EP2663625A1 - Use of optionally oxidized thioethers of alcohol alkoxylates in detergents and cleaning agents - Google Patents

Abstract

The invention relates to the use of (oxidized) thioethers of alcohol alkoxylates in detergents and cleaning agents, especially in dishwashing detergents, and to detergents and cleaning agents, especially dishwashing detergents, containing (oxidized) thioethers of alcohol alkoxylates. Said (oxidized) thioethers are especially suitable for use as surfactants having rinse aid function (rinse aid surfactants). The term "oxidized" refers to the sulfur atom in the thioether, which may be present in oxidized form as a sulfoxide (SO) or sulfonyl (SO2).

Description

 Use of optionally oxidized thioethers of alcohol alkoxylates in detergents and cleaners

description

The present invention relates to the use of (oxidized) thioethers of alcohol alkoxylates in detergents and cleaners, especially in dishwashing detergents, and detergents and cleaners, especially dishwashing detergents containing (oxidized) thioethers of alcohol alkoxylates. These (oxidized) thioethers are suitable in particular as surfactants with rinse aid function (rinse aid surfactants). "Oxidized" refers to the sulfur atom in the thioether which may be in oxidized form as the sulfoxide (SO) or sulfonyl (SO2).

Surfactants are substances that can lower the interfacial tension. Typically, surfactants have a characteristic structure and have at least one hydrophilic and at least one hydrophobic functional group. If both parts of the molecule are in equilibrium, the substance will accumulate and align at an interface, i. hydrophilic groups, for example, in an aqueous phase and the hydrophobic groups in the direction of other solid, liquid or gaseous phases. Another special feature of surfactants is the formation of higher aggregates, the so-called micelles. In these, the surfactant molecules arrange in such a way that the polar groups form, for example, a spherical shell. This causes substances such as dirt particles in an aqueous solution to become soluble to form micelles. Therefore, surfactants are particularly suitable for cleaning surfaces and as an additive in detergents.

Surfactants having a hydrophobic and a hydrophilic block are widely used. However, their tendency to foaming makes them for many applications not or only partially usable. For applications where strong foaming is not desired, nonionic surfactants have therefore been developed which have a second hydrophobic block, which limits the foam volume.

The second hydrophobic block can be derived, for example, from a fatty alcohol. However, the use of dishwashing detergents which contain such a surfactant, in particular dishwashing detergents for dishwashers, frequently results in residues remaining on the dishes cleaned therewith (so-called "spotting" in the case of the formation of punctiform linings or "filming") "in the case of film-like coverings). The second hydrophobic block may alternatively be derived from a fatty acid. In the case of dishwashing detergents which contain such surfactants, the problem of deposit formation is no longer so great; However, due to the ester group, these surfactants are sensitive to hydrolysis, which severely restricts their usability in alkaline formulations and at relatively high temperatures, in particular during prolonged washing operations.

Thioethers of alcohol alkoxylates and their oxidized form (i.e., the sulfoxides and sulfones) are basically known; e.g. from US 3,627,845. This document describes the use of such compounds as biologically active agents, e.g. as fungicides, acaricides and anthelmintics, and as surface active agents in agrochemical formulations and coating agents. A use as a detergent or cleaning agent is not mentioned.

The object of the present invention was to provide compounds which do not have the disadvantages of the surfactants of the prior art. In particular, the compounds should have no or no strong foaming tendency; they should leave less residue, especially spotting residue, on dishes washed therewith, and they should not or at least be less susceptible to hydrolysis than the fatty acid ester-based surfactants. In particular, however, the compounds should have the highest possible melting point, so that they can also be formulated in solid detergents and cleaners.

The object is achieved by the use of compounds of the formula I R-0-f CH ₂ CH (R ¹⁾ m} -OHCH2CH2-0-fCH2CH (R ²⁾ -0} n-CH2CH2-S (0) x R '(I in which

R is C ₈ -C ₂ 4 alkyl;

R 'is C ₆ -C 18 -alkyl;

R ¹ and R ² independently and independently of their occurrence for

Ci-Cs-alkyl;

m is a number from 10 to 100;

 I and n independently represent a number from 0 to 15; and

x is 0, 1 or 2; in detergents or cleaners, especially in dishwashing detergents. In addition, the invention relates to detergents or cleaners, in particular dishwashing agents, containing at least one compound of the formula I as defined above. In the context of the present invention, C 1 -C 8 -alkyl is a linear or branched alkyl radical having 1 to 5 carbon atoms. Examples of these are methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl and position isomers thereof. Cβ-Cis-alkyl represents a linear or branched alkyl radical having 6 to 18 carbon atoms. Examples of these are hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, 2-propylheptyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl and positional isomers thereof. Cs-C24-alkyl is a linear or branched alkyl radical having 8 to 24 carbon atoms. Examples of these are octyl, 2-ethylhexyl, nonyl, decyl, 2-propylheptyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, henicosyl, docosyl, tricosyl, tetracosyl and positional isomers thereof.

Branched Cs-C24 alkyl are the positional isomers of octyl, such as 2-ethylhexyl, the positional isomers of n-nonyl, the positional isomers of n-decyl, such as 2-propylheptyl, the positional isomers of n-undecyl, the positional isomers of n-dodecyl, the position isomers of n-tridecyl, the positional isomers of n-tetradecyl, the positional isomers of n-pentadecyl, the positional isomers of n-hexadecyl, the positional isomers of n-heptadecyl, the positional isomers of n-octadecyl, the positional isomers of n-nonadecyl , the positional isomers of n-eicosyl, the positional isomers of n-henicosyl, the positional isomers of n -docosyl, the positional isomers of n-tricosyl, and the positional isomers of n-tetracosyl.

Cio-Ci4-alkyl is a linear or branched alkyl radical having 10 to 14 carbon atoms. Examples of these are decyl, 2-propylheptyl, undecyl, dodecyl, tridecyl, tetradecyl and positional isomers thereof. Branched C 1 -C 4 -alkyl are the positional isomers of n-decyl such as 2-propylheptyl, the positional isomers of n-undecyl, the positional isomers of n-dodecyl, the positional isomers of n-tridecyl and the positional isomers of n-tetradecyl. Cio-C 15 -alkyl is a linear or branched alkyl radical having 10 to 15 carbon atoms. Examples of these are decyl, 2-propylheptyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl and positional isomers thereof. Branched cio-cis-alkyl are the positional isomers of n-decyl, such as 2-propylheptyl, the positional isomers of n-undecyl, the positional isomers of n-dodecyl, the positional isomers of n-tridecyl, the positional isomers of n-tetradecyl and the positional isomers of n-pentadecyl. Cs-Cis-alkyl is a linear or branched alkyl radical having 8 to 15 carbon atoms. Examples thereof are the radicals mentioned above for C 1 -C 6 -alkyl and also octyl, 2-ethylhexyl, nonyl and positional isomers thereof.

Branched Cs-Cis-alkyl are the positional isomers of octyl, such as 2-ethylhexyl, the positional isomers of n-nonyl, the positional isomers of n-decyl, such as 2-propylheptyl, the positional isomers of n-undecyl, the positional isomers of n-dodecyl, the positional isomers of n-tridecyl, the positional isomers of n-tetradecyl, and the positional isomers of n-pentadecyl. Ci2-alkyl stands for dodecyl and its position isomers.

The following remarks on preferred embodiments, in particular on preferred embodiments of the compounds I, their use and the agents containing them, apply both alone and in any conceivable combination with one another. Unless otherwise stated, the statements apply both to the use according to the invention and to the detergents and cleaners according to the invention.

The compounds I used according to the invention may be chemically pure substances or mixtures of different compounds I. As a rule, because of its preparation process and the educts used therein, which may be technical products or product mixtures, it will be mixtures of different compounds I, which can be understood, for example, to be the variables R, R ', I, m, n and /. or x differ.

In the compounds I, R is preferably Cs-Cis-alkyl, particularly preferably Cio-Cis-alkyl and especially Cio-C-alkyl. In a specific embodiment, the alkyl radical R is branched. Specific examples of R are 2-propylheptyl, tridecyl and des- positional isomers such as isotridecyl (ie branched tridecyl radicals and mixtures thereof), n-dodecyl (lauryl), n-tetradecyl (myristyl) and mixtures thereof.

R 'is preferably C 1 -C 4 -alkyl and in particular C 1 -C 2 -alkyl (dodecyl); espe- cially for n-dodecyl.

R ¹ and R ² independently of one another preferably represent methyl. m is preferably from 20 to 50, more preferably from 25 to 50, more preferably from 25 to 45, and most preferably from 25 to 40.

I and n independently of one another preferably represent a number from 0 to 5 and particularly preferably 0, 1, 2 or 3. In particular, I and n represent 0. If at least one of the indices I or n does not stand for 0, the Ethylenoxy repeat units (-CH2-CH2-O-) and the repeating units (-CH ₂ -CH (R ¹ ) -O- and / or (-CH ₂ -CH (R ² ) -O-) randomly or in blocks Preferably, they are arranged in blocks, ie all optional repeating units -CH 2 -CH (R ¹ ) -O- form a block which is followed by the ethyleneoxy block (-CH 2 -CH 2 -O-) _m connect all optionally repeating units -CH ² -CH (R ² ) -O- as a block, x preferably stands for 0 or 1. The compounds I are distinguished by a relatively high melting point, preferably the melting point is at least 35 ° C., eg 35 to 50 ° C, preferably 35 to 47 ° C and especially 35 to 45 ° C, particularly preferably at least 38 ° C, eg 38 to 50 ° C, preferably 38 to 47 ° C and especially 38 to 45 ° C; and in particular at least 40 ° C, for example 40 to 50 ° C, preferably 40 to 47 ° C and in particular 40 to 45 ° C.

Processes for the preparation of compounds I are known in principle; for example from US 3,627,845. Thus, in the case where I is other than 0, an alcohol R-OH with an epoxide

and then reacted with ethylene oxide. The product obtained is then in the event that n is different from 0, with an epoxide

 0 reacted. This is followed by the reaction with a mercaptoethanol R'-S-Ch Ch -OH to give compound I. If x is to stand for 1 or 2, the resulting thioether is subsequently oxidized.

The reaction with the epoxides is preferably carried out in anhydrous medium under base catalysis. The reaction preferably takes place under an inert gas atmosphere, such as nitrogen or argon. Preferably, the reaction is carried out in bulk, i. without further solvents. Suitable bases include, for example, inorganic bases such as alkali metal hydroxides, e.g. Lithium, sodium or potassium hydroxide, alkaline earth metal hydroxides, e.g. Magnesium or calcium hydroxide, alkali metal carbonates, e.g. Lithium, sodium or potassium carbonate, or alkaline earth metal carbonates, e.g. Magnesia or calcium carbonate. Preference is given to sodium and potassium hydroxide. The reaction temperature is preferably 50 to 200 ° C, more preferably 100 to 150 ° C. The reaction is preferably carried out under elevated pressure, e.g. at 1, 1 to 10 bar or 1, 2 to 5 bar, which is built up by the inert gas and / or the epoxide (in particular ethylene oxide). In a preferred embodiment, a pre-pressure with inert gas, usually nitrogen, is built up prior to introduction of the epoxide. Preferably, this form is in the range of 1.1 to 5 bar, more preferably from 1 .2 to 3 bar and in particular from 1 .2 to 2 bar. The addition of the epoxide (in particular ethylene oxide) then generally leads to a further pressure increase. The pressure during the actual reaction is in the range of preferably from 1 .2 to 10 bar, more preferably from 2 to 8 bar. After the reaction, the resulting product mixture can be neutralized if desired.

The condensation with the mercaptoethanol is preferably carried out under acidic catalysis. Suitable acids are, for example, p-toluenesulfonic acid, methanesulfonic acid, phosphoric acid and acid ion exchangers. During the reaction, preferably, the formed reaction water is removed, e.g. by azeotropic distillation or stripping with an inert gas. If the water of reaction is to be removed by azeotropic distillation, the condensation is advantageously carried out in a solvent which forms a minimum azeotrope with water, such as toluene or the xylenes. After the reaction, the resulting product mixture can be neutralized if desired.

The oxidation of the sulfur atom in the obtained thioether to give the sulfoxide (x = 1) or sulfone (x = 2) can be carried out by means of conventional oxidizing agents, such as hydrogen peroxide, brown oxide. stone, a permanganate, m-chloroperbenzoic acid or a perchlorate. Whether the oxidation proceeds to the sulfoxide or to the sulfone can be determined inter alia by the choice of the oxidizing agent, its concentration and by the reaction temperature.

The compounds I can be used according to the invention in the form of the solution obtained in their preparation. Preferably, however, they are isolated by conventional methods and, if desired, purified. The compounds of the formula I can in principle be used in all common detergents and cleaners.

In the context of the present invention, detergents are understood to mean those agents which are used for cleaning flexible materials with high absorbency, e.g. of materials having a textile character, while cleaning agents in the context of the present invention are understood to mean those agents which are suitable for cleaning closed-surface materials, i. with a surface which has no or only a few and small pores and consequently has no or only a low absorbency.

Examples of flexible materials with high absorbency are those which contain or consist of natural, synthetic or semisynthetic fiber materials and which therefore generally have at least in part a textile character. The fibrous or fibrous materials may in principle be in any form found in use or in manufacture and processing. For example, fibers may be present randomly in the form of flake or debris, ordered in the form of threads, yarns, threads, or in the form of fabrics such as nonwovens, loden fabrics or felt, fabrics, knitted fabrics in all conceivable weave types. The fibers may be raw fibers or fibers at any stage of processing. Examples are natural protein or cellulose fibers, such as wool, silk, cotton, sisal, hemp or coconut fibers, or synthetic fibers, such as polyester, polyamide or polyacrylonitrile fibers.

Examples of materials that have little or no pores and little or no absorbency are metal, glass, enamel or ceramic. Typical objects from these materials are, for example, metal sinks, cutlery, glass and porcelain dishes, bathtubs, sinks, tiles, cured synthetic resins, such as decorative melamine resin surfaces on kitchen furniture or painted metal surfaces such as refrigerators and car bodies, printed circuit boards. printed circuit boards, microchips, sealed or lacquered woods, eg parquet or wall coverings, window frames, doors, plastic coverings such as floor coverings made of PVC or hard rubber, or hard or soft foams with largely closed surfaces.

Examples of detergents containing the compounds I include dishwashing detergents such as hand dishwashing detergents or dishwasher detergents, metal degreasers, glass cleaners, floor cleaners, all-purpose cleaners, high-pressure cleaners, neutral cleaners, alkaline cleaners, acid cleaners, spray degreasers, dairy cleaners, large kitchen cleaners, apparatus cleaners in the industry, in particular the chemical industry, cleaner for car wash and also household all-purpose cleaner.

The compounds I are preferably used in dishwashing detergents. With particular preference, they are used in machine dishwashing detergents. Dishwashing agents, in particular machine dishwashing detergents, with rinse aid function are preferred among these.

The detergents and cleaners containing the compounds I are preferably solid at room temperature (20 ° C.).

The solid detergents and cleaning agents may be powdered or tabular products ("tabs"). Preferably, they are tablet-shaped products ("tabs"). Particularly preferred are tablet-shaped dishwashing detergents, in particular tablet-shaped dishwasher detergents.

Tablet-shaped dishwashing detergents may be simple tabs or else so-called "2 in 1", "3 in 1", "5 in 1", "7 in 1" products and the like (multifunctional products; x in 1 "products with x = integer). For details on these formulations can be found in Hermann G. Hauthal, G. Wagner (ed.), Cleaning and care products in the household, publishing house for chemical industry, H. Ziolkowsky GmbH, Augsburg 2003, Chapter 4.2, pages 161-184. "2 in Γ products also contain a rinse aid in addition to the usual components of dishwasher detergents." 3 in 1 "products also contain a water softener." 5 in 1 "products generally also contain a glass preservative and a rinse aid." 7 in 1 "products also contain a stainless steel gloss agent and an encrusting agent. Preferably, the compounds I are used in tablet-form multifunctional machine dishwashing detergents, where they completely or partially replace the customary rinse aids. The compounds I have both an effect as a surfactant and as a rinse aid. Therefore, the invention also relates to the use of the compounds I as a surfactant and / or as a rinse aid. In particular, the invention relates to the use of the compounds I as a surfactant with a clear rinse effect or as a rinse aid surfactant. The compounds I used according to the invention are distinguished, in particular, by an outstanding deposit-inhibiting action when used in the rinse cycle of the automatic dishwashing machine. They act both against inorganic and against organic deposits inhibiting. The inorganic coverings are, in particular, calcium and magnesium phosphate, carbonate, silicate and / or phosphonate, which are formed from the calcium and magnesium salts contained in the water and the builders contained in conventional dishwashing detergents. The organic coverings are, in particular, dirt components from the wash liquor, such as, for example, protein, starch and fat deposits. The compounds I used according to the invention are also active in relation to so-called carry-over coverings, which originate from the residual water quantity in the bottom of the dishwasher and which contain, inter alia, dishwasher residues and possibly also dirt residues from the previous wash cycle of the dishwasher.

Another object of the invention are detergents or cleaning agents containing at least one compound of formula I. With regard to suitable washing or cleaning agents, reference is made to the above statements.

The washing and cleaning agents are preferably dishwashing agents, of which machine dishwashing detergents are preferred. In particular, it concerns dishwashing detergents, in particular machine dishwashing detergents, with a rinse aid function.

The washing and cleaning agent according to the invention is preferably solid at room temperature (20 ° C.). With regard to suitable and preferred solid washing and cleaning agents, reference is made to the above statements. In particular, the washing and cleaning agents according to the invention are tablet-shaped multifunctional machine dishwashing detergents. In these compounds I may be contained in the final rinse; however, they are preferably present as a solid in the tablet-shaped dishwashing detergent. The dishwashing agent according to the invention preferably comprises the following constituents:

a) at least one compound of the formula I;

b) at least one builder (also referred to as sequestering agent, builder, complexing agent, chelator, chelating agent or softening agent);

c) optionally at least one enzyme; and

d) optionally at least one bleaching agent; and

e) optionally at least one further additive which is preferably selected from surfactants other than a), bases, corrosion inhibitors, defoamers, dyes, fragrances, fillers, tableting aids, disintegrating agents, thickeners, solubilizers, organic solvents and water. These constituents are preferably present in the following proportions in the dishwashing composition according to the invention: a) at least one compound of the formula I: from 0.1 to 20% by weight;

b) at least one builder: from 5 to 80% by weight;

c) at least one enzyme: from 0 to 8% by weight;

d) at least one bleaching agent: from 0 to 30% by weight; and

e) at least one further additive: from 0 to 50% by weight.

The weight percentages relate to the total weight of the dishwashing detergent. The amounts by weight of a) to e) add up to 100 wt .-%.

The dishwashing agent according to the invention particularly preferably comprises at least one enzyme. The abovementioned constituents are particularly preferably contained in the following proportions in the dishwashing composition according to the invention: a) at least one compound of the formula I: from 0.1 to 10% by weight;

b) at least one builder: from 20 to 80% by weight;

c) at least one enzyme: from 0.1 to 6% by weight;

d) at least one bleaching agent: from 0 to 30% by weight; and

e) at least one further additive: from 0 to 50% by weight. The percentages by weight relate to the total weight of the dishwashing detergent. The amounts by weight of a) to e) add up to 100 wt .-%.

More preferably, the dishwashing agent of the invention further comprises at least one bleaching agent.

More preferably, the abovementioned constituents are present in the following proportions in the dishwashing composition according to the invention: a) at least one compound of the formula I: from 0.1 to 10% by weight;

b) at least one builder: from 20 to 80% by weight;

c) at least one enzyme: from 0.1 to 6% by weight;

d) at least one bleaching agent: from 5 to 25% by weight; and

e) at least one further additive: from 0 to 50% by weight.

The percentages by weight relate to the total weight of the dishwashing detergent. The amounts by weight of a) to e) add up to 100 wt .-%.

With regard to suitable and preferred compounds I, reference is made to the above statements.

Builders, sometimes referred to as sequestrants, builders, chelating agents, chelants, or softeners, bind alkaline earth metals and other water-soluble metal salts without precipitation. They help to break up dirt, disperse dirt particles, help to loosen dirt and sometimes have their own washing effect. In addition, when they are solid and used in powdered formulations, they keep the powder free-flowing.

Suitable builders can be both organic and inorganic in nature. Examples are aluminosilicates, carbonates, phosphates and polyphosphates, polycarboxylic acids, polycarboxylates, hydroxycarboxylic acids, phosphonic acids, for example hydroxyalkylphosphonic acids, phosphonates, aminopolycarboxylic acids and their salts, and polymers containing carboxylic acid groups and salts thereof. Suitable inorganic builders are, for example, crystalline or amorphous aluminosilicates with ion-exchanging properties, such as zeolites. Various types of zeolites are suitable, in particular zeolites A, X, B, P, MAP and HS in their Na form or in forms in which Na is partially exchanged with other cations such as Li, K, Ca, Mg or ammonium. Suitable zeolites are described, for example, in US Pat. 4604224. Crystalline silicates suitable as builders are, for example, silicates or sheet silicates, for example 5-Na ₂ Si ₂ O ₅ or B-Na ₂ Si ₂ O ₅ (SKS 6 or SKS 7). The silicates may be used in the form of their alkali metal, alkaline earth metal or ammonium salts, preferably as Na, Li and Mg silicates. Amorphous silicates, such as, for example, sodium metasilicate, which has a polymeric structure, or amorphous disilicate (Britesil® H 20 manufacturer: Akzo) can also be used. Preferred among these is sodium disilicate.

Suitable inorganic builders based on carbonate are carbonates and bicarbonates. These can be used in the form of their alkali metal, alkaline earth metal or ammonium salts. Preference is given to using Na, Li and Mg carbonates or bicarbonates, in particular sodium carbonate and / or sodium bicarbonate. Typical phosphates used as inorganic builders are alkali metal orthophosphates and / or polyphosphates, such as e.g. Pentasodium.

Suitable organic builders are, for example, C ₄ -C 30 -di-, -tri- and -tetracarboxylic acids, such as succinic acid, propanetricarboxylic acid, butanetetracarboxylic acid, cyclopentane-tetracarboxylic acid and alkyl- and alkenylsuccinic acids with C ₂ -C ₂ 0-alkyl- or alkenyl- residues.

Suitable organic builders are furthermore hydroxycarboxylic acids and polyhydroxycarboxylic acids (sugar acids). These include C ₄ -C 20 -hydroxycarboxylic acids, such as, for example, acetic acid, tartaric acid, gluconic acid, mucic acid, lactic acid, glutaric acid, citric acid, tartronic acid, glucoheptonic acid, lactobionic acid and sucrose mono-, di- and tricarboxylic acid. Preferred among these are citric acid and its salts.

Suitable organic builders are also phosphonic acids, e.g. Hydroxyalkylphosphonic acids, aminophosphonic acids and the salts thereof. These include e.g. Phosphonobutanetricarboxylic acid, aminotris-methylenephosphonic acid, ethylenediaminetetraethylenephosphonic acid, hexamethylenediamine tetramethylenephosphonic acid, diethylenetriaminepentamethylenephosphonic acid, morpholino-methanediphosphonic acid, 1-hydroxy-C 1 -C 10 -alkyl-1, 1-diphosphonic acids, such as 1-hydroxyethane-1,1-diphosphonic acid. Preference is given here to 1-hydroxyethane-1, 1-diphosphonic acid and salts thereof.

Suitable organic builders are, furthermore, aminopolycarboxylic acids, such as nitrilotriacetic acid (NTA), nitrile monooligigipropionic acid, nitrilotripropionic acid, Alaninediacetic acid (.beta.-ADA), ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid, 1,3-propylenediaminetetraacetic acid, 1,2-propylenediaminetetraacetic acid, N- (alkyl) ethylenediaminetriacetic acid, N- (hydroxyalkyl) ethylenediaminetriacetic acid, ethylenediaminetriacetic acid, Cyclohexylene-1,2-diaminetetraacetic acid, iminodisuccinic acid, ethylenediamine disuccinic acid, serinediacetic acid, isoserinediacetic acid, L-aspartic diacetic acid, L-glutamic diacetic acid, methylglycine diacetic acid (MGDA) and the salts of the abovementioned aminopolycarboxylic acids. Preferred among these are L-glutamic diacetic acid, methylglycine diacetic acid and their salts. Suitable organic builders are also polymeric compounds containing carboxylic acid groups, such as acrylic acid homopolymers. These preferably have a number average molecular weight in the range from 800 to 70,000 g / mol, particularly preferably from 900 to 50,000 g / mol, in particular from 1,000 to 20,000 g / mol, especially from 1,000 to 10,000 g / mol. The term acrylic acid homopolymer also encompasses polymers in which the carboxylic acid groups are partially or completely neutralized. These include acrylic acid homopolymers in which the carboxylic acid groups are present partially or completely in the form of alkali metal salts or ammonium salts. Preference is given to acrylic acid homopolymers in which the carboxylic acid groups are protonated or in which the carboxylic acid groups are present partially or completely in the form of sodium salts.

Suitable polymeric compounds containing carboxylic acid groups are also oligomaleic acids, as described, for example, in EP-A 451 508 and EP-A 396 303. Suitable polymeric compounds containing carboxylic acid groups are also terpolymers of unsaturated C 4 -C 8 -dicarboxylic acids, comonomers being monoethylenically unsaturated monomers from group (i) given below in amounts of up to 95% by weight, from group (ii) in amounts of up to 60% by weight and from group (iii) in amounts of up to 20% by weight. Examples of suitable unsaturated C 4 -C 8 -dicarboxylic acids are maleic acid, fumaric acid, itaconic acid and citraconic acid. Preference is given to maleic acid. The group (i) comprises monoethylenically unsaturated C3-Cs monocarboxylic acids such as, for example, acrylic acid, methacrylic acid, crotonic acid and vinylacetic acid. Preferably, from group (i), acrylic acid and methacrylic acid are used. Group (ii) comprises monoethylenically unsaturated C 2 -C 22 -olefins, vinylalkyl ethers having C 1 -C 8 -alkyl groups, styrene, vinyl esters of C 1 -C 8 -carboxylic acids, (meth) acrylamide and vinylpyrrolidone. From group (ii), preference is given to using C 2 -C 6 -olefins, vinylalkyl ethers having C 1 -C 4 -alkyl groups, vinyl acetate and vinyl propionate. If the polymers of group (ii) contain vinyl esters in copolymerized form, these may also be partially or completely converted into vinyl alcohol Structural units are hydrolyzed. Suitable copolymers and terpolymers are known, for example, from US Pat. No. 3,887,806 and DE-A 4313909. Group (iii) comprises (meth) acrylic esters of C 1 -C 8-alcohols, (meth) acrylonitrile, (meth) acrylamides of C 1 -C 8 -amine, N-vinylformamide and N-vinylimidazole.

Suitable polymeric carboxylic acid group-containing compounds are also homopolymers of the monoethylenically unsaturated Cs-Cs monocarboxylic acids, such as e.g. Acrylic acid, methacrylic acid, crotonic acid and vinylacetic acid, especially acrylic acid and methacrylic acid, copolymers of dicarboxylic acids, e.g. Copolymers of maleic acid and acrylic acid in a weight ratio of 10:90 to 95: 5, particularly preferably those in a weight ratio of 30:70 to 90:10 with molecular weights of 1000 to 150,000; Terpolymers of maleic acid, acrylic acid and a vinyl ester of a C1-C3 carboxylic acid in a weight ratio of 10 (maleic acid): 90 (acrylic acid + vinyl ester) to 95 (maleic acid): 10 (acrylic acid + vinyl ester), wherein the weight ratio of acrylic acid to vinyl ester can vary in the range of 30:70 to 70:30; Copolymers of maleic acid with C2-Cs olefins in the molar ratio 40:60 to 80:20, with copolymers of maleic acid with ethylene, propylene or isobutene in the molar ratio 50:50 are particularly preferred. Suitable polymeric compounds containing carboxylic acid groups are furthermore copolymers of from 50 to 98% by weight of ethylenically unsaturated weak carboxylic acids with from 2 to 50% by weight of ethylenically unsaturated sulfonic acids, as described, for example, in EP-A-0877002. Suitable weak ethylenically unsaturated carboxylic acids are, in particular, C 3 -C 6 -monocarboxylic acids, such as acrylic acid and methacrylic acid. Suitable ethylenically unsaturated sulfonic acids are 2-acetylamidomethyl-1-propanesulfonic acid, 2-methacrylic acid amido-2-methyl-1-propanesulfonic acid, 2-methacrylamindo-2-hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2- propenyloxy) propanesulfonic acid, 2-methyl-2-propene-1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate, sulfomethylacrylamide, sulfomethylmethacrylamide and salts of these acids. The copolymers may further contain copolymerized 0 to 30 wt .-% of ethylenically unsaturated C4-C8 dicarboxylic acids, such as maleic acid, and 0 to 30 wt .-% of at least one monomer which is copolymerizable with the aforementioned monomers. The latter are, for example, C 1 -C 4 -alkyl esters of (meth) acrylic acid, C 1 -C 4

Hydroxyalkyl esters of (meth) acrylic acid, acrylamide, alkyl-substituted acrylamide, Ν, Ν-dialkyl-substituted acrylamide, vinylphosphonic acid, vinyl acetate, allyl alcohols, sulfonated allyl alcohols, styrene and other vinylaromatics, acrylonitrile, N-vinylpyrrolidone, N-vinylformamide, N-vinylimidazole or N-vinylpyridine. The weight The average molecular weight of these copolymers is in the range of 3,000 to 50,000. Especially suitable are copolymers having about 77% by weight of at least one ethylenically unsaturated C3-C6 monocarboxylic acid and about 23% by weight of at least one ethylenically unsaturated sulfonic acid.

Graft polymers of unsaturated carboxylic acids on low molecular weight carbohydrates or hydrogenated carbohydrates, cf. US-A 5227446, DE-A 4415623 and DE-A 4313909 are also suitable. Examples of suitable unsaturated carboxylic acids are maleic acid, fumaric acid, itaconic acid, citraconic acid, acrylic acid, methacrylic acid, crotonic acid and vinylacetic acid and also mixtures of acrylic acid and maleic acid which are grafted in amounts of from 40 to 95% by weight, based on the component to be grafted. For modification, in addition up to 30% by weight, based on the component to be grafted, of further monoethylenically unsaturated monomers may be present in copolymerized form. Suitable modifying monomers are the abovementioned monomers of groups (ii) and (iii). As a graft base are degraded polysaccharides such as acidic or enzymatically degraded starches, inuline or cellulose, protein hydrolysates and reduced (hydrogenated or hydrogenated aminated) degraded polysaccharides such as mannitol, sorbitol, aminosorbitol and N-alkylglucamine suitable as well as polyalkylene glycols having molecular weights up to M _w = 5000 such. Polyethylene glycols, ethylene oxide / propylene oxide, and the like. Ethylene oxide / butylene oxide or ethylene oxide / propylene oxide / butylene oxide block copolymers and alkoxylated mono- or polyhydric Ci-C ₂₂ -alcohols (see US-A-5756456).

Likewise suitable are polyglyoxylic acids, as described, for example, in EP-B-001004, US Pat. No. 5,399,286, DE-A-4106355 and EP-A-656914. The end groups of the polyglyoxylic acids can have different structures.

Furthermore, polyamidocarboxylic acids and modified polyamidocarboxylic acids are suitable; these are known, for example, from EP-A-454126, EP-B-51 1037, WO-A94 / 01486 and EP-A-581452.

Also, polyaspartic acids or co-condensates of aspartic acid with other amino acids, C4-C25 mono- or dicarboxylic acids and / or C4-C25 mono- or - diamines can be used as polymeric compounds containing carboxylic acid groups. Particular preference is given to using polyaspartic acids prepared in phosphorus-containing acids and modified with C 1 -C 22 -mono- or -dicarboxylic acids or with C 6 -C 22 -mono- or -diamines. Among the polymeric compounds containing carboxylic acid groups, polyacrylic acids are also preferred in partially or completely neutralized form.

Also suitable as organic builders are iminodisuccinic acid, oxydibasic acid, aminopolycarboxylates, alkylpolyaminocarboxylates, aminopolyalkylene phosphonates, polyglutamates, hydrophobically modified citric acid, such as e.g. Agaricinic acid, poly (alpha) -hydroxyacrylic acid, N-acylethylenediamine triacetates such as lauroylethylenediamine triacetate and alkylamides of ethylenediaminetetraacetic acid such as EDTA tallowamide. Furthermore, oxidized starches can also be used as organic builders.

Preferably, a mixture of different builders is used as component b).

The mixture of different builders preferably comprises at least two of the following constituents: at least one carbonate (eg sodium carbonate), at least one silicate (eg sodium disilkat), at least one polymeric carboxylic acid group-containing compound or at least one polymeric carboxylic acid group-containing compound in which the carboxylic acid groups are partially or completely neutralized ( eg polyacrylic acid), at least one (poly) hydroxycarboxylic acid or a salt thereof (eg citric acid or a citrate), at least one aminopolycarboxylic acid or a salt thereof (eg methylglycinediacetic acid or a salt thereof, eg a sodium salt thereof), at least one phosphonic acid (eg 1-hydroxyethane 1 - (1, 1-diphosphonic acid); H EDP), at least one phosphate. The mixture particularly preferably contains at least one carbonate, at least one silicate and at least one polymeric (partially) neutralized carboxylic acid group-containing compound and optionally at least one of the following: at least one (poly) hydroxycarboxylic acid or a salt thereof, at least one phosphonic acid, at least one phosphate. Specifically, the mixture contains at least one carbonate, at least one silicate, at least one polymeric optionally (partially) neutralized carboxylic acid group-containing compound, at least one (poly) hydroxycarboxylic acid or a salt thereof and at least one phosphonic acid, and optionally at least one phosphate.

In such a mixture, the ingredients are preferably contained in the following amounts:

b1) at least one carbonate: 10 to 50% by weight;

b2) at least one silicate: 1 to 10% by weight;

b3) at least one polymeric optionally (partially) neutralized carboxylic acid group-containing compound: 5 to 20 wt .-%; b4) at least one (poly) hydroxycarboxylic acid or a salt thereof: 0 to 50% by weight

0 // o.,

b5) at least one aminopolycarboxylic acid or a salt thereof: 0 to 60% by weight; b6) at least one phosphonic acid: 0.2 to 1% by weight;

b7) at least one phosphate: 0 to 60 wt .-%.

The percentages by weight are based on the total weight of the builder. The amounts by weight of b1) to b7) add up to 100% by weight. The enzymes are preferably selected from hydrolases, such as proteases, esterases, glucosidases, lipases, amylases, cellulases, mannanases, other glycosyl hydrolases and mixtures of the abovementioned enzymes. All of these hydrolases contribute to the soil dissolution and removal of proteinaceous, fatty or starchy contaminants. For bleaching also Oxireduktasen can be used. Particularly suitable are enzymatic active substances obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus and Humicola insolens.

Suitable hydrolases are e.g. α-glucosidases (EC number 3.2.1.20), proteases (Ovozyme® (ex Novozymes), EC number 3.2.1.20), amylases [Purastar® (ex Genencor), Termamyl® (ex Novozymes), Stainzyme® (ex Novozymes ), Duramyl® (from Novozymes)], mannanases [Purabrite® (from Genencor), Mannastar® (from Genencor), Mannaway® (from Novozymes)] and cellulases [Carezyme® (from Novozymes), Cellucome® (from Novozymes ), Endolase, Puradax® (from Genencor)]. Suitable amylases include in particular α-amylases (EC number 3.2.1.1), iso-amylases, pululanases and pectinases. As cellulases are preferably cellobiohydrolases, endoglucanases and ß-glucosidases, which are also called cellobiases, or mixtures thereof used. Since different cellulase types differ by their CMCase and avicelase activities, the desired activities can be set by targeted mixtures of the cellulases.

Suitable lipases are esterases, such as Lipex and Lipolase. Examples of lipolytic enzymes are the known cutinases.

Peroxidases or oxidases have also proved suitable in some cases

The dishwashing agent according to the invention preferably contains at least one protease and / or amylase. The dishwashing composition according to the invention preferably contains an enzyme mixture. For example, enzyme mixtures which contain or consist of the following enzymes are preferred:

Protease and amylase,

 Protease and lipase (or lipolytic enzymes),

 Protease and cellulase,

 Amylase, cellulase and lipase (or lipolytic enzymes),

Protease, amylase and lipase (or lipolytic enzymes)

 Protease, lipase (or lipolytic enzymes) and cellulase.

Particularly preferred are protease and / or amylase-containing mixtures. Preferred proteases in the aforementioned mixtures are subtilisin-type proteases (Savinase, etc .; EC No. 3.4.21.62).

The enzymes may be adsorbed to carriers to protect against premature degradation. Optionally, the washing and cleaning agent of the invention may further comprise enzyme stabilizers, e.g. Calcium propionate, sodium formate or boric acids or their salts, and / or oxidation inhibitors included.

The bleaching agents d) are preferably bleaching systems which, in addition to bleaching agents, optionally also contain bleach activators, bleach catalysts and / or bleach stabilizers.

Suitable bleaching agents are, for example, percarboxylic acids, e.g. Diperoxododecanedicarboxylic acid, phthalimidopercaproic acid or monoperoxophthalic acid or terephthalic acid, salts of percarboxylic acids, e.g. Sodium percarbonate, adducts of hydrogen peroxide with inorganic salts, e.g. Sodium perborate monohydrate, sodium perborate tetrahydrate, sodium carbonate perhydrate or sodium phosphate perhydrate, adducts of hydrogen peroxide to organic compounds, e.g. Urea perhydrate, or of inorganic peroxy salts, e.g. Alkali metal persulfates, or peroxodisulfates.

Suitable bleach activators are, for example, polyacylated sugars, for example pentaacetylglucose; Acyloxybenzenesulfonic acids and their alkali and alkaline earth metal salts, for example, sodium p-nonanoyloxybenzenesulfonate or sodium p-benzoyloxybenzenesulfonate; - Ν, Ν-diacylated and Ν, Ν, Ν ', Ν'-tetraacylated amines, for example Ν, Ν, Ν', Ν'- tetraacetylmethylenediamine and ethylenediamine (TAED), Ν, Ν-diacetylaniline, N, N-diacetyl -ptoluidine or 1, 3-diacylated hydantoins such as 1,3-diacetyl-5,5-dimethylhydantoin; N-alkyl-N-sulfonylcarbonamides, eg N-methyl-N-mesylacetamide or N-methylN-mesylbenzamide; N-acylated cyclic hydrazides, acylated triazoles or urazoles, eg monoacetylmaleic hydrazide; Ο, Ν, Ν-trisubstituted hydroxylamines, for example 0-benzoyl-N, N-succinylhydroxylamine, O-acetyl-N, N-succinylhydroxylamine or Ο, Ν, Ν-triacetylhydroxylamine; Ν, Ν'-diacylsulfurylamides, for example N, N'-dimethyl-N, N'-diacetylsulfurylamide or Ν, Ν'-diethyl-N, N'-dipropionylsulfurylamide; acylated lactams such as acetylcaprolactam, octanoylcaprolactam, benzoylcaprolactam or carbonylbiscaprolactam; Anthranil derivatives such as 2-methylanthranil or 2-phenylanthranil; Triacylcyanurates, eg triacetyl cyanurate or tribenzoyl cyanurate; Oxime esters and bisoxime esters such as O-acetylacetone oxime or bis-isopropyliminocarbonate; Carboxylic acid anhydrides, eg acetic anhydride, benzoic anhydride, m-chlorobenzoic anhydride or phthalic anhydride; Enol esters such as isopropenyl acetate; 1, 3-diacyl-4,5-diacyloxy-imidazolines, for example 1, 3-diacetyl-4,5-diacetoxyimidazoline; Tetraacetylglycoluril and tetrapropionylglycoluril; diacylated 2,5-diketopiperazines, eg 1, 4-diacetyl-2,5-diketopiperazine; ammonium-substituted nitriles such as N-methylmorpholinium acetonitrile methylsulfate; Acylation products of propylene diurea and 2,2-dimethyl-propylene diurea, eg tetraacetyl-propylene diurea; a-acyloxypolyacylmalonamides, eg a-acetoxy-N, N'-diacetylmalonamide; Diacyldioxohexahydro-1,3,5-triazines, for example 1,5-diacetyl-2,4-dioxohexahydro1, 3,5-triazine; Benz (4H) 1, 3-oxazin-4-ones with alkyl radicals, for example methyl, or aromatic radicals, for example phenyl, in the 2-position.

A bleaching system of bleaches and bleach activators may optionally also contain bleach catalysts. Suitable bleach catalysts are, for example, quaternized imines and sulfonimines which are described, for example, in US Pat. No. 5,360,569 and EP-A 453,003. Particularly effective bleach catalysts are manganese complexes, which are described, for example, in WO-A 94/21777. Such compounds, in the case of their use in detergents and cleaners, at most in amounts of up to 1, 5 wt .-%, in particular up to 0.5 wt .-%, in the case of very active manganese complexes in amounts up to 0.1 wt. -%, incorporated. In addition to the described bleaching system comprising bleaches, bleach activators and, if appropriate, bleach catalysts, the use of systems with enzymatic peroxide release or of photoactivated bleach systems is also possible for the detergents and cleaners according to the invention. Surfactants from group e) other than component a) may be cationic, anionic, zwitterionic or nonionic.

Suitable nonionic surfactants are, for example, alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 20, preferably 1 to 12 moles of ethylene oxide (EO) per mole of alcohol in which the alcohol radical is linear or preferably 2- Position may be methyl branched or contain linear and methyl-branched radicals in the mixture, as they are usually present in Oxoalkoholresten. In particular, however, alcohol ethoxylates having linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for

Example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol preferred. Preferred ethoxylated alcohols include, for example, C ₁₂ -Ci4-alcohols with 3 EO, 4 EO or 7 EO, Cn-alcohol with 7 EO, C13-Cis alcohols containing 3 EO, 5 EO, 7 EO or 8 EO, C ₂ -C ₈ alcohols containing 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of Ci2-Ci4 alcohol containing 3 EO and Ci2-cis-alcohol containing 7 EO. The degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number. Also suitable are alcohol ethoxylates which have a narrow homolog distribution (narrow rank ethoxylates, NRE). In addition to these nonionic surfactants, it is also possible to use fatty alcohols with more than 12 EO. Examples include tallow fatty alcohol with 14 EO, 25 EO or 30 EO. Nonionic surfactants containing EO and PO groups together in the molecule can also be used. Here, block copolymers with EO-PO block units or PO-EO block units can be used, but also EO-PO-EO copolymers or PO-EO-PO copolymers. Of course, it is also possible to use mixed alkoxylated nonionic surfactants in which EO and PO units are not distributed in blocks, but randomly. Such products are obtainable by simultaneous action of ethylene oxide and propylene oxide on fatty alcohols. In addition, as further nonionic surfactants and alkyl glycosides of the general formula (1)

R ^a O (G) _y (1) are used, wherein R ^{a is} a primary straight-chain or methyl-branched, in particular 2-methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G for a glycoside unit with 5 or 6 carbon atoms, preferably glucose. The degree of oligomerization y, which determines the distribution ment of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably y is 1, 2 to 1, 4.

Another class of suitable nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having from 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl esters as described, for example, in Japanese Patent Application JP 58/217598 or preferably prepared according to the process described in International Patent Application WO-A-90/13533.

Nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.

Further suitable surfactants are polyhydroxy fatty acid amides of the formula (2),

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

The group of polyhydroxy fatty acid amides also includes compounds of the formula (3) wherein R ^{e is} a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{f is} a linear, branched or cyclic alkylene radical having 2 to 8 carbon atoms or an arylene radical having 6 to 8 carbon atoms and Ra is a linear, branched or cyclic Alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, preference being given to C 1 -C 4 -alkyl or phenyl radicals, and [Z] ^{1 being} a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this radical. [Z] ¹ is preferably obtained by reductive amination of a 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 WO-A-95/07331, by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst into the desired polyhydroxy fatty acid amides.

Suitable anionic surfactants are, for example, those of the sulfonate type and sulfates. As surfactants of the sulfonate type preferably C9-C13 alkylbenzenesulfonates, Olefinsulfonate, i. Mixtures of alkene and Hydroxyalkansul- fonates and disulfonates, as obtained for example from Ci2-Ci8 monoolefins with terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation, into consideration. Also suitable are alkanesulfonates which are obtained from C 12 -alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. Likewise suitable are the esters of α-sulfo fatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.

Further suitable anionic surfactants are sulfated fatty acid glycerol esters. Fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and mixtures thereof, as obtained in the preparation by esterification of a monoglycerol with 1 to 3 mol of fatty acid or in the transesterification of triglycerides with 0.3 to 2 mol of glycerol become. Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids containing 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid. Alk (en) ylsulfates are the alkali metal salts and, in particular, the sodium salts of the sulfuric monoesters of C 12-18 fatty alcohols, for example coconut oil fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 -C 20 oxo alcohols and those half esters secondary Alcohols of these chain lengths are preferred. Also preferred are alk (en) ylsulfates of said chain length, which contain a synthetic, produced on a petrochemical basis straight-chain alkyl radical, which have an analogous degradation behavior as the adequate compounds based on oleochemical raw materials. From a washing-technical point of view, preference is given to the C 12 -C 16 -alkyl sulfates and C 12 -C 20 -alkyl sulfates and also C -C -alkyl sulfates. Also, 2,3-alkyl sulfates, which are prepared, for example, according to US Pat. Nos. 3,234,258 or 5,075,041 and can be obtained as commercial products of the Shell Oil Company under the name DAN®, are suitable anionic surfactants. Also, the sulfuric monoesters of ethoxylated with 1 to 6 moles of ethylene oxide straight or branched C7-C2i alcohols, such as 2-methyl-branched Cg-Cn alcohols having an average of 3.5 moles of ethylene oxide (EO) or Ci ₂ -Ci ₈ fatty alcohols with 1 to 4 EO, are suitable. Due to their high foaming behavior, they are only used in detergents in relatively small amounts, for example in amounts of from 1 to 5% by weight.

Further suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contain Ce-Cie fatty alcohol residues or mixtures of these. Particularly preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty alcohols. Sulfosuccinates, whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are again particularly preferred. Likewise, it is also possible to use alk (en) ylsuccinic acid having preferably 8 to 18 carbon atoms in the Al k (en) yl chain or salts thereof.

Suitable anionic surfactants are also soaps. Suitable are saturated and unsaturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, (hydrogenated) erucic acid and behenic acid and, in particular, soap mixtures derived from natural fatty acids, for example coconut, palm kernel, olive oil or tallow fatty acids. The anionic surfactants including the soaps may be in the form of their sodium, potassium or ammonium salts, as well as soluble salts of organic bases such as mono-, di-triethanolamine. The anionic surfactants are preferably present in the form of their sodium or potassium salts, in particular in the form of the sodium salts.

Cationic surfactants are, for example, ammonium salts, such as Cs-C16-dialkyldimethylammonium halides, dialkoxydimethylammonium halides or imidazolinium salts with a long-chain alkyl radical. Amphoteric surfactants are, for example, derivatives of secondary or tertiary amines such as e.g. Cβ-Cis-alkylbetaines or Cβ-Cis-alkylsulfobetaines or amine oxides such as alkyldimethylamine oxides.

Solvents contained in component e) are derived, for example, from the group of monohydric or polyhydric alcohols, alkanolamines or glycol ethers. They are preferably selected from ethanol, n- or i-propanol, butanols, glycol, propane or butane diol, 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, diisopropylene glycol monomethyl or ethyl ether, methoxy, ethoxy or butoxy triglycol, i-butoxyethoxy-2-propanol, Methyl-3-methoxybutanol, propylene glycol t-butyl ether and mixtures of these solvents. Examples of foam inhibitors or defoamers of component e) are soaps, paraffins or silicone oils, which may optionally be applied to support materials.

Suitable bases of component e) are, in particular, the carbonates mentioned above in the builders.

In an alternatively preferred embodiment of the invention, the washing and cleaning agents according to the invention are gel-like. The gel-type detergents and cleaners are preferably gelatinous dishwashing agents, of which gel-type machine dishwashing detergents are particularly preferred. In particular, these are gelatinous dishwashing detergents, preferably machine dishwashing detergents, with a rinse aid function. Gel-like detergents and cleaners are understood as meaning fluid agents which have a viscosity at room temperature (20 ° C.) which is higher than that of water, but which are still sufficiently fluid that they can be metered without problems using customary dosing aids. The gel-like detergents and cleaners according to the invention preferably have a viscosity of from 0.5 to 100, particularly preferably from 0.5 to 50 and in particular from 1 to 30, Pa s at 20 ° C.

The gelatinous dishwashing detergent according to the invention preferably comprises the following constituents:

a) at least one compound of the formula I;

b) at least one builder (also referred to as sequestering agent, builder, complexing agent, chelator, chelating agent or softening agent);

c) optionally at least one enzyme;

d) optionally at least one bleaching agent;

e1) water;

e2) at least one thickener; and

e3) optionally at least one further additive, which is preferably selected from surfactants other than a), bases, corrosion inhibitors, defoamers, dyes, fragrances, fillers, solubilizers and organic solvents.

These constituents are preferably present in the following proportions in the gel dishwashing detergent according to the invention: a) at least one compound of the formula I: from 0.1 to 20% by weight;

b) at least one builder: from 5 to 80% by weight;

c) at least one enzyme: from 0 to 8% by weight;

d) at least one bleaching agent: from 0 to 30% by weight;

e1) water: from 10 to 90% by weight;

e2) at least one thickener: from 0.1 to 8% by weight; and

e3) at least one further additive: from 0 to 25% by weight.

The percentages by weight relate to the total weight of the dishwashing detergent. The amounts by weight of a) to e3) add up to 100 wt .-%.

The dishwashing agent according to the invention particularly preferably comprises at least one enzyme. The abovementioned constituents are particularly preferably contained in the following proportions in the gel dishwashing detergent according to the invention: a) at least one compound of the formula I: from 0.1 to 10% by weight;

b) at least one builder: from 5 to 60% by weight;

c) at least one enzyme: from 0.1 to 6% by weight;

d) at least one bleaching agent: from 0 to 30% by weight; and

e1) water: from 10 to 90% by weight;

e2) at least one thickener: from 0.1 to 6% by weight; and

e3) at least one further additive: from 0 to 25% by weight.

The percentages by weight relate to the total weight of the dishwashing detergent. The amounts by weight of a) to e3) add up to 100 wt .-%. More preferably, the abovementioned constituents are present in the following proportions in the gel dishwashing detergent according to the invention: at least one compound of the formula I: from 0.1 to 10% by weight;

 at least one builder: from 5 to 40% by weight;

 at least one enzyme: from 0.1 to 6% by weight;

 at least one bleaching agent: from 0 to 25% by weight; and

 Water: from 20 to 80% by weight;

 at least one thickener: from 0.3 to 5% by weight; and

 at least one further additive: from 0 to 25% by weight.

The percentages by weight relate to the total weight of the dishwashing detergent. The amounts by weight of a) to e3) add up to 100 wt .-%.

The thickeners serve to impart the desired viscosity to the dishwashing agent according to the invention.

In principle, any known thickeners (rheology modifiers) are suitable, provided they do not exert a negative influence on the effect of the dishwashing detergent. Suitable thickeners may be both of natural origin and of synthetic nature.

Examples of thickeners of natural origin are xanthan gum, locust bean gum, guar gum, carrageenan, agar, tragacanth, gum arabic, alginates, modified starches such as hydroxyethyl starch, starch phosphate esters or starch acetates, dextrins, pectins and cellulose derivatives such as carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, methylcellulose and the like.

Thickeners of natural origin are also inorganic thickeners, such as polysilicic acids and clay minerals, e.g. Phyllosilicates, as well as the silicates mentioned in the builders.

Examples of synthetic thickeners are polyacrylic and polymethacrylic compounds, such as (partially) crosslinked homopolymers of acrylic acid, for example with an allyl ether of sucrose or pentaerythritol or homopolymers crosslinked with propylene

Acrylic acid (carbomer), e.g. the Carbopo D grades from BF Goodridge (eg Carbopol® 676, 940, 941, 934 and the like) or the Polyge D grades from 3V Sigma (eg Polygel® DA), copolymers of ethylenically unsaturated mono- or dicarboxylic acids, for example terpolymers of Acrylic acid, methacrylic acid or maleic acid with methyl or ethyl acrylate and a (meth) acrylate derived from long chain ethoxylated alcohols, for example the Acuso D brands from Rohm & Haas (eg Acusol® 820 or 1206A), copolymers of two or more monomers , which are selected from acrylic acid, methacrylic acid and their Ci-C4-alkyl esters, eg Copolymers of methacrylic acid, butyl acrylate and methyl methacrylate or of butyl acrylate and methyl methacrylate, e.g. the Aculyn® and Acuso D brands from Rohm & Haas (eg Aculyn® 22, 28 or 33 and Acusol® 810, 823 and 830), or crosslinked high molecular weight acrylic acid copolymers, for example with an allyl ether of sucrose or pentaerythritol cross-linked copolymers of C 1 -C 30 -alkyl acrylates having one or more monomers selected from acrylic acid, methacrylic acid and their C 1 -C 4 -alkyl esters (eg Carbopol® ETD 2623, Carbopol® 1382 or Carbopol® AQUA 30 from Rohm & Haas).

Examples of synthetic thickeners are further reaction products of maleic acid polymers with ethoxylated long-chain alcohols, e.g. the Surfonic L series from Texaco Chemical Co. or Gantrez AN-1 19 from ISP; Polyethylene glycols, polyamides, polyimines and polycarboxylic acids.

Also suitable are mixtures of the above-mentioned. Thickener. Preferred thickeners are xanthans and the abovementioned polyacrylic and polymethacrylic compounds.

With regard to suitable and preferred components a) to d) and e3), reference is made to the above statements. The compounds I used according to the invention are distinguished by a high melting point in comparison to conventional surfactants of the prior art, which allows their use in solid detergents and cleaners. They have no or no strong foaming tendency, they have a good deposit-inhibiting action on dishes washed therewith, in particular with regard to spotting, and they are not susceptible to hydrolysis.

The application will now be further illustrated by the following non-limiting examples.

Examples

1 . synthesis Examples

General rule

1 .1 Preparation of alkyloxyethylene glycol dodecylmercaptoethanols 1 .1 .1 Preparation of the alcohol ethoxylate:

In a Mettler autoclave, the alcohol to be alkoxylated (isotridecanol, 2-propylheptanol or C 1 -C 10 -alcohol; 1, 0 eq) is treated with an aqueous KOH solution which contains 50% by weight of KOH. added. The amount of KOH is 0.2 wt .-% of the product to be produced. With stirring, the mixture is dehydrated at 100 ° C and 20 mbar for 2 h. Then it is rinsed three times with N2, a pre-pressure of about 1.3 bar N2 is set and the temperature is raised to 120.degree. The ethylene oxide (n mol eq.) Is metered in so that the temperature remains between 125 and 135 ° C. The mixture is then stirred for 5 h at 125 ° C, rinsed with N2, cooled to 70 ° C and the reactor emptied. The crude product is degassed on a rotary evaporator for 2 h at 100 ° C (<20 mbar vacuum). This basic crude product can be deionized with commercially available Mg silicates, which are then filtered off. Alternatively, the neutralization can also be carried out with the aid of acetic acid. The bright product is characterized by means of a ¹ H-NMR spectrum in CDCl 3 and a gel permeation chromatography and an OH number determination and the yield is determined (> 98%). 1 .1 .2 Reaction with dodecylmercaptoethanol

The alkoxylate from Example 1 .1.1 (1 mol eq.), Para-toluenesulphonic acid (0.005 mol eq.) And toluene are initially charged in a 500 ml apparatus with water separator. The reaction mixture is heated to reflux. Dodecylmercaptoethanol (x mol eq.) Is added dropwise. The resulting water is removed via a water separator overnight. The reaction mixture is cooled, neutralized with sodium carbonate (0.005 mol eq.), Filtered and freed completely of solvent at 100 ° C and 6 mbar. A white solid product is obtained. The structure was determined by TAI NMR (% reacted OH groups). Residual amount of toluene (always <0.5%) and dodecylmercaptoethanol were determined by GC.

 according to TAI-NMR

 ** according to quant. GC

 1-C13 = "isotridecanol"; Mixture of different tridecanol isomers

 EO = ethylene oxide

 PO = propylene oxide

 2PH = 2-propylheptanol 1 .2. Oxidation of product C to the corresponding sulfoxide D

In a 250 ml flask, 71.6 g of product C (40 mmol, 1 mol eq.) Described above were melted, initially charged in water and heated to 70.degree. Hydrogen peroxide (50%) (4.1 g, 60 mmol, 1 .5 mol eq.) Was added dropwise. The reaction mixture was stirred at 70 ° C for 2 hours, then cooled and concentrated at 100 ° C and 6 mbar. 69.2 g (96% yield) of a solid yellow product were obtained. The absence of hydrogen peroxide was checked by IR and the conversion (100%) determined by ¹ H NMR. Method description for TAI-NMR:

In order to be able to determine (quantitatively) superimposed signals of primary and / or secondary alcohols in the ¹ H NMR spectrum, a sample in CDC is mixed with an excess of TAI (trichloroacetyl isocyanate). The isocyanate reacts immediately with the alcohol groups to carbamate. The compounds CI ₃ CC (O) NHC (O) -OCH R or CI ₃ CC (Q) NHC (O) -OCH-RR ^' contained therein have different, typical shifts for OCH 2 and OCH RR in the ¹ H NMR spectrum ^"on. The typical displacement range for" primary carbamates "is 4.0 to 4.5 ppm, while that for" secondary carbamates is "at 5.0 to 5.3 ppm.

2 application examples

Various surfactants were tested in this application. A is a comparative polymer.

PO = propylene oxide

 EO = ethylene oxide

 DeO = 1, 2-decene oxide

 1-C13 = "isotridecanol"; Mixture of different tridecanol isomers

 2PH = 2-propylheptanol

2.1 Melting Point Determinations The solidification points were measured by DSC (Differential Scanning Calorimetry).

Surfactant A B C D E F

Melting point [° C] 33.1 40.1 41.8 41.1 44.1 44.9 2.2 Foam volume in the dishwasher

The foam volume was determined indirectly by measuring the foaming over the speed of the spray arm of the dishwasher. For this purpose, 10 ml of stirred chicken egg, 19 g of a base dishwashing detergent (48 parts of sodium metasilicate x 5H2O, 45 parts of sodium triphosphate, 5 parts of sodium carbonate) and 1 g of the surfactant (AF) in the dishwasher (Miele Disinfector G 7735 CD MCU; Version S04.01). At different temperatures, the number of revolutions of the spray arm was then measured. When the foam level is high, the spray arm is slowed down, at low levels it can work at the highest possible speed (about 125 rpm). The top speed of the dishwasher is usually about 125 rpm when there is no foam. The maximum speed in the dishwashing machine was set artificially in this experiment (by drilling on the spray arm, position of the nozzles) in order to obtain a wider range which makes products more distinguishable.

The rotational speed was measured at 40, 50 and 60 ° C. The following table lists rotor speeds in rpm at different temperatures.

2.3 rinse test

All examples were carried out with a basic formulation of the following composition:

1 part by weight of protease (Ovozyme® 64 T)

 0.2 parts by weight of amylase (Stainzyme® 12 T)

 3 parts by weight of surfactant

 10 parts by weight of polyacrylic acid with a molecular weight of 4000 g / mol (Sokalan® PA 25 Cl) 10.5 parts by weight of sodium percarbonate

 4 parts by weight of tetraacetylethylenediamine

 2 parts by weight of sodium disilicate (Britesil® H 265 LC)

 18.8 parts by weight of sodium carbonate

33 parts by weight of Na citrate dihydrate 15 parts by weight of methylglycinediacetic acid trisodium salt (Trilon® M) 0.5 part by weight of 1-hydroxyethane- (1, 1-diphosphonic acid) (HEDP; Cublen® K 8514 GR) Ovozyme® and Stainzyme® are trademarks of Novozymes, Sokalan® and Trilon® are trademarks of BASF SE, Britesil® is a trademark of PQ Corp., Cublen® is a trademark of Zschimmer & Schwarz Mohlsdorf GmbH & Co KG.

All rinse-aid tests were carried out in a dishwashing machine from Miele (type G1222 SCL). The program was chosen to be 50 ° C (R-time 2) for the wash cycle and 65 ° C for the rinse cycle. The tests were carried out with hardened water with a water hardness of 21 ° dH (Ca / Mg): HC0 ₃ (3: 1): 1 .35. No separate rinse aid was added and the built-in water softening (ion exchanger) was not regenerated with regenerating salt. The above formulation was dosed at 21 g each. For each rinse, 100 g of ballast dirt consisting of fat, protein and starch was added. As a test harness served in every cleaning knife from Cromargan, blue melamine plates, drinking glasses and porcelain plates. One hour each was waited between the rinsing cycles, 10 minutes with the door closed, 50 minutes with the door open.

After completion of the sixth rinse cycle, the dishes were visually patterned in a darkened chamber under light behind a pinhole and evaluated on a score scale from 1 (= high residue) to 10 (= no residue) for stains, streaks, and film-like deposits.

Rating filming A B C D E F

 Knife 6 6 5 6 5 6

Drinking glass 6 5 5 7 5 5

Melamine plate 6 7 7 9 7 7

Total 18 18 17 22 17 18 2.4 Stability tests across the scope

Experiment analogous to 2.2. The rotational speed was measured at maximum temperature (57 ° C-70 ° C) over a period of 2 hours. The following table shows the rotational speed in rpm. Below the rotational speed, the exact temperatures are listed in square brackets.

Time 10 20 30 40 50 60 70 80 90 100 110 120

 [Min]

 A 129 127 128 125 127 127 127 127 126 126 124 122

 [60] [61] [62] [64] [64] [65] [67] [68] [68] [68] [68] [69]

 B 119 121 122 118 117 117 116 114 111 108 104 97

 [57] [58] [59] [60] [61] [62] [63] [64] [65] [66] [67] [68]

 C 114 115 118 117 122 126 125 125 126 123 124 125

 [58] [60] [61] [62] [63] [64] [65] [66] [67] [68] [69] [70]

 D 117 119 118 120 120 122 122 120 120 121 119 120

 [58] [60] [61] [62] [64] [65] [66] [67] [68] [68] [69] [70]

 E 123 124 122 122 121 119 119 115 113 113 109 111

 [59] [60] [61] [63] [64] [65] [66] [67] [68] [69] [70] [70]

 F 103 97 97 99 104 102 105 104 104 105 104 102

 [58] [58] [59] [60] [61] [62] [63] [64] [65] [63] [66] [67]

Claims

claims

1 . Use of compounds of the formula I

R-0-f CH ₂ CH (R ¹⁾ m} -OHCH2CH2-0-fCH2CH (R ²⁾ -0} n-CH2CH2-S (0) x R '(I) wherein

R is C ₈ -C ₂ 4 alkyl;

R 'is C ₆ -C 18 -alkyl;

R ¹ and R ^{2 are} independently of one another and independently of their occurrence for Ci-C5-alkyl;

 m is a number from 10 to 100;

 I and n independently represent a number from 0 to 15; and x is 0, 1 or 2; in detergents or cleaners.

2. Use according to claim 1, wherein the washing and cleaning agents are selected from dishwashing detergents.

3. Use according to claim 2, wherein the washing and cleaning agents are selected from machine dishwashing detergents.

4. Use according to one of claims 2 or 3, wherein the washing and cleaning agents are selected from dishwashing detergents with rinse aid.

5. Use according to one of the preceding claims, wherein the detergents and cleaning agents are solid.

6. Use according to any one of claims 1 to 4, wherein the washing and cleaning agents are gel-like.

7. Use according to one of the preceding claims, wherein the compounds I are used as surfactants.

8. Use according to one of the preceding claims, wherein the compounds I are used as rinse aid surfactant.

9. Use according to one of the preceding claims, wherein R is C10-C15 alkyl.

10. Use according to one of the preceding claims, wherein R 'is C10-C14-alkyl, preferably Ci2-alkyl.

1 1. Use according to any one of the preceding claims wherein R ¹ and R ^{2 are} independently of one another and independently of their occurrence methyl.

Use according to any one of the preceding claims, wherein m is a number from 25 to 50.

Use according to any one of the preceding claims, wherein I and n are 0.

14. Use according to one of the preceding claims, wherein x is 0 or 1.

15. Use according to one of the preceding claims, wherein the melting point of the compounds I is at least 35 ° C, preferably at least 38 ° C.

16. A washing or cleaning composition containing at least one compound of the formula I as defined in any one of claims 1 and 9 to 15.

17. A washing or cleaning agent according to claim 16, which is a dishwashing detergent.

18. A washing or cleaning composition according to claim 17, which is a machine dishwashing detergent.

19. Washing or cleaning agent according to claim 17 or 18, which is a dishwashing detergent with rinse aid.

20. A washing or cleaning agent according to any one of claims 16 to 19, which is solid at room temperature.

21. Washing or cleaning agent according to one of claims 18 to 20, comprising the following constituents: a) at least one compound of the formula I;

 b) at least one builder;

 c) optionally at least one enzyme;

 d) optionally at least one bleaching agent; and

 e) optionally at least one further additive selected from surfactants other than a), bases, corrosion inhibitors, defoamers, dyes, perfumes, fillers, tabletting aids, disintegrants, thickeners, solubilizers, organic solvents and water.

22. Washing or cleaning agent according to claim 21, comprising the following constituents:

 a) at least one compound of the formula I: from 0.1 to 20% by weight;

 b) at least one builder: from 5 to 80% by weight;

 c) at least one enzyme: from 0 to 8% by weight;

 d) at least one bleaching agent: from 0 to 30% by weight; and

 e) at least one further additive: from 0 to 50% by weight; based on the total weight of the detergent or cleaning agent.

Detergents or cleaners according to claim 21 or 22, comprising following components:

 a) at least one compound of the formula I: from 0.1 to 10% by weight;

 b) at least one builder: from 20 to 80% by weight;

 c) at least one enzyme: from 0.1 to 6% by weight;

 d) at least one bleaching agent: from 0 to 30% by weight; and

 e) at least one further additive: from 0 to 50% by weight; based on the total weight of the detergent or cleaning agent.

Detergents or cleaning compositions according to any one of claims 21 to 23, send the following constituents:

 a) at least one compound of the formula I: from 0.1 to 10% by weight;

 b) at least one builder: from 20 to 80% by weight;

 c) at least one enzyme: from 0.1 to 6% by weight;

 d) at least one bleaching agent: from 5 to 25% by weight; and

e) at least one further additive: from 0 to 50% by weight; based on the total weight of the detergent or cleaning agent.

25. Washing or cleaning agent according to one of claims 21 to 24, wherein as component b) a mixture of different builder is used which contains at least 2 of the following constituents: at least one carbonate, at least one silicate, at least one polymeric carboxylic acid group-containing compound or at least one polymeric carboxylic acid group-containing compound in which the carboxylic acid groups are partially or completely neutralized, at least one (poly) hydroxycarboxylic acid or a salt thereof, at least one aminopolycarboxylic acid or a salt thereof, at least one phosphonic acid, at least one phosphate.

26. A washing or cleaning agent according to any one of claims 16 to 19 and 21 to 25, which is gel at room temperature.

Detergents or cleaners according to Claim 26, comprising the following constituents:

 a) at least one compound of the formula I;

 b) at least one builder;

 c) optionally at least one enzyme;

 d) optionally at least one bleaching agent;

 e1) water;

 e2) at least one thickener; and

 e3) optionally at least one further additive selected from surfactants other than a), bases, corrosion inhibitors, defoamers, dyes, fragrances, fillers, solubilizers and organic solvents.

Washing or cleaning agent according to claim 27, comprising the following constituents:

 a) at least one compound of the formula I: from 0.1 to 20% by weight;

 b) at least one builder: from 5 to 80% by weight;

 c) at least one enzyme: from 0 to 8% by weight;

 d) at least one bleaching agent: from 0 to 30% by weight;

 e1) water: from 10 to 90% by weight;

 e2) at least one thickener: from 0.1 to 8% by weight; and

e3) at least one further additive: from 0 to 25% by weight; based on the total weight of the detergent or cleaning agent.

29. Washing or cleaning agent according to claim 27 or 28, comprising the following constituents:

 a) at least one compound of the formula I: from 0.1 to 10% by weight;

 b) at least one builder: from 5 to 60% by weight;

 c) at least one enzyme: from 0.1 to 6% by weight;

 d) at least one bleaching agent: from 0 to 30% by weight; and

 e1) water: from 10 to 90% by weight;

 e2) at least one thickener: from 0.1 to 6% by weight; and

 e3) at least one further additive: from 0 to 25% by weight; based on the total weight of the detergent or cleaning agent.

Washing or cleaning agent according to one of claims 27 to 29, comprising the following constituents:

 a) at least one compound of the formula I: from 0.1 to 10% by weight;

 b) at least one builder: from 5 to 40% by weight;

 c) at least one enzyme: from 0.1 to 6% by weight;

 d) at least one bleaching agent: from 0 to 25% by weight; and

 e1) water: from 20 to 80% by weight;

 e2) at least one thickener: from 0.3 to 50% by weight; and

 e3) at least one further additive: from 0 to 25% by weight; based on the total weight of the detergent or cleaning agent.