WO2001074981A1 - Liquid washing agent containing 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

 "Liquid detergent with alkylene glycol carboxylic acid ester"

The present invention relates to liquid detergents which contain liquid alkylene glycol carboxylic acid esters and have good washing performance and excellent pourability at low temperatures.

Liquid detergents are in demand by consumers because of their dust-free applicability, their easy dosing and the generally better and faster solubility. In addition, there is a strong need for liquid detergents which are as concentrated as possible in order to achieve a high washing performance with a low dosage. Concentrated liquid detergents are distinguished by the fact that they contain a particularly high content of detergent substances, so that parts of the water or the organic solvent are replaced by surfactants. Aqueous liquid detergents show considerable deficits in the selection of detergent components to be used. It is almost impossible to incorporate a bleaching system into aqueous agents, since the bleaching agents continuously lose activity due to hydrolysis and the agents thus show reduced washing performance on bleachable stains. In addition, since conventional surfactant systems for liquid detergents, especially in the presence of anionic surfactants, become solid in the absence of water at temperatures below 10-15 ° C., water can only be dispensed with as a carrier medium if organic solvent is used instead. However, these are not wash-active and often lead to pollution of the environment.

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

EP 225 654 describes concentrated liquid detergents in which the liquid phase is composed of nonionic surfactants which are formed by the 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 they are only used as solids in already liquid formulations. JP 57/05 17 99 describes an aqueous cleaning agent composition in which 0.5 to 10.0% by weight of solid fatty acid glycol ester with particle sizes of 5 to 30 μm is dispersed.

JP 63/13 99 96 describes the preparation of a non-aqueous homogeneous dispersion of 1 to 35% by weight of surfactant and fatty acid glycol esters which are solid at room temperature and are present in the dispersion in amounts of 0.1 to 35% by weight.

SU 960 244 describes a concentrated paste containing bleach for cleaning textiles, which contains both 7 to 17% by weight of fatty acid polyethylene glycol ester and 10 to 20% by weight of ethylene glycol.

However, the concentrated detergents described in the prior art frequently show problems with regard to their pourability at low temperatures and with regard to their washing performance.

The object of the present invention was to provide a liquid detergent or cleaning agent which can be easily poured at low temperatures and which also has 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, which contains liquid alkylene glycol carboxylic acid esters.

As an essential component, the agent according to the invention contains one or more liquid alkylene glycol carboxylic acid esters. By using liquid alkylene glycol carboxylic acid esters in the agent according to the invention, it is advantageously possible to dispense with the introduction of other organic solvents or to reduce their use. This not only has a positive ecological effect, but also increases the washing performance, since the usual organic solvents otherwise used in detergent or cleaning agent formulations are replaced by washing-active liquid alkylene glycol carboxylic acid esters.

Another object of the invention is therefore the use of liquid alkylene glycol carboxylic acid esters as a fluid replacement medium for organic solvents and / or water in washing or cleaning agents.

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

R ¹ CO (CH ₂ CH ₂ O) "H (I)

in R ¹ for 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 wholly or partly replaced by propylene oxide units (PO). The degrees of ethoxylation or degrees of propoxylation given represent statistical mean values, which can be an integer or fractional number for a specific product.

Typical examples are alkoxylation products, in particular ethoxylation and propoxylation products, and also their mixtures (simultaneous or subsequent alkoxylation with EO and PO), benzoic acid and its derivatives, caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid, myristic acid acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, arachic acid, gadoleic acid, behenic acid and erucic acid and their technical mixtures, the in the pressure splitting of natural fats and oils, in the reduction of aldehydes from Roelen's oxosynthesis or in the dimerization of unsaturated fatty acids.

Alkylene glycol carboxylic acid esters which are liquid below 25 ° C., preferably below 10 ° C., particularly preferably below 5 ° C. and in particular below 2 ° C. are preferred.

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 2 ° C., are preferably used in the agent according to the invention. Carboxylic acids having 1 EO, in particular nonanoic acid with 1 EO or benzoic acid and their derivatives are used with 1 EO - In a preferred embodiment, _6- C ι ₄ are.

The alkylene glycol carboxylic acid esters are used in amounts of from 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% by weight and in particular from 36% by weight to 50% by weight, based in each case on the total agent.

In the following, the amounts are given in percent by weight and, unless otherwise stated, relate to the total composition. 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 mol ethylene oxide (EO) and / or 1 to 10 mol propylene oxide (PO) per mol alcohol, used. Particularly preferred are C ₈ -C ₁₆ alcohol alkoxylates, advantageously ethoxylated and / or propoxylated Cios alcohol alkoxylates, in particular C ₁₂ -C ₁₆ 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. However, alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 to 9 EO, C _-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 of this are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

Also suitable are alkoxylated amines, advantageously ethoxylated and / or propoxylated, in particular primary and secondary amines with preferably 1 to 18 carbon atoms per alkyl chain and an average of 1 to 12 mol ethylene oxide (EO) and / or 1 to 10 mol propylene oxide (PO) per Mole of amine. In addition, alkyl glycosides of the general formula RO (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 having 8 to 22, preferably 12 to 18, carbon 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 preferably used nonionic surfactants, which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters, as they are are described, for example, in Japanese patent application JP 58/217598 or which are preferably produced by the process described in international patent application WO-A-90/13533.

Nonionic surfactants of the amine oxide type, for example N-coconut alkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can also be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of them.

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

R ⁴

R ^ CO-N-tZ ¹ ]

in which R ³ CO is an aliphatic acyl radical having 6 to 22 carbon atoms, R ^{4 is} hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z ¹ ] represents a linear or branched polyhydroxyalkyl radical having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups. The polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive airiation 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

R ⁶ -OR ⁷

R ⁵ -CO-N- [Z ² ]

in which R ^{5 represents} a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{6 represents} a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R ^{7 represents} a linear, branched or cyclic alkyl radical or Aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, C ₁ - 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 residue.

[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, for example according to the teaching of international application WO-A-95/07331, be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.

In the context of the present invention, liquid detergents are preferred which contain 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 from the group of the alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, alcohols, preferably 10 to 20 and in particular 12 to 18 carbon atoms.

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. The addition of unsaturated carboxylic acids, such as 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 Seifen-Öle-Fette-Wwachs, 108, 373 (1982). Further overviews on this topic can be found, for example, by A. O'Lennick et al. in HAPPI, Nov. 70 (1986), S. Holzman et al. in tens. Surf.Det. 1986, 23: 309, 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)

R ⁹

, I

R ⁸ -N- (CH ₂ ) _n COOX (I)

R ¹⁰

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, decyidimethylamine, dodecylmethylamine, dodecyldimethylamine, dodecylethylmethylamine, C _12/14 cocoalkyldimethylamine, myristyldimethylamine, cetyldimethylamine, ryldimethylamine, stearylemylmethylamine, oleyldimethylamine, C ₁₆ / ι ₈ -

Tallow alkyl dimethylamine and their technical mixtures.

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

R ¹³ CO-NH- (CH ₂ ) _m - ¹ N- (CH ₂ ) _n COOX (II)

R ¹²

in which R 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 having 1 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, aeleostearic acid, elaostearic acid , Gadoleic acid, behenic 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. Preferred is the use of a condensation product of the C _8/18 is - 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: (^ W ^ V) X ^" . R ¹⁴ stands for C 1 -C ₈ -alk (en) yL, R ¹⁵ to R ¹⁷ independently of one another for C" H ₂ " ₊₁ _ _p _ _x {Y ¹ (CO) R ¹⁸ } ^ (Y ² H) _Λ;, where n stands for integers without 0 and /? And x stands for integers or 0. Y ¹ and Y ² stand independently of one another for 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 are particularly preferred for which the nitrogen group is substituted with two long acyl and two short alk (en) yl radicals. In addition, the agents according to the invention can 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. ₁₃ -Alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates such as are obtained, for example, from C ₁₂ . _18- Monoolefϊnen obtained with 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-sulfofatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.

! Other suitable anionic surfactants are sulfated fatty acid glycerol esters. Fatty acid glycerol esters are to be understood as the mono-, di- and triesters and their mixtures as obtained in the production by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol become.

Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated

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.

As alk (en) yl sulfates, the alkali and in particular the sodium salts of the sulfuric acid semiesters of the C ₂ -C ₈ fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁₀ -C ₂₀ oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) 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 1 -C ₁₆ -alkyl sulfates and C ₁₂ -C ₁₅ -alkyl sulfates and C ₁₄ -C ₁₅ -alkyl sulfates are preferred for reasons of washing technology. Also 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 Shell Oil Company under the name DAN ^® are suitable anionic surfactants.

The sulfuric acid monoesters of straight-chain or branched C ₇ ethoxylated with 1 to 6 mol of ethylene oxide. ₂₁ alcohols, such as 2-methyl-branched Cp-π alcohols with an average of 3.5 moles 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. Saturated fatty acid soaps are suitable, 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. 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 also 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, in particular in the form of the sodium salts. Preferred liquid detergents additionally contain anionic surfactants, preferably from the group of the alkyl sulfates, alkanesulfonates, alkylbenzenesulfonates, sulfuric acid monoesters and fatty acid soaps.

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

In addition, the agents according to the invention can contain organic solvents such as ethanol, n- or i-propanol, butanols, 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, l- Contain butoxyethoxy-2-propanol, butoxy-propoxy-propanol (BPP), 3-methyl-3-methoxybutanol, propylene glycol t-butyl ether and mixtures of these solvents, preferably in amounts not above 20% by weight, however, solvent-free agents are particularly preferred.

In the context of the present invention, the term “solvent-free” is to be understood as meaning agents which contain only small amounts or traces of the solvents listed above. In the “solvent-free” agents of the present invention, small amounts of solvents are therefore tolerable, which are preferably less than 2% by weight .-%, in particular less than 0.3% by weight, in each case based on the total agent.

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

In the context of the present invention, the term “non-aqueous” is to be understood as meaning agents which contain only small amounts of free water, ie not as water of crystallization or in other containing bound water. Since even non-aqueous solvents and raw materials (especially such technical qualities) have certain water contents, completely water-free agents can only be produced on an industrial scale with great effort and high costs. In the “non-aqueous” compositions of the present invention, small amounts of free water are therefore tolerable, which are below 5% by weight, preferably below 2% by weight, based in each case on the finished composition.

If necessary, non-aqueous agents can preferably contain bleaching agents. Of 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 bleaching agents that can be used are, for example, peroxopyrophosphates, citrate perhydrates and HO _2- providing peracid salts or peracids, such as persulfates. The urea peroxohydrate percarbamide can also be used, which can be described by the formula H ₂ N-CO-NH auch ₂ O. 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 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, paphthalimide, and 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, diperoxysebacic acid, diperoxybrassylthanoic acid, 1-diperoxybassyldiacid, diperoxybassyldiacid, diperoxybrassyl acid, diperoxybasic acid, , 4-diacid, N, N-terephthaloyl-di (6-aminopercaproic acid) can be used. The amount of bleach in the agents according to the invention is usually between see 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 total composition.

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. Preference is given to polyalkylated alkylenediamines, in particular tetraacetylethylene diamine (TAED), alkylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), aylated glycolurils, in particular tetraacetylglycoluril (TAGU ), N-acylimides, especially N-nonanoylsuccinimide (NOSI), aeylated phenol sulfonates, especially n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, especially phthalic anhydride, aeylated polyhydric alcohol triethyl acyl triethyl acyl triethyl acyl triethyl acyl triethyl acyl triethyl acyl triethyl acyl triethyl acyl triethyl acetic acid, , 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), aeylated sugar derivatives, in particular pentaacetyl glucose (PAG), pentaacetyl fructose, tetraacetylxylose and octaacetyl lactose as well as a cetylated, 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 16769 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 = CrC ₂ alkyl, preferably methyl and R ²¹ = C _r C ₂ alkyl, preferably methyl.

Bleach activators of this type are present in the customary quantitative range, preferably in amounts of 1% by weight to 15% by weight, in particular 2% by weight to 10% by weight, based on the total agent.

In addition to the conventional bleach activators listed above or in their place, the sulfonimines and / or bleach-enhancing transition metal salts or transition metal complexes known from European patents EP 0446 982 and EP 0 453 003 can also be present as so-called bleaching catalysts. The transition metal compounds in question include in particular the manganese, iron, cobalt, ruthenium or molybdenum-salt complexes known from German patent application DE 19529905 and their N-analog compounds known from German patent application DE 19620267, which are known from German patent application DE 195 36082 known manganese, iron, cobalt, ruthenium or molybdenum carbonyl complexes, the manganese, iron, cobalt, ruthenium, molybdenum, titanium, and vanadium and described in the German patent application DE 196 05 688 Copper complexes with nitrogen-containing tripod ligands, the cobalt, iron, copper and ruthenium amine complexes known from German patent application DE 19620411, the manganese, copper and cobalt complexes described in German patent application DE 44 16 438, the cobalt complexes described in European patent application EP 0 272 030, the manganese complexes known from European patent application EP 0 693 550, i The manganese, iron, cobalt and copper complexes known from the European patent EP 0 392 592, which consist of the international patent applications WO 96/23859, WO 96/23860 and WO 96/23861 known cobalt complexes and / or those in European patent EP 0443 651 or European patent applications EP 0458 397, EP 0458 398, EP 0 549271, EP 0 549 272, EP 0 544490 and EP 0 544 519 described manganese complexes. The bleach-enhancing active ingredient combination obtainable according to European patent application EP 0 832 969 can also be used in the compositions. Combinations of bleach activators and transition metal bleach catalysts are known, for example, from German patent application DE 196 13 103 and international patent application WO 95/27775. Bleach-enhancing transition metal complexes, in particular with the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, are used in customary amounts, preferably in an amount of up to 1% by weight, in particular 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 agent.

In addition to the substances mentioned, the agents according to the invention can contain further ingredients of detergents and 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 Active ingredients, 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 and solid agents.

The agents according to the invention can contain builders. All builders commonly used in detergents and cleaning agents can be incorporated into the agents according to the invention, 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 _{x + 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 x 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 disilicate Na ₂ Si ₂ O ₅ • yH ₂ O are preferred, whereby β-sodium disilicate can be obtained, for example, by the method 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 provide 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 within the scope of the present constricting invention is preferably usable, for example, also a co-crystallizate of zeolite X and zeolite A (ca. 80 wt .-% zeolite X) which is marketed by CONDEA Augu- sta SpA under the trade name AX VEGOBOND ^® and by the formula

nNa ₂ O • (ln) 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 also be used as over-dried zeolites with lower water contents and are then suitable due to their hygroscopicity for removing unwanted traces of free water.

Of course, it is also possible to use the generally known phosphates as builder substances, provided that such use should not be avoided for ecological reasons. The sodium salts of orthophosphates, pyrophosphates and in particular tripolyphosphates are particularly suitable.

Organic builder substances which can be used as cobuilders and which of course also serve to regulate viscosity are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids being understood to mean those carboxylic acids which carry more than one acid function. These are, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA) and their derivatives, and mixtures of these. 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. In addition to their builder effect, the acids typically also have the property of an acidifying component and serve thus also for setting a lower and milder pH value of detergents or cleaning agents. Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof can be mentioned in particular. Other acidifiers that can be used are known pH regulators such as sodium hydrogen carbonate and sodium hydrogen sulfate.

Polymeric polycarboxylates are also suitable as builders, for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative 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 particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship 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 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates with molecular weights of 2,000 to 10,000 g / mol, and particularly preferably 3,000 to 5,000 g / mol, can in turn be preferred from this group.

Suitable polymers can also comprise substances which consist partly or completely of units of vinyl alcohol or its derivatives.

Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable. Your relative mole Cooling mass, 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 be used either as an aqueous solution or preferably as a powder.

To improve water solubility, the polymers can also contain allylsulfonic acids, such as, for example, in EP-B-0727448 allyloxybenzenesulfonic acid and methallylsulfonic acid, as monomers.

Also particularly preferred are biodegradable polymers composed of more than two different monomer units, for example those which, according to DE-A-43 00772, are monomers salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or according to DE-C- 4221 381 contain as monomers salts of acrylic acid and 2-alkylallylsulfonic acid as well as 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 and preferably contain acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers.

Also to be mentioned as further preferred builder substances are polymeric aminodicarboxylic acids, their salts or their precursor substances. Particularly preferred are polyaspartic acids or their salts and derivatives, of which it is disclosed in the German patent application DE-A-195 40 086 that, in addition to cobuilder properties, they also have a bleach-stabilizing effect. Polyvinylpyrrolidones, polyamine derivatives such as quaternized and / or ethoxylated hexamethylene diamines are also suitable.

Further suitable builder substances are polyacetals, which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups, for example as described in European patent application EP-A-0 280 223. Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and their mixtures and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid. Also suitable as organic builder substances are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches. The hydrolysis can be carried out by customary, for example acid or enzyme-catalyzed, processes. They are preferably hydrolysis products with average molar masses in the range from 400 to 500,000 g / mol. A polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30, is preferred, DE being a customary measure of the reducing action of a polysaccharide compared to dextrose, which has a DE of 100 , is. Both 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 molar masses in the range from 2,000 to 30,000 g / mol can be used. A preferred dextrin is described in British patent application 94 19091.

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-0232 202, EP-A-0427349, EP-A-0472 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 , 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, preferably ethylenediaminisisuccinate, are further suitable cobuilders. Ethylene diamine N, N'-disuccinate (EDDS), the synthesis of which is described, for example, in US Pat. No. 3,158,615, is preferably used in the form of its sodium or magnesium salts. Also preferred in this context are glycerol disuccinates and glycerol trisuccinates, as described, for example, in US Pat. Nos. 4,524,009, 4,639,325, in European patent application EP-A-0 150 930 and in Japanese Patent application JP-A-93/339 896 can be described. Suitable amounts for use in formulations containing zeolite and / or silicate are 3 to 15% by weight.

Further usable organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may optionally also be in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups. Such cobuilders are described, for example, in international 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 water-soluble builders as builders, preferably from the group of the oligo- and polycarboxylates, the carbonates and the crystalline and / or amorphous silicates. Among these compounds, the salts of citric acid have proven to be particularly suitable, the alkali and, in particular, the sodium salts being preferred.

Solid particles can be prevented from settling in the washing or cleaning agents by adding rheological additives. These anti-settling agents often also function as builders or cobuilders and have therefore already been described above. Layer silicates such as bentonites and their organic modifications, polyacrylates, polycarboxylic acids, polysaccharides and their derivatives, activated polyamide derivatives, polyurethanes, polyvinylpyrrolidones, castor oil derivatives, polyamine derivatives such as quaternized and or ethoxylated hexamethylene diamines and any mixtures thereof can be mentioned as particularly suitable anti-settling agents.

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.

Suitable enzymes are in particular those from the classes of hydrolases such as proteases, esterases, lipases or lipolytically active enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. All these Hydrolases help remove stains such as protein, grease or starchy stains and graying in laundry. Cellulases and other glycosyl hydrolases can also help to retain color and increase the softness of the textile by removing pilling and microfibrils. Oxireductases can also be used to bleach or inhibit the transfer of color. Enzymatic active ingredients obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus and Humicola insolens are particularly suitable. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used. Enzyme mixtures, for example, from protease and amylase or protease and lipase or lipolytically active enzymes or protease and cellulase or from cellulase and lipase or lipolytically active enzymes or from protease, amylase and lipase or lipolytically active enzymes or protease, lipase or lipolytically active enzymes and cellulase, but especially protease and / or lipase-containing mixtures or mixtures with lipolytically active enzymes of particular interest. Known cutinases are examples of such lipolytically active enzymes. Peroxidases or oxidases have also proven to be suitable in some cases. Suitable amylases include in particular α-amylases, iso-amylases, pullulanases and pectinases. Cellobiohydrolases, endoglucanases and β-glucosidases, which are also called cellobiases, or mixtures thereof, are preferably used as cellulases. Since different types of cellulase differ in their CMCase and avicelase activities, the desired activities can be set by targeted mixtures of the cellulases.

The enzymes can be adsorbed or coated as a shaped body on carriers in order to protect them against premature decomposition. The proportion of the enzymes, enzyme mixtures or enzyme granules can be, for example, approximately 0.1 to 5% by weight, preferably 0.12 to approximately 2% by weight.

The salts of polyphosphonic acids, in particular, come as stabilizers, in particular for per-compounds and enzymes which are sensitive to heavy metal ions l-hydroxyethane-l, l-diphosphonic acid (HEDP), diethylenetriaminepentamethylenephosphonic acid (DETPMP), aminotri (methylenephosphonic acid) (ATMP) 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 0.5 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 can be indicated. All known acids or alkalis can be used here, provided that their use is not prohibited for application-related or ecological reasons or for reasons of consumer protection. The amount of these adjusting agents usually does not exceed 2% by weight of the total formulation.

In order to avoid the decomposition of certain ingredients of active detergent formulations catalyzed by heavy metals, substances can be used which complex heavy metals. The group of complexing agents includes, for example, the alkali metal salts of nitrilotriacetic acid (NTA) and alkali metal salts of anionic polyelectrolytes such as polyacrylates, polymaleates and polysulfonates. Low molecular weight hydroxycarboxylic acids such as citric acid, tartaric acid, malic acid or gluconic acid and their salts are also suitable. A preferred class of complexing agents are the phosphonates, which are present in preferred liquid detergent formulations in amounts of 0.01 to 3% by weight, preferably 0.02 to 2% by weight and in particular 0.03 to 1.5% by weight. -% are included. These preferred compounds include, in particular, organophosphonates such as, for example, l-hydroxyethane-l, l-diphosphonic acid (HEDP), aminotri (methylene-phosphonic acid) (ATMP), diethylenetriamine-penta (methylenephosphonic acid) (DTPMP or DETPMP) and 2-phosphonobutane-l , 2,4-tricarboxylic acid (PBS-AM), which are mostly used in the form of their ammonium or alkali metal salts. Colorants and fragrances are added to the agents according to the invention in order to improve the aesthetic impression of the products and, in addition to the washing or cleaning performance, to provide the consumer with a visually and sensorially "typical and unmistakable" product. Individual fragrance compounds, for example the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type, can be used as perfume oils or fragrances. Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert.-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methylphenyl glycinate, allylcyclohexylpropylate propionate. The ethers include, for example, benzylethyl ether, the aldehydes, for example, the linear alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal, the ketones, for example, the jonones, etc. -Isomethylionon and methyl-cedrylketone, the alcohols anethol, citronellol, eugenol, gera iol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons mainly include the terpenes such as limonene and pinene. However, preference is given to using mixtures of different fragrances which together produce an appealing fragrance. Perfume oils of this type can also contain natural fragrance mixtures such as are obtainable from plant sources, for example pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage oil, camel 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 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 it can also be advantageous to apply the fragrances to carriers which increase the adhesion of the perfume to the laundry and ensure a long-lasting fragrance of the textiles due to a slower fragrance release. Cyclodextrins, for example, have proven useful as such carrier materials, and the cyclodextrin-perfume complexes can additionally be coated with further auxiliaries. In order to improve the aesthetic impression of the agents according to the invention, they can be colored with suitable dyes. Preferred dyes, the selection of which is not difficult for the person skilled in the art, have a high storage stability and insensitivity to the other ingredients of the compositions and to light, and no pronounced substantivity towards textile fibers in order not to dye them.

Foam inhibitors that can be used in the compositions are, for example, soaps, paraffins or silicone oils, which can optionally be applied to carrier materials.

Graying inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the dirt from being re-absorbed. For this purpose, water-soluble colloids of mostly organic nature are suitable, for example glue, gelatin, salts of ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Water-soluble polyamides containing acidic groups are also suitable for this purpose. Soluble starch preparations and starch products other than those mentioned above can also be used, e.g. degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone can also be used. However, cellulose ethers such as carboxymethyl cellulose (sodium salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof in amounts of 0.1 to 5% by weight, based on the total agent, are preferred , used

Since textile fabrics, in particular made from rayon, wool, cotton and their mixtures, can tend to wrinkle because the individual fibers are sensitive to bending, kinking, pressing and squeezing transversely to the direction of the fibers, the agents can contain synthetic anti-crease agents. These include, for example, synthetic 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 products based on lecithin or modified phosphoric acid esters. To combat microorganisms, detergents or cleaning agents can contain antimicrobial agents. Depending on the antimicrobial spectrum and mechanism of action, a distinction is made between bacteriostatics and bactericides, fungistats and fungicides etc. Important substances from these groups are, for example, benzalkonium chlorides, alkylarylsulfonates, halogenophenols and phenol mercuric acetate. In the context of the teaching according to the invention, the terms antimicrobial activity and antimicrobial active substance have the customary meaning, as used, for example, by KH Wallhäußer in "Practice of Sterilization, Disinfection - Preservation: Germ Identification - Industrial Hygiene" (5th ed. - Stuttgart; New York: Thieme, 1995 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, isohiazolines, phthalimide derivatives, pyridine derivatives, antimicrobial surface-active compounds, guanidines, antimicrobial amphoteric compounds, quinolines, 1,2-dibromo-2,4-dicyanobutane, iodo- 2-propyl-butyl-carbamate, Io d, 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'-di-chloro-2'-hydroxydiphenyl ether (dichlosan) , 2,4,4'-trichloro-2'-hydroxydiphenyl ether (tri-chlosan), chlorhexidine, N- (4-chlorophenyl) -N- (3,4-dichlorophenyl) urea, N, N '- ( 1, 10-decanediyldi-1-pyridinyl-4-ylidene) bis (l-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 "^, ^ '-phenyldiguanido-N5, N ₅ ') -hexane-tetrahydochloride, 1, 6-Di- (Nι, Nι '-phenyl-Ni jNrmethyldigu anido-NsjNs ') -hexane dihydrochloride, 1,6-di- (N _b Ni'-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, ό-Di-fN i'-beta- - methoxyphenyl) diguanido-N ₅ , N ₅ '] -hexane-dihydrochloride, l, 6-di- (Nι , Nι'-alpha-methyl- .beta.-phenyldiguanido-N ₅ , N5 ') - hexane dihydrochloride, 1, 6-di- (Nι, Nι' -p-nitrophenyldiguanido-N ₅ , N ₅ ') hexane dihydrochloride, omega: omega-di- (Ni.Ni '- phenyldiguanido-N ₅ , N ₅ ') -di-n-propylether-dihydrochloride,

chlorophenyldiguanido-N ₅ , N ₅ ') -di-n-propylether-te-trahydrochloride, 1, 6-di- (N ι, N i' -2,4-dichlorophenyldiguanido-N ₅ , N ₅ ') hexane-tetrahydro -chloride, 1, 6-di- (Nj, Nι '-p- mefhylphenyldiguanido- N ₅ , N ₅ ') hexane dihydrochloride, l, 6-di- (N ₁ , N ₁ '-2,4,5- trichloropheny ldiguanido-N ₅ , N ₅ ') hexane-tetrahy drochloride, 1, 6-di- [N i, Nι' -alpha- (p-chlorophenyl) ethyldiguanido-N ₅ , N ₅ '] hexane-dihydrochloride, omega: omega-di- (Nι, Nι'-p-chlorophenyldiguanido-N ₅ , N ₅ ') m-xylene-dihydrochloride, 1, 12-Di- (Nι, Nι' -p- chlorophenyldiguanido-NsjNs') dodecane-dihydrochloride, 1, 10-Di- (N i, N ₁ '-pheny ldiguani- do- N ₅ , N5') - decan-tetrahy drochloride, l, 12-Di- (Nι, Nι'-phenyldiguanido-N5, N ₅ ' ) dodecane tetrahydrochloride, ljό-di-fuNi'-o-chlorophenyldiguanido-N5, N ₅ ') hexane dihydrochloride, Lό-Di-fNbNj'-o-chlorophenyldiguanido-N ₅ , N') hexane tetrahydrochloride, ethylene-bis - (l-tolyl biguanide), ethylene bis (p-tolyl biguanide), E hylene bis (3,5-dimethylphenyl biguanide), E 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 salts such as acetates, gluconates, hydrochlorides, hydrobromides, citrates, bisulfites, fluorides, polymaleates, N-cocoalkyl sarcosinates, phosphites, hypophosphites, perfluorooctanoates, sili- cate, sorbate, salicylate, maleate, tartrate, fumarate, ethylenediaminetetraacetate, iminodiacetate, cinnamate, thiocyanate, arginate, pyromellitate, tetracarboxybutyrate, benzoate, glutarate, monofluorophosphate, perfluoropropionate and any mixtures thereof. Halogenated xylene and cresol derivatives, such as p-chlorometacresol or p-chloro-meta-xylene, and natural antimicrobial active ingredients of vegetable origin (for example from spices or herbs), animal and microbial origin are also suitable. Antimicrobial surface-active quaternary compounds, a natural antimicrobial active ingredient of plant origin and / or a natural antimicrobial agent of animal origin, extremely preferably at least one natural antimicrobial agent 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 agent 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. 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 ^J ) (R ² ) (R ³ ) (R ⁴ ) NX ^~ , in which R ¹ to R ^{4 have the} same or different d-caralkyl radicals, C - C ₂₈ aralkyl radicals or heterocyclic radicals, where two or, in the case of an aromatic integration, such as in pyridine, even three radicals together with the nitrogen atom form the heterocycle, for example a pyridmium or imidazolinium compound, and X ^{~ represent} halide ions, sulfate ions, hydroxide ions or are 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 Methyl chloride, benzyl chloride, dimethyl sulfate, dodecyl bromide, but also ethylene oxide can be produced. The alkylation of tertiary amines with a long alkyl radical and two methyl groups is particularly easy, and the quaternization of tertiary amines with two long radicals and one methyl group can also be carried out using methyl chloride under mild conditions. Amines which have three long alkyl radicals or hydroxy-substituted alkyl radicals are not very reactive and are preferably quaternized with dimethyl sulfate.

Suitable QAC are, for example, benzalkonium chloride (N-alkyl-N, N-dimethylbenzylammonium chloride, CAS No. 8001-54-5), benzalkon B (m,? -Dichlorobenzyl- dimethyl-C12-alkylammonium chloride, CAS No. 58390-78-6), benzoxonium chloride (benzyl-dodecyl-bis (2-hydroxyemyl) ammonium chloride), cetrimonium bromide (N-hexadecyl-N, N-trimemyl-ammonium bromide, CAS No. 57-09-0), Benzetonium chloride (N, N-dimethyl-N- [2- [2- | - (l, l, 3,3-tetramethylbutyl) phenoxy-ethy] ethyl] ethylbenzylammonium chloride, CAS No. 121-54-0) , Dialkyldimethylammonium chloride such as di-n-decyldimethylammonium chloride (CAS No. 7173-51-5-5), didecyldimethylammonium bromide (CAS No. 2390-68-3), dioctyldimethylammoniumchloric, 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 Cg-Cig-alkyl radicals, in particular C ₂ -C ₄ -Aklyl-berιzyl-dimethyl-ammonium chloride.

Benzalkonium halides and / or substituted benzalkonium halides are for example commercially available as Barquat ^® ex Lonza, Marquat® ^® ex Mason, Vari quat ^® ex Witco / Sherex and Hyamine ^® ex Lonza and as Bardac ^® ex Lonza. Other commercially obtainable antimicrobial agents are N- (3-chloroallyl) - hexaminiumchlorid as Dowicide and Dowicil ^{® ®} ex Dow, benzethonium chloride such as Hyamine ^® 1622 ex Rohm & Haas, methylbenzethonium as Hyamine ^® 10X ex Rohm & Haas, cetylpyridinium chloride such as Cepacol ex Merrell Labs ,

The antimicrobial active ingredients are used in amounts of from 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% by weight .-% 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 classes of substances 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 Esters of 3,3'-thiodipropionic acid with Cι.ι ₈ alkanols, in particular Cio-is-alkanols, metal ion deactivators, which are able to complex the auto-oxidation catalyzing metal ions, such as copper, 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 additionally added to the agents. Antistatic agents increase the surface conductivity and thus enable the flow of charges that have formed to improve. External antistatic agents are generally substances with at least one hydrophilic molecular ligand and give a more or less hygroscopic film on the surfaces. These mostly surface-active antistatic agents can be divided into nitrogen-containing (amines, amides, quaternary ammonium compounds), phosphorus-containing (phosphoric acid esters) and sulfur-containing (alkyl sulfonates, alkyl sulfates) 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) dimethylbenzylammonium chlorides disclosed here are suitable as antistatic agents for textiles or as an additive to the non-aqueous liquid detergents according to the invention, an additional finishing effect being 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 the 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 polydimethylsiloxanes, which can optionally be derivatized and then ammo-functional or quaternized or have 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, the Silicones in amounts between 0.2 and 5 wt .-%, based on the total agent can be used.

The agents can contain UV absorbers, which absorb onto the treated textiles and improve the lightfastness of the fibers and / or the lightfastness of the other formulation components. UV absorbers are understood to mean organic substances (light protection filters) which are able to absorb ultraviolet rays and release the absorbed energy in the form of longer-wave radiation, for example heat. Compounds which have these desired properties are, for example, the compounds and derivatives of benzophenone which are active by radiationless deactivation and have substituents in the 2- and / or 4-position. In addition, substituted benzotriazoles, such as the water-soluble benzenesulfonic acid-3- (2H-benzottiazol-2-yl) -4-hydroxy-5- (methylpropyl) monosodium salt (Ciba ^® Fast H), in 3- phenyl-substituted acrylates (cinnamic acid derivatives) , where appropriate with cyano groups in the 2-position, salicylates, organic Ni complexes and natural substances such as umbelliferone and the body's own urocanoic acid. Of particular importance are Bi- phenyl and above all, stilbene derivatives described, for example in EP 0728749 A and commercially Tinosorb FD ^{® ®} or Tinosorb FR ex Ciba than. The UV-B absorbers that may be mentioned are 3-benzylidene camphor or 3-benzylidene norcampher and its derivatives, for example 3- (4-methylbenzylidene) camphor, as described in EP 0693471 B1; 4-aminobenzoic acid derivatives, preferably 2-ethyl-hexyl 4- (dimethylamino) benzoate, 2-octyl 4- (dimethylamino) benzoate and amyl 4- (dimethylamino) benzoate; Esters of cinnamic acid, preferably 2-ethylhexyl 4-methoxycinnamate, propyl 4-methoxycinnamate, isoamyl 4-methoxycinnamate, 2-ethylhexyl 2-cyano-3, 3-phenylcinnamate (oc-tocrylene); Esters of salicylic acid, preferably salicylic acid 2-ethylhexyl ester, 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, for example, 2,4,6-trianilino- (p-carbo-2'-ethyl- -hexyloxy) -l, 3,5-triazine and octyl triazone, such as described in EP 0818450 AI or dioctyl butamido triazone (Uvasorb® HEB); Propane-1,3-diones such as 1- (4-tert-butylphenyl) -3- (4'-methoxyphenyl) propane-1,3-dione; Ketotricyclo (5.2.1.0) decane derivatives, as described in EP 0694521 B1. Also suitable are 2-phenylbenzimidazole-5-sulfonic acid and its alkali, alkaline earth, ammonium, alkylammonium, alkanolammonium and glucammonium salts; Sulfonic acid derivatives of benzophenones, preferably 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its salts; Sulfonic acid derivatives of 3-benzylidene camphor, such as 4- (2-oxo-3-bornylidene methyl) benzol sulfonic acid and 2-methyl-5- (2-oxo-3-bornylidene) sulfonic acid and their salts.

Derivatives of benzoylmetbane are particularly suitable as typical UV-A filters, such as, for example, 1- (4'-tert-butylphenyl) -3- (4'-mefhoxyphenyl) propane-1,3-dione, 4-butyl- 4'-methoxydibenzoylmethane (Parsol 1789), l-phenyl-3- (4'-isopropylphenyl) propane-l, 3-dione and enamine compounds, as described in DE 19712033 AI (BASF). The UN-A and UV-B filters can of course also be used in mixtures. In addition to the soluble substances mentioned, insoluble light-protection pigments, namely finely dispersed, preferably nanoized metal oxides or salts, are also suitable for this purpose. Examples of suitable metal oxides are, in particular, zinc oxide and titanium dioxide and, in addition, oxides of iron, zirconium, silicon, manganese, aluminum and cerium and mixtures thereof. Silicates (talc), barium sulfate or zinc stearate can be used as salts. The oxides and salts are already used in the form of the pigments for skin-care and skin-protecting emulsions and decorative cosmetics. The particles should have an average diameter of less than 100 nm, preferably between 5 and 50 nm and in particular between 15 and 30 nm. They can have a spherical shape, but it is also possible to use particles which have an ellipsoidal shape or a shape which differs from the spherical shape in some other way. The pigments can also be surface-treated, ie hydrophilized or hydrophobicized. Typical examples are coated titanium dioxides such as titanium dioxide T 805 (Degussa) or Eusolex® T2000 (Merck). Silicones, and in particular trialkoxyoctylsilanes or simethicones, are particularly suitable as hydrophobic coating agents. Micronized zinc oxide is preferred used. Further suitable UV light protection filters can be found in the overview by P.Finkel in SÖFW-Journal 122, 543 (1996).

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

Optical brighteners (so-called "whiteners") can be added to the agents according to the invention in order to eliminate graying and yellowing of the treated textiles. These substances attach to the fibers and bring about a brightening and simulated bleaching effect by converting invisible ultraviolet radiation into visible longer-wave light, whereby the ultraviolet light absorbed from the sunlight is emitted as a slightly bluish fluorescence and results in pure white with the yellow tone of the grayed or yellowed laundry. For example, salts of 4,4'-bis (2-anilino-4-morpholino-l, 3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of similar structure which carry a diefhanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group instead of the morpholino group brightener of the type of. substituted diphenyl be present, for example, 2-sul alkali metal salts of ^4,4-bis ( fostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) 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'-stilbenedisulfonic acids (flavonic acids), 4,4'-distyryl-biphenyls, methylumbelliferones, coumarins, dihydroquinolinones, 1,3-diarylpyrazolines and Νaphthalic acid - rhyme, benzoxazole, benzisoxazole and benzimidazole systems as well as the pyrene derivatives substituted by heterocycles. Mixtures of the aforementioned brighteners can also be used.

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

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

The agents according to the invention are produced in a manner known per se by mixing the ingredients in stirred tanks. If it is desired for a certain end product, the solids contained in the agents according to the invention can be further comminuted by a wet grinding step in order to further increase the separation stability of the agents. For such operations familiar to the person skilled in the art, for example, colloid mills, roller mills or annular gap or agitator ball mills are suitable. The carboxylic acid alkoxylates to be used according to the invention can be added at any point in such a conventional manufacturing process. Usually, the bleaching agents and bleach activators that may be present are not incorporated into the agents together prior to grinding, since 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 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 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 (for example detergent pastes for automatic dispensers in commercial washing machines), a significant higher viscosity should be indicated - this can lead to dimensionally stable masses in which a viscosity in the above sense can no longer be meaningfully stated.

Examples

The following example El demonstrates a composition of the liquid detergents according to the invention. VI was selected as the comparative composition. The information in Table 1 appears in percent by weight and relates to the total average. Table 1

The washing properties of the agent E1 according to the invention were determined in a washing test in a washing machine in comparison to VI. 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. Test conditions: UV filter at 460 nm, aperture 30 mm, light type D65. The measured color difference values give the visual impression of changes in color of colored textiles after washing. The color location of a sample in the color space was determined in accordance with the publication CIE No. 15.2, 1986 by measuring L, a and b values. ^'

The washing performance was comparable over 15 stains; however, there was an improved washing effect for the lipstick soiling (lipstick: Marbert No. 40) (Table 2). Table 2: Average remission values (3-fold determination) for a lipstick soiling (lipstick: Marbert No. 40) refined on polyester cotton

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

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.

Sokalan ^® CP 5 ex BASF: maleic acid-acrylic acid copolymer sodium salt (30:70) Dehydol ^® LT7 ex Cognis GmbH (C12-18 + 7EO) Dehypon ^® LS54 ex Cognis GmbH (C12-14 + 5EO, 4 PO)

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

The viscosity measurements of the agents E2 to E7 according to the invention show a dependence of the viscosity on the shear rate. For E2 to E7, the viscosity decreases with increasing shear rate. The agents thus show pseudoplastic or thixotropic behavior.

Claims

claims

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 in that the agent liquid alkylene glycol carboxylic acid esters in amounts of 0.1 wt .-% to 99 wt .-%, preferably from 5 wt .-% to 80 wt .-% and particularly preferred from 21% by weight to 70% by weight, based in each case on the total composition.

3. Liquid detergent according to one of the preceding claims, characterized in that the agent contains liquid ethylene glycol carboxylic acid esters.

4. liquid detergent according to one of the preceding claims, characterized in that the means as Ethylenglycolcarbonsäureester C _6-1 carboxylic acids with 1 EO, in particular nonanoic acid with 1 EO or benzoic acid and their derivatives with 1 EO contains.

5. Liquid detergent according to one of the preceding claims, characterized in that the agent nonionic (s) surfactant (s) in amounts of 0.01 wt .-% to 90 wt .-%, preferably 1 wt .-% to 80 wt. -% and in particular 5 wt .-% to 70 wt .-%, based on the total agent contains.

6. Liquid detergent according to one of the preceding claims, characterized in that the agent anionic surfactants in amounts of 0.01 wt .-% to 80 wt .-%, preferably from 1 wt .-% to 60 wt .-%, particularly preferred from 5% by weight to 40% by weight, based in each case on the total composition.

7. Liquid detergent according to one of the preceding claims, characterized in that the agent contains betaines or cationic surfactants.

8. Liquid detergent according to one of the preceding claims, characterized in that the agent contains no other organic solvents.

9. Liquid detergent according to one of the preceding claims, characterized in 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 washing or cleaning agents.

11. Use of liquid alkylene glycol carboxylic acid esters according to claim 10, characterized in that the alkylene glycol carboxylic acid esters in amounts of 0.1 wt.% To 99 wt.%, Preferably 5 wt.% To 80 wt.% And particularly preferably 21 % By weight to 70% by weight, based in each case on the total composition, can be used.