, Me thylumbelliferone, coumarins, dihydroquinolinones, 1,3-diarylpyrazolines, naphthalic acid mide, benzoxazole, benzisoxazole and benzimidazole systems as well as by heterocycles  substituted pyrene derivatives. Mixtures of the aforementioned brighteners can also be used be applied.

The optical brighteners are usually used in amounts between 0.01 and 0.6% by weight, based on the total agent used.

Suitable antiredeposition agents, which are also referred to as soil repellents, are for example nonionic cellulose ethers such as methyl cellulose and methylhydroxypro pylcellulose with a proportion of methoxy groups of 15 to 30 wt .-% and Hy droxypropyl groups from 1 to 15 wt .-%, each based on the nonionic Cellu loose ether and the polymers of phthalic acid known from the prior art and / or terephthalic acid or its derivatives, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionic and / or nonio nisch modified derivatives of these. Particularly preferred of these are the sul Formed derivatives of phthalic acid and terephthalic acid polymers.

The agents according to the invention are prepared in a manner known per se Mix the ingredients in stirred tanks. Unless it's for a specific end product is desired, the solids contained in the agents according to the invention can by be further crushed a wet grinding step to ensure the separation stability of the agents further increase. For such operations familiar to the person skilled in the art, are suitable for for example colloid mills, roller mills or annular gap or agitator ball mills. The addition of the carboxylic acid alkoxylates to be used according to the invention can be started any place in such a usual manufacturing process. Usually the any bleach and bleach activators that may be present are not together incorporated into the agents before grinding, because the intimate contact of the substances during grinding can promote decomposition.

The viscosity of the liquid agent can be adapted to the special requirements of different areas of application. In this way, viscous and easily movable agents can be formulated, 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 200 and 50,000 mPas, values between 1,000 and 10,000 mPas being preferred and values between 3,000 and 7,000 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 no longer applies can be meaningfully specified.

Examples

The following example E1 demonstrates a composition of the invention Liquid detergent. V1 was selected as the comparative composition. The details in Table 1 appear in percent by weight and refer to the total average.

Table 1

The washing properties of the agent E1 according to the invention were carried out in a washing machine in a washing machine compared to V1.

Washing conditions

Washing machine: Miele W 918; Short program 30 ° C and 60 ° C; 17.5 liters of city water at 17 ° d; 3.0 kg clean laundry and 0.5 kg test fabric. The dosing was carried out via a dosing ball;
Dirt load: 16 usual stains

The washed and dried test fabrics (polyester / cotton finished) were examined for their reflectance values using the Datacolor SF 500-3 device. Exam conditions: UV filter at 460 nm, aperture 30 mm, light type D65.

The measured color distance values give the visual impression of color changes colored textiles after washing again. By measuring L, a and b values became the color locus of a sample in the color space according to publication CIE No. 15.2, 1986 certainly.

The washing performance was comparable over 15 stains; for the lipstick Soiling (lipstick: Marbert No. 40), however, showed an improved washing effect kung (Table 2).  

Table 2

averaged remission values (3-fold determination) for a lipstick stain (lipstick: Marbert No. 40) refined on polyester / cotton

The results show that the agent according to the invention on lipstick stains shows a significantly improved washing effect.

Table 3 represents further agents E2 to E6 according to the invention.

Table 3

Quantities are given in percent by weight, based on the total agent, Viscosity values in mPas.

The viscosity values in Table 3 were determined using a Brookfield RTV, 20 ° C., spindle no. 2 measured with the shear rates specified there.

The viscosity measurements of the agents E2 to E7 according to the invention show a dependency viscosity of the shear rate. For E2 to E7 the viscosity increases Increase in shear rate from. The agents thus show a pseudoplastic or thixotropic behavior.

Claims (11)

1. Liquid detergent, characterized in that the agent contains liquid alkylene glycol carboxylic acid esters. 2. Liquid detergent according to one of the preceding claims, characterized records that the agent liquid alkylene glycol carboxylic acid esters in amounts of 0.1% by weight to 99% by weight, preferably from 5% by weight to 80% by weight, and in particular more preferably from 21% by weight to 70% by weight, in each case based on the total amount tel, contains. 3. Liquid detergent according to one of the preceding claims, characterized records that the agent contains liquid ethylene glycol carboxylic acid esters. 4. Liquid detergent according to one of the preceding claims, characterized in that the agent contains as ethylene glycol carboxylic acid ester C _6-14 carboxylic acids with 1 EO, in particular nonanoic acid with 1 EO or benzoic acid and their derivatives with 1 EO. 5. Liquid detergent according to one of the preceding claims, characterized records that the agent non-ionic surfactant (s) in amounts of 0.01 wt .-% to 90 wt .-%, preferably 1% by weight to 80% by weight and in particular 5% by weight to 70% by weight, based on the total mean. 6. Liquid detergent according to one of the preceding claims, characterized records that the agent anionic surfactants in amounts of 0.01 wt .-% to 80% by weight, preferably from 1% by weight to 60% by weight, particularly preferably from 5 wt .-% to 40 wt .-%, each based on the total agent contains. 7. Liquid detergent according to one of the preceding claims, characterized records that the agent contains betaines or cationic surfactants.   8. Liquid detergent according to one of the preceding claims, characterized records that the agent contains no other organic solvents. 9. Liquid detergent according to one of the preceding claims, characterized indicates that the agent is non-aqueous. 10. Use of liquid alkylene glycol carboxylic acid esters as a fluid replacement medium for organic solvents and / or water in detergents or cleaning agents. 11. Use of liquid alkylene glycol carboxylic acid esters according to claim 10, characterized characterized in that the alkylene glycol carboxylic acid esters in amounts of 0.1 wt .-% up to 99% by weight, preferably from 5% by weight to 80% by weight and particularly preferably from 21% by weight to 70% by weight, based in each case on the total composition become.