KR20140040085A - Use of optionally oxidized thioethers of alcohol alkoxylates in detergents and cleaning agents - Google Patents

Abstract

The present invention relates to the use of (oxidized) thioethers of alcohol alkoxylates in detergents and cleaners, especially dishwashing detergents, and to detergents and cleaners, in particular dishwashing detergents containing (oxidized) thioethers of alcohol alkoxylates. . The (oxidized) thioether is particularly suitable for use as a surfactant having a rinse aid function (rinse aid surfactant). The term “oxidation” relates to a sulfur atom of a thioether, which may exist in oxidized form as sulfoxide (SO) or sulfonyl (SO ₂ ).

Description

Use of optionally oxidized thioethers of alcohol alkoxylates in detergents and cleaners {USE OF OPTIONALLY OXIDIZED THIOETHERS OF ALCOHOL ALKOXYLATES IN DETERGENTS AND CLEANING AGENTS}

The present invention relates to the use of (oxidized) thioethers of alcohol alkoxylates in cleaning and cleaning compositions, especially dishwashing compositions, and to cleaning and cleaning compositions, in particular tableware, comprising (oxidized) thioethers of alcohol alkoxylates. It relates to a cleaning composition. The (oxidized) thioethers are particularly suitable as surfactants with a rinse aid function (rinse aid surfactant). "Oxidized" refers to a sulfur atom in a thioether which may exist in oxidized form as sulfoxide (SO) or sulfonyl (SO ₂ ).

Surfactants are substances that can lower the interfacial tension. Typically, surfactants have a characteristic structure and have one or more hydrophilic and one or more hydrophobic functional groups. If the two parts of the molecule are balanced with respect to each other, material will accumulate and at the interface, ie the hydrophilic group points are arranged, for example, in the aqueous phase and in the direction of the other solid, liquid or gas phase. A further specific feature of the surfactant is the formation of larger aggregates known as micelles. In the aggregate, the surfactant molecules are aligned in such a way that the polar groups form, for example, spherical surfaces. This has the effect that the substance such as dirt particles are dissolved in aqueous solution using the formation of micelles. The surfactants are therefore particularly suitable for cleaning surfaces as additives in cleaning compositions.

Surfactants with hydrophobic blocks and hydrophilic blocks are broad. However, the tendency to form their foams makes the surfactants unsuitable for many applications or only to a limited extent. Thus, for applications where strong foam formation is not desired, nonionic surfactants have been developed having a second hydrophobic block that limits the foam volume.

The second hydrophobic block can be derived from fatty alcohols, for example. However, the use of dishwashing compositions comprising such surfactants, in particular dishwashing compositions for machine dishwashers, often leaves residues in dishes which are cleaned using the composition (precipitate formation; spot deposits, if "dot" Or "membrane" for precipitates such as membranes).

The second hydrophobic block can alternatively be derived from fatty acids. In the case of dishwashing compositions comprising such surfactants, the problem of deposit formation is no longer a big problem; However, such surfactants are susceptible to hydrolysis due to ester groups which significantly limit their usefulness in alkaline formulations and at relatively high temperatures, especially in long term cleaning operations.

Thioethers of alcohol alkoxylates and their oxidized forms (ie sulfoxides and sulfones) are known theoretically from, for example, US Pat. No. 3,627,845. This document describes the use of such compounds as biologically active compositions, such as fungicides, acaricides and antiparasitic agents, and as surface-active substances in agrochemical formulations and coating compositions. No use as a cleaning or cleaning composition is mentioned.

The subject matter of the present invention is to provide compounds which do not have the disadvantages of conventional surfactants. More particularly the compound should not be strong even if it tends to form foam; The compound should leave low levels of residues, especially membrane residues, in dishwashed dishes, and at least less unstable to hydrolysis than fatty acid ester-based surfactants, even if they are unstable to hydrolysis. However, more particularly the compounds should have a maximum melting point so that they can also be formulated into solid wash and wash compositions.

The object of the present invention is achieved by using compounds of the formula (I) in washing or cleaning compositions, in particular dishwashing compositions:

[Wherein,

R is C ₈ -C ₂₄ -alkyl;

R 'is C ₆ -C ₁₈ -alkyl;

R ¹ and R ² are each independently at each occurrence C ₁ -C ₅ -alkyl;

m is 10 to 100;

l and n are each independently 0-15;

x is 0, 1 or 2].

The invention also relates to a cleaning or cleaning composition, in particular a dishwashing composition, comprising at least one compound of the formula (I) as defined above.

In the context of the present invention, C ₁ -C ₅ -alkyl is a linear or branched alkyl radical having 1 to 5 carbon atoms. Examples thereof are methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl and positional isomers thereof.

C ₆ -C ₁₈ -alkyl is a linear or branched alkyl radical having 6 to 18 carbon atoms. Examples thereof are hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, 2-propylheptyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl and positional isomers thereof. to be.

C ₈ -C ₂₄ -alkyl is a linear or branched alkyl radical having 8 to 24 carbon atoms. Examples thereof include octyl, 2-ethylhexyl, nonyl, decyl, 2-propylheptyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heni Kosyl, docosyl, tricosyl, tetracosyl and positional isomers thereof.

Branched C ₈ -C ₂₄ -alkyl is a positional isomer of octyl, such as 2-ethylhexyl, a positional isomer of n-nonyl, a positional isomer of n-decyl, such as 2-propylheptyl, a positional isomer of n-undecyl, n Position isomers of dodecyl, position isomers of n-tridecyl, position isomers of n-tetradecyl, position isomers of n-pentadecyl, position isomers of n-hexadecyl, position isomers of n-heptadecyl, n-octadecyl Positional isomers of decyl, positional isomers of n-nonadecyl, positional isomers of n-eicosyl, positional isomers of n-henicyl, positional isomers of n-docosyl, positional isomers of n-tricosyl, and n-tetracosyl Position isomer.

C ₁₀ -C ₁₄ -alkyl is a linear or branched alkyl radical having 10 to 14 carbon atoms. Examples thereof are decyl, 2-propylheptyl, undecyl, dodecyl, tridecyl, tetradecyl and positional isomers thereof.

Branched C ₁₀ -C ₁₄ -alkyl is a positional isomer of n-decyl, such as 2-propylheptyl, a positional isomer of n-undecyl, a positional isomer of n-dodecyl, a positional isomer of n-tridecyl and n-tetra The positional isomer of decyl.

C ₁₀ -C ₁₅ -alkyl is a linear or branched alkyl radical having 10 to 15 carbon atoms. Examples thereof are decyl, 2-propylheptyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl and positional isomers thereof.

Branched C ₁₀ -C ₁₅ -alkyl is a positional isomer of n-decyl, such as 2-propylheptyl, a positional isomer of n-undecyl, a positional isomer of n-dodecyl, a positional isomer of n-tridecyl, n-tetra Positional isomers of decyl and positional isomers of n-pentadecyl.

C ₈ -C ₁₅ -alkyl is a linear or branched alkyl radical having 8 to 15 carbon atoms. Examples thereof are the radicals mentioned above for C ₁₀ -C ₁₅ -alkyl, and also octyl, 2-ethylhexyl, nonyl and positional isomers thereof.

Branched C ₈ -C ₁₅ -alkyl is a positional isomer of octyl, such as 2-ethylhexyl, a positional isomer of n-nonyl, a positional isomer of n-decyl, such as 2-propylheptyl, a positional isomer of n-undecyl, n Positional isomers of dodecyl, positional isomers of n-tridecyl, positional isomers of n-tetradecyl and positional isomers of n-pentadecyl.

C ₁₂ -alkyl is dodecyl and its positional isomers.

With regard to the following preferred embodiments, reference is made in particular to the formula (I), its use and the preferred embodiment of the composition comprising the same, either alone or in any possible combination with another. Unless stated to the contrary, the above remarks apply to both the use of the invention and the cleaning and cleaning compositions of the invention.

Compounds I used according to the invention can be chemically pure substances or mixtures of different compounds I. In general, different compounds I (for example with different definitions of variables R, R ', l, m, n and / or x), due to the preparation method therefor and the reactants which may be industrial products or product mixtures used therein Mixtures will be included.

In compound I, R is preferably C ₈ -C ₁₅ -alkyl, more preferably C ₁₀ -C ₁₅ -alkyl, in particular C ₁₀ -C ₁₄ -alkyl. In certain embodiments, alkyl radicals R are branched. Specific examples of R include 2-propylheptyl, tridecyl and positional isomers thereof such as isotridecyl (ie, branched tridecyl radicals and mixtures thereof), n-dodecyl (lauryl), n-tetradecyl (myristyl ) And mixtures thereof.

R 'is preferably C ₁₀ -C ₁₄ -alkyl, in particular C ₁₂ -alkyl (dodecyl); Especially n-dodecyl.

R ¹ and R ² are preferably each independently methyl.

m is preferably 20 to 50, more preferably 25 to 50, even more preferably 25 to 45, in particular 25 to 40.

l and n are preferably each independently 0 to 5, more preferably 0, 1, 2 or 3. More particularly, l and n are each 0.

When at least one of the indices l or n is not 0, ethyleneoxy repeat units (-CH ₂ -CH ₂ -O-) and different repeat units (-CH ₂ -CH (R ¹ ) -O-) and / or ( -CH ₂ -CH (R ² ) -O-) may be arranged randomly or in blocks. It is preferably arranged in blocks; In other words, every l repeating units -CH ₂ -CH (R ¹ ) -O- that may be present form a block, followed by an ethyleneoxy block (-CH ₂ -CH ₂ -O-) _m , and thus This is followed by all n repeat units -CH ₂ -CH (R ² ) -O- that may exist in the block.

x is preferably 0 or 1.

Compound I is noteworthy with regard to its relatively high melting point. The melting point is preferably at least 35 ° C., for example 35 to 50 ° C., preferably 35 to 47 ° C., in particular 35 to 45 ° C .; More preferably 38 ° C. or higher, for example 38 to 50 ° C., preferably 38 to 47 ° C., especially 38 to 45 ° C., especially 40 ° C. or higher, for example 40 to 50 ° C., preferably 40 to 47 ° C. , In particular 40 to 45 ° C.

Processes for the preparation of compound I are known theoretically, for example from US Pat. No. 3,627,845. For example, if l is not 0, the alcohol R-OH is reacted with ethylene oxide after reacting with the following epoxides:

.

.

If n is not zero, the product obtained is then reacted with the following epoxides:

.

.

It is then reacted with mercaptoethanol R'-S-CH ₂ CH ₂ -OH to yield Compound I. If x should be 1 or 2, the thioether obtained is then oxidized.

The reaction with the epoxide is preferably carried out in anhydrous medium under base catalyst. The reaction is preferably carried out under an inert atmosphere such as nitrogen or argon. The reaction is preferably carried out in bulk, ie without additional solvent. Suitable bases are for example inorganic bases such as alkali metal hydroxides such as lithium, sodium or potassium hydroxides, alkaline earth metal hydroxides such as magnesium or calcium hydroxides, alkali metal carbonates such as lithium, sodium or potassium Carbonates, or alkaline earth metal carbonates such as magnesium or calcium carbonate. Sodium hydroxide and potassium hydroxide are preferred. The reaction temperature is preferably 50 to 200 ° C, more preferably 100 to 150 ° C. The reaction is preferably carried out under elevated pressure, for example 1.1 to 10 bar or 1.2 to 5 bar, built up by an inert gas and / or epoxide (especially ethylene oxide). In a preferred embodiment, the construction of an initial pressure with an inert gas, generally nitrogen, is preceded by the introduction of the epoxide. This initial pressure is preferably in the range from 1.1 to 5 bar, more preferably from 1.2 to 3 bar, in particular from 1.2 to 2 bar. In general, the addition of epoxides (particularly ethylene oxide) then leads to further pressure increases. The pressure during the actual reaction is preferably in the range of 1.2 to 10 bar, more preferably 2 to 8 bar. Upon completion of the conversion, the product mixture obtained can be neutralized if desired.

Condensation with mercaptoethanol is preferably carried out under acidic catalysts. Suitable acids are, for example, p-toluenesulfonic acid, methanesulfonic acid, phosphoric acid and acidic ion exchangers. During the reaction, the water of the reaction formed is preferably removed, for example by azeotropic distillation or stripping with an inert gas. If the water of the reaction is removed by azeotropic distillation, condensation is advantageously carried out in a solvent, such as toluene or xylene, to form a minimum azeotrope with water. Upon completion of the conversion, the product mixture obtained can be neutralized if desired.

The sulfur atoms in the thioethers obtained can be oxidized to sulfoxide (x = 1) or sulfone (x = 2) by conventional oxidizing agents such as hydrogen peroxide, manganese dioxide, permanganate, m-chloroperbenzoic acid or perchlorate. Whether oxidation proceeds to sulfoxide or to sulfone can be determined by factors including the choice of oxidant, its concentration and reaction temperature.

Compound I can be used according to the invention in the form of a solution obtained in its preparation. However, the compounds can preferably be isolated and purified if desired by conventional methods.

The compounds of formula (I) are theoretically usable in all usual cleaning and cleaning compositions.

In the context of the present invention, a cleaning composition is understood to mean a composition used for the cleaning of a flexible material having a high absorption rate, for example a material having a textile characteristic, whereas in the context of the present invention the cleaning composition is a continuous surface, In other words, it is understood to mean a composition used for cleaning a material having a surface having only a small amount of pores but only a low water absorptive rate even if there are pores.

Examples of flexible materials with high absorption are materials that include or consist of natural, synthetic or semisynthetic fibrous materials, and thus generally have at least partially textile characteristics. The fibrous material, or consisting of fibers, may be present in theory in any form that occurs in use or in production and processing. For example, the fibers may be in disordered form in the form of staples or aggregates, ordered forms in the form of fibers, yarns, threads, or in the form of nonwovens, roden or felt, woven fabrics, knits, such as in fabrics, such as all possible bond forms. . The fibers can be raw fibers or fibers in any processing state. 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 only small voids, if any, and have only low absorption, even if there is absorption, are metal, glass, enamel or ceramic. Typical objects made of such materials include, for example, metal sinks, cutlery, glass and porcelain dishes, bathtubs, washbasins, tiles, flags, cured synthetic resins, for example decorative melamine resin surfaces of kitchen furniture, Or finished metal surfaces, eg refrigerators and bodies, printed circuit boards, microchips, packaged or varnished wood, for example parquet or wall paneling, window frames, doors, plastic sheaths such as PVC or hard rubber Rigid sheets, or rigid or soft foams having substantially continuous surfaces.

Examples of cleaning compositions comprising compound I include dishwashing compositions, such as manual dishwashing compositions or mechanical dishwashing compositions (= dishwashing compositions for machine dishwashers), metal degreasing agents, glass cleaners, floor cleaners, multipurpose cleaners, high pressure cleaners, Neutral cleaners, alkaline cleaners, acid cleaners, spray degreasers, dairy cleaners, industrial kitchen cleaners, industrial and especially chemical industry equipment cleaners, car wash cleaners, and also household multipurpose cleaners.

Compound I is preferably used in dishwashing compositions. It is more preferably used in mechanical dishwashing compositions. Among these, preferred are dishwashing compositions with a rinse aid function, in particular mechanical dishwashing compositions.

Washing and cleaning compositions comprising compound I are preferably solid at room temperature (20 ° C.).

Solid cleaning and cleaning compositions can be powdered or tableted products ("tabs"). The composition is preferably a tableted product ("tablet"). More preferably, the composition is a tableted dishwashing composition, in particular a tableted machine dishwashing composition.

A tableted dishwashing composition may be a simple tableted product or a "2 in 1", "3 in 1", "5 in 1", "7 in 1" product, etc. (multifunctional products; generally "x in 1" products (x = Integer)). A more detailed description of such formulations can be found in "Hermann G. Hauthal, G. Wagner (eds.), Reinigungs- und Pflegemittel im Haushalt [Domestic Claning and Care Composition], Verlag fuer chemische Industrie, H. Ziolkowsky GmbH, Augsburg 2003, chapter 4.2 , pages 161-184 ". The "2 in 1" product contains the usual components of the mechanical dishwashing composition, as well as additional rinse aids. "3 in 1" products also contain a water softener. "5 in 1" products generally also include glass protectants and rinse strength enhancers. "7 in 1" products also include precious metal polishes and skin removers.

Compound I is preferably used in tableted, multifunctional mechanical dishwashing compositions, where the compound replaces, in whole or in part, conventional rinse aids.

Compound I has the effect as a surfactant and a rinse aid. The present invention therefore also relates to the use of compound I as surfactant and / or rinse aid. More particularly, the present invention relates to the use of compound I as a surfactant with a rinse aid effect or as a rinse aid surfactant.

Compounds I used according to the invention are particularly potent for good settling-suppressing action when used in the rinse cycle of a mechanical dishwasher. The compound has an inhibitory action on both inorganic and organic precipitates. Inorganic precipitates are in particular calcium and magnesium phosphates, calcium and magnesium carbonates, calcium and magnesium silicates and / or calcium and magnesium phosphonates, which are calcium and magnesium salts present in water and builders present in conventional dishwashing compositions. It is formed from. Organic precipitates are, in particular, dirt components from rinse liquors such as proteins, starch and fats and oils precipitates. Compounds I used according to the invention also originate from the residual amount of water at the bottom of the dishwasher and in particular comprise dishwashing composition residues and possibly also residues from previous washing cycles of the machine dishwasher. It is effective against so-called residual precipitates.

The present invention further provides a cleaning or cleaning composition comprising at least one compound of formula (I). With regard to suitable cleaning or cleaning compositions, reference is made to those mentioned above.

Washing and cleaning compositions are preferably dishwashing compositions, of which mechanical dishwashing compositions are preferred. This is especially a dishwashing composition with a rinse aid function, in particular a machine dishwashing composition.

The washing and cleaning compositions of the invention are preferably solid at room temperature (20 ° C.). With regard to suitable and preferred solid cleaning and cleaning compositions, reference is made to those mentioned above. More particularly, the cleaning and cleaning compositions of the present invention are tableted multifunctional mechanical dishwashing compositions. The compound I may be present therein in a rinse core; Preferably, the compound is present as a solid in the purified dishwashing composition.

The dishwashing composition of the present invention preferably comprises the following components:

a) at least one compound of formula (I);

b) one or more builders (also referred to as metal ion disintegrants, skeletal materials, complexing agents, chelators, chelating agents or emollients);

c) optionally one or more enzymes; And

d) optionally one or more bleaches; And

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

Such ingredients are preferably present in the dishwashing compositions of the present invention in the following proportions:

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

b) one or more builders: 5 to 80 weight percent;

c) one or more enzymes: 0 to 8% by weight;

d) at least one bleach: 0-30% by weight; And

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

Weight percent is based on the total weight of the dishwashing composition. The weight of a) to e) is 100% by weight in total.

The dishwashing composition of the present invention more preferably comprises one or more enzymes.

More preferably, the aforementioned components are present in the dishwashing compositions of the present invention in the following proportions:

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

b) one or more builders: 20 to 80% by weight;

c) one or more enzymes: 0.1 to 6 weight percent;

d) at least one bleach: 0-30% by weight; And

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

Weight percent is based on the total weight of the dishwashing composition. The weight from a) to e) totals 100% by weight.

Even more preferably, the dishwashing composition of the present invention also comprises one or more bleaches.

Even more preferably, the aforementioned ingredients are present in the dishwashing compositions of the present invention in the following proportions:

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

b) one or more builders: 20 to 80% by weight;

c) one or more enzymes: 0.1 to 6 weight percent;

d) at least one bleach: 5-25% by weight; And

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

Weight percent is based on the total weight of the dishwashing composition. The weight from a) to e) totals 100% by weight.

With regard to suitable and preferred compounds I, reference is made to those mentioned above.

Builders are sometimes referred to as metal ion disintegrants, structural materials, complexing agents, chelators, chelating or emollients, bonded alkaline earth metals and other water soluble metal salts that do not precipitate. Builders break down dirt, disperse dirt components, help the dirt separate, and in some cases have a self-cleaning effect. In addition, when the builder is a solid and used in a powder formulation, the powder remains free to flow.

Suitable builders can be organic or inorganic in nature. Examples are aluminosilicates, carbonates, phosphates and polyphosphates, polycarboxylic acids, polycarboxylates, hydroxycarboxylic acids, phosphonic acids, for example hydroxyalkylphosphonic acids, phosphonates, aminopolycarboxylic acids Acids and salts thereof, and polymeric compounds containing carboxylic acid groups and salts thereof.

Suitable inorganic builders are, for example, crystalline or amorphous aluminosilicates such as zeolites having ion-exchange properties. Several types of zeolites, in particular the sodium form, or zeolites A, X, B, P, MAP and HS, in which Na is partly exchanged with other cations such as Li, K, Ca, Mg or ammonium, are suitable. Suitable zeolites are described, for example, in US-A-4604224. Crystalline silicates suitable as builders are, for example, disilicates 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 can be used in the form of alkali metal, alkaline earth metal or ammonium salts, preferably as sodium, lithium and magnesium silicates. Amorphous silicates such as sodium metasilicate with polymer structure, or amorphous disilicates (Britesil® H 20, Akzo) are also available. Among them, sodium disilicate is preferable.

Suitable carbonate-based inorganic builder materials are carbonates and hydrogencarbonates. They can be used in the form of alkali metal, alkaline earth metal or ammonium salts. Preference is given to using sodium, lithium and magnesium carbonates or sodium, lithium and magnesium hydrogencarbonates, in particular sodium carbonate and / or sodium hydrogencarbonate.

Common phosphates used as inorganic builders are alkali metal orthophosphates and / or polyphosphates, for example pentasodium triphosphate.

Suitable organic builders are, for example, C ₄ -C ₃₀ -di-, -tri- and -tetracarboxylic acids, for example succinic acid, propanetricarboxylic acid, butanetetracarboxylic acid, cyclopentanetetracarboxylic acid And alkyl- and alkenylsuccinic acids with C ₂ -C ₂₀ -alkyl or -alkenyl radicals.

Suitable organic builders are also hydroxycarboxylic acids and polyhydroxycarboxylic acids (sugar acids). These are C ₄ -C ₂₀ -hydroxycarboxylic acids, for example malic acid, tartaric acid, glutonic acid, slime acid, lactic acid, glutaric acid, citric acid, tartronic acid, glucoheptonic acid, lactobionic acid, and sucrose mono- , -Di- and tricarboxylic acids. Among them, citric acid and salts thereof are preferred.

Suitable organic builders are also phosphonic acids such as hydroxyalkylphosphonic acids, aminophosphonic acids and salts thereof. These include, for example, phosphonobutanetricarboxylic acid, aminotrismethylenephosphonic acid, ethylenediaminetetraethylenephosphonic acid, hexamethylenediaminetetramethylenephosphonic acid, diethylenetriaminepentamethylenephosphonic acid, morpholinomethanediphosphonic acid , 1-hydroxy-C ₁ -to C ₁₀ -alkyl-1,1-diphosphonic acids such as 1-hydroxyethane-1,1-diphosphonic acid. Of these, preferred are 1-hydroxyethane-1,1-diphosphonic acid and salts thereof.

Suitable organic builders additionally include aminopolycarboxylic acids, such as nitrilotriacetic acid (NTA), nitrilomonoacetic dipropionic acid, nitrilotripropionic acid, β-alanine diacetic acid (β-ADA), ethylenediaminetetraacetic acid (EDTA) , Diethylenetriamine pentaacetic acid, 1,3-propylenediaminetetraacetic acid, 1,2-propylenediaminetetraacetic acid, N- (alkyl) ethylenediaminetriacetic acid, N- (hydroxyalkyl) ethylenediaminetriacetic acid, ethylenediamine Triacetic acid, cyclohexylene-1,2-diaminetetraacetic acid, iminodisuccinic acid, ethylenediaminedisuccinic acid, serine diacetic acid, isoserine diacetic acid, L-asparagine diacetic acid, L-glutamine diacetic acid, methylglycine diacetic acid ( MGDA), and salts of the aminopolycarboxylic acids described above. Among them, preferred are L-glutamine diacetic acid, methylglycine diacetic acid and salts thereof.

Suitable organic builders are additionally polymeric compounds containing carboxylic acid groups, for example acrylic acid homopolymers. It preferably has a number average molecular weight in the range from 800 to 70,000 g / mol, more preferably from 900 to 50,000 g / mol, in particular from 1000 to 20,000 g / mol, in particular from 1000 to 10,000 kg / mol. The term “acrylic acid homopolymer” also includes polymers in which some or all of the carboxylic acid groups are present in neutralized form. This includes acrylic acid homopolymers in which some or all of the carboxylic acid groups are present 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 some or all of the carboxylic acid groups are present 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, wherein the polymerized comonomers are in the amounts specified below in an amount of up to 95% by weight of group (i), 60% by weight. Monoethylenically unsaturated monomers from group (ii) in amounts of up to% and group (iii) in amounts up to 20% by weight. Suitable unsaturated C ₄ -C ₈ -dicarboxylic acids in this context are, for example, maleic acid, fumaric acid, itaconic acid and citraconic acid. Preferred is maleic acid. Group (i) includes monoethylenically unsaturated C ₃ -C ₈ -monocarboxylic acids, for example acrylic acid, methacrylic acid, crotonic acid and vinylacetic acid. From group (i), preference is given to using acrylic acid and methacrylic acid. Group (ii) is a monoethylenically unsaturated C ₂ -C ₂₂ - olefin, C ₁ -C ₈ - alkyl vinyl ether, styrene, C ₁ -C ₈ alkyl group having a carboxylic acid vinyl ester, (meth) acrylamides of And vinylpyrrolidone. From group (ii), preference is given to using C ₂ -C ₆ -olefins, vinyl alkyl ethers having C ₁ -C ₄ -alkyl groups, vinyl acetate and vinyl propionate. If the polymer of group (ii) comprises vinyl esters in polymerized form, the polymer may also be present partially or fully hydrolyzed into vinyl alcohol structural units. Suitable copolymers and terpolymers are known, for example, from US Pat. No. 3887806 and DE-A 4313909. Group (iii) is a (meth) acrylic ester of C ₁ -C ₈ -alcohol, (meth) acrylonitrile, (meth) acrylamide of C ₁ -C ₈ -amine, N-vinylformamide and N-vinyl Includes midazoles.

Suitable polymeric compounds containing carboxylic acid groups are also monoethylenically unsaturated C ₃ -C ₈ -monocarboxylic acids, for example acrylic acid, methacrylic acid, crotonic acid and vinylacetic acid, in particular acrylic acid and methacrylic acid alone. Polymers, copolymers of dicarboxylic acids, for example copolymers of maleic acid and acrylic acid in a weight ratio of 10:90 to 95: 5, more preferably in a weight ratio of 30:70 to 90:10, having a molar mass of 1000 to 150,000. ; Terpolymers of vinyl esters of maleic acid, acrylic acid and C ₁ -C ₃ -carboxylic acid (weight ratio is 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 within the range of 30:70 to 70:30); 40:60 to 80:20 molar ratio copolymer of maleic acid and C ₂ -C ₈ -olefin, particularly preferred is a copolymer of 50:50 molar ratio of maleic acid and ethylene, propylene or isobutene.

Suitable polymeric compounds containing carboxylic acid groups can also be used, for example, of from 50 to 98% by weight of ethylenically unsaturated weak carboxylic acid and from 2 to 50% by weight of ethylenically unsaturated sulfonic acid as described in EP-A-0877002. Copolymer. Suitable weak ethylenically unsaturated carboxylic acids are especially 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-methacrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-hydroxypropanesulfonic acid, allylsulfonic acid , Metallyl sulfonic acid, allyloxybenzene sulfonic acid, metarylylbenzenebenzene sulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propene-1-sulfonic acid, styrenesulfonic acid, vinyl Sulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate, sulfomethylacrylamide, sulfomethylmethacrylamide and salts of these acids. The copolymers also include in copolymerized form, from 0 to 30% by weight of ethylenically unsaturated C ₄ -C ₈ -dicarboxylic acid, such as maleic acid, and from 0 to 30% by weight of one or more monomers copolymerizable with the above-mentioned monomers. can do. The at least one copolymerizable monomer is for example C ₁ -C ₄ -alkyl ester of (meth) acrylic acid, C ₁ -C ₄ -hydroxyalkyl ester of (meth) acrylic acid, acrylamide, alkyl-substituted acrylic Amide, N, N-dialkyl-substituted acrylamide, vinylphosphonic acid, vinyl acetate, allyl alcohol, sulfonated allyl alcohol, styrene and other vinyl aromatics, acrylonitrile, N-vinylpyrrolidone, N-vinylform Amide, N-vinylimidazole or N-vinylpyridine. The weight average molecular weight of the copolymer is within the range of 3000 to 50,000. Particularly suitable copolymers are those having about 77% by weight of at least one ethylenically unsaturated C ₃ -C ₆ -monocarboxylic acid and about 23% by weight of at least one ethylenically unsaturated sulfonic acid.

Also suitable are graft polymers of unsaturated carboxylic acids to low molecular weight carbohydrates or hydrogenated carbohydrates (comp. US-A 5227446, DE-A 4415623 and DE-A 4313909). Suitable unsaturated carboxylic acids in this context are, for example, 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 intended to be grafted. It is grafted in an amount of 40 to 95% by weight based on the components. In the case of modifications, up to 30 weights of further monoethylenically unsaturated monomer can also be present in polymerized form, based on the component to be grafted. Suitable modifying monomers are the monomers of the groups (ii) and (iii) described above. Suitable graft bases are degraded polysaccharides such as acidic or enzymatically degraded starches, inulin or cellulose, protein hydrolysates and reduced (hydrogenated or hydrogenated amination) degraded polysaccharides such as mannitol, sorbitol , Polyalkylene glycols, aminosorbitol and N-alkylglucamine and likewise having a molar mass of M _w = 5000 or less, for example polyethylene glycol, ethylene oxide / propylene oxide or ethylene oxide / butylene oxide or ethylene oxide / oxidation Propylene / butylene oxide block copolymers and alkoxylated mono or polyvalent C ₁ -C ₂₂ -alcohols (comp. US-A-5756456).

Polyglyoxylic acids are also suitable as described, for example, in EP-B-001004, US-A-5399286, DE-A-4106355 and EP-A-656914. The end groups of polyglyoxylic acid may have different structures.

Additionally polyamidocarboxylic acids and modified polyamidocarboxylic acids are suitable; These are known, for example, from EP-A-454126, EP-B-511037, WO-A-94 / 01486 and EP-A-581452.

Cocondensates of polyaspartic acid or aspartic acid with additional amino acids, C ₄ -C ₂₅ -mono- or -dicarboxylic acids and / or C ₄ -C ₂₅ -mono- or -diamines contain carboxylic acid groups It can also be used as a polymeric compound. Especially preferred are prepared from phosphoric acid and C ₆ -C ₂₂ - is to use a modified using a diamine polyaspartic acid-mono-or-dicarboxylic acids or C ₆ -C ₂₂ - mono-or.

Of the polymeric compounds containing carboxylic acid groups, polyacrylic acids comprising partial or fully neutralized forms are preferred.

Suitable organic builders also include iminodisuccinic acid, oxydisuccinic acid, aminopolycarboxylates, alkyl polyaminocarboxylates, aminopolyalkylenephosphonates, polyglutamate, hydrophobically modified citric acid such as agaric acid, poly -α-hydroxyacrylic acid, N-acylethylenediamine triacetate such as lauroylethylenediamine triacetate and alkylamides of ethylenediaminetetraacetic acid, such as EDTA tallow amide.

It is also possible to use starch oxide as an organic builder.

Preference is given to using, as component b), mixtures of different builders.

The mixture of different builders preferably comprises two or more of the following components: one or more carbonates (eg sodium carbonate), one or more silicates (eg sodium disilicate), one containing carboxylic acid groups One or more polymeric compounds (e.g., polyacrylic acid), one or more (poly) hydroxycarboxylic acids or salts thereof (e.g., citric acid or Citrate), one or more aminopolycarboxylic acids or salts thereof (eg, methylglycine diacetic acid or salts thereof, eg sodium salts thereof), one or more phosphonic acids (eg, 1-hydroxyethane-1- (1, 1-diphosphonic acid); HEDP), at least one phosphate. More preferably, the mixture comprises one or more carbonates, one or more silicates and one or more polymeric, optionally (partially) neutralizing compounds containing carboxylic acid groups, and optionally one or more of the following components: one or more ( Poly) hydroxycarboxylic acids or salts thereof, one or more phosphonic acids, one or more phosphates. The mixture is especially one or more carbonates, one or more silicates, one or more polymeric, optionally (partly) neutralizing compounds containing carboxylic acid groups, one or more (poly) hydroxycarboxylic acids or salts thereof, and one or more phosph Phonic acid, and optionally one or more phosphates.

In the mixture, the components are preferably present in the following amounts:

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

b2) one or more silicates, 1 to 10% by weight;

b3) at least one polymeric, optionally (partially) neutralizing compound containing carboxylic acid groups: 5-20% by weight;

b4) at least one (poly) hydroxycarboxylic acid or salt thereof: 0-50% by weight;

b5) at least one aminopolycarboxylic acid or salt thereof: 0 to 60% by weight;

b6) at least one phosphonic acid: 0.2 to 1 weight percent;

b7) at least one phosphate: 0-60% by weight.

Weight percent is based on the total weight of the builder. The weights of b1) to b7) total 100% by weight.

The enzyme is preferably selected from hydrolases, such as proteases, esterases, glucosidases, lipases, amylases, cellulases, mannases, other glycosylhydrolases, and mixtures of the enzymes described above. All these hydrolases contribute to the dissolution and removal of dirt from protein-, oil- or starch-containing stains. For bleaching, it is also possible to use redox enzymes. Active enzyme components obtained from bacterial stains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus and Humicola insolens This is particularly suitable.

Suitable hydrolases are for example α-glucosidase (EC No. 3.2.1.20), proteases (Ovozyme® (manufactured by Novozymes); EC No. 3.2.1.20), amylases [Purastar® (from Genencor), Termamyl® (Novozymes) ), Stainzyme® (manufactured by Novozymes), Duramyl® (manufactured by Novozymes)], mannaze [Purabrite® (manufactured by Genencor), Mannastar® (manufactured by Genencor), Mannaway® (manufactured by Novozymes)] and cellulase [manufactured by Carezyme® (manufactured by Novozymes) ), Celluzyme® (manufactured by Novozymes), endolase, Puradax® (manufactured by Genencor)]. Suitable amylases include especially α-amylases (EC number 3.2.1.1), iso-amylases, pullulans and pectins. The cellulases used are preferably cellobiohydrolases, endoglucanases and β-glucosidase (also known as cellobiases) or mixtures thereof. Since different cellulase types have different CMCase and avicelase activity, the desired activity can be established by a controlled mixture of cellulase.

Suitable lipases are esterases such as Lipex and Lipolase. An example of a lipolytic active enzyme is a known cutinase.

Peroxidases or oxidases have also been found to be suitable in some cases.

The dishwashing composition of the present invention preferably comprises one or more proteases and / or amylases.

The dishwashing composition of the present invention preferably comprises an enzyme mixture. For example, enzyme mixtures comprising or consisting of the following enzymes are preferred:

Proteases and amylases,

Proteases and lipases (or lipolytically active enzymes),

Proteases and cellulases,

Amylases, cellulases and lipases (or lipolytically active enzymes),

Proteases, amylases and lipases (or lipolytically active enzymes),

Proteases, lipases (or lipolytic active enzymes) and cellulases.

Particular preference is given to proteases and / or amylase-containing mixtures. Preferred proteases in the abovementioned mixtures are proteases of the subtilisin type (Savinase et al .; EC No. 3.4.21.62).

The enzyme can be adsorbed on the carrier to protect it from premature degradation.

Optionally, the cleaning and cleaning compositions of the present invention may also include enzyme stabilizers such as calcium propionate, sodium formate or boric acid or salts thereof, and / or antioxidants.

Bleach d) is preferably a bleach system in addition to bleach, optionally also optionally including a bleach activator, a bleach catalyst and / or a bleach stabilizer.

Suitable bleaches are, for example, percarboxylic acids, for example diperoxododecanedicarboxylic acid, phthalimidopercaproic acid or monoperoxophthalic acid or -terephthalic acid, salts of percarboxylic acid, for example sodium perkar Carbonates, adducts of hydrogen peroxide to inorganic salts, for example sodium perborate monohydrate, sodium perborate tetrahydrate, sodium carbonate perhydrate or sodium phosphate perhydrate, addition of hydrogen peroxide to organic compounds Water, for example urea perhydrate, or inorganic peroxo salts, for example alkali metal persulfates or peroxodisulfates.

Suitable bleach activators include, for example, polyacrylated sugars such as pentaacetylglucose; Acyloxybenzenesulfonic acid and its alkali metal and alkaline earth metal salts such as sodium p-nonanoyloxybenzenesulfonate or sodium p-benzoyloxybenzenesulfonate; N, N-diacylated and N, N, N ', N'-tetraacylated amines such as N, N, N', N'-tetraacetylmethylenediamine and -ethylenediamine (TAED), N, N -Diacetylaniline, N, N-diacetyl-p-toluidine or 1,3- diacylated hydantoin such as 1,3-diacetyl-5.5-dimethylhydantoin; N-alkyl-N-sulfonylcarbonamides such as N-methyl-N-mesylacetamide or N-methyl-N-mesylbenzamide; N-acylated cyclic hydrazides, acylated triazoles or uraazoles such as monoacetylmaleic acid hydrazide; O, N, N-trisubstituted hydroxylamines, such as O-benzoyl-N, N-succinylhydroxylamine, O-acetyl-N, N-succinylhydroxylamine or O, N, N-tri Acetylhydroxylamine; N, N'- diacylsulfurylamide, z. B. N, N'-dimethyl-N, N'-diacetylsulfurylamide or N, N'-diethyl-N, N'-dipropionylsulfurylamide; Acylated lactams such as acetylcaprolactam, octanoylcaprolactam, benzoylcaprolactam or carbonylbiscaprolactam; Anthranyl derivatives such as 2-methylanthranyl or 2-phenylanthranyl; Triacyl cyanurates such as triacel cyanurate or tribenzoyl cyanurate; Oxime esters and bisoxime esters such as O-acetylacetone oxime or bisisopropyl iminocarbonate; Carboxylic anhydrides such as acetic anhydride, benzoic anhydride, m-chlorobenzoic anhydride or phthalic anhydride; Enol esters such as isopropenyl acetate; 1,3-diacyl-4,5-diacyloxyimidazoline, for example 1,3-diacetyl-4,5-diacetoxyimidazoline; Tetraacetylglycoluril and tetrapropionylglycoluril; Diacylated 2,5-diketopiperazine, for example 1,4-diacetyl-2,5-diketopiperazine; Ammonium-substituted nitriles such as N-methylmorpholinioacetonitrile methylsulfate; Acylated products of propylenediurea and 2,2-dimethylpropylenediurea, for example tetraacetylpropylenediurea; α-acyloxypolyacylmalonamides such as α-acetoxy-N, N′-diacetylmalonamide; Diacyldioxohexahydro-1,3,5-triazine, for example 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine; Benz- (4H) -1,3-oxazin-4-one with an alkyl radical in the 2 position, for example methyl or an aromatic radical, for example phenyl.

Bleach systems consisting of bleach and bleach activator may optionally also comprise a bleach catalyst. 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. For their use in cleaning and cleaning compositions the compounds are incorporated in amounts up to 1.5% by weight, in particular up to 0.5% by weight and in amounts of up to 0.1% by weight for highly active manganese complexes.

In addition to the described bleach systems consisting of bleaches, bleach activators and optionally bleach catalysts, it is also possible to use systems with enzymatic peroxide release or photoactivated bleach systems for the cleaning and cleaning compositions of the invention.

In addition to component a), the surfactants of group e) may be cationic, anionic, zwitterionic or nonionic.

Suitable nonionic surfactants are, for example, alkoxylated, advantageously ethoxylated, in particular 1 to 20, preferably 1 to 12 mol of ethylene oxide (EO) and preferably 8 to 18 carbons per mole of alcohol. Primary alcohols having atoms, wherein the alcohol radicals may be linear or preferably 2-methyl-branched or may comprise linear and methyl-branched radicals in a mixture, as typically present in oxo alcohol radicals. . However, particularly preferred are those having linear radicals formed from alcohols of natural origin having an average of 2 to 8 EO and 12 to 18 carbon atoms per mole of alcohol, for example coconut alcohol, palm alcohol, tallow alcohol or oleyl alcohol. Alcohol ethoxylate. Preferred ethoxylated alcohols include, for example, C ₁₂ -C ₁₄ -alcohols with 3 EO, 4 EO or 7 EO, C ₉ -C ₁₁ -alcohols with 7 EO, 3 EO, 5 EO, 7 EO or 8 EO C ₁₃ -C ₁₅ -alcohols having, C ₁₂ -C ₁₈ -alcohols having 3 EO, 5 EO or 7 EO and mixtures thereof, such as C ₁₂ -C ₁₄ -alcohols having 3 EO and C ₁₂ -having 7 EO Contains a mixture of C ₁₈ -alcohols. The degrees of ethoxylation shown are statistical mean values, which may be integers or fractions for certain products. Also suitable are alcohol ethoxylates (narrow range ethoxylates, NRE) with a narrow homology distribution. In addition to these nonionic surfactants, fatty alcohols having more than 12 EO can also be used. Examples thereof are tallow alcohols having 14 EO, 25 EO or 30 EO. Nonionic surfactants can also be used that include EO and PO groups together in a molecule. In this case, block copolymers having EO-PO block units or PO-EO block units, and also EO-PO-EO copolymers or PO-EO-PO copolymers can be used. It will be appreciated that mixed-alkoxylated nonionic surfactants in which the EO and PO units are not blocky and are randomly distributed may also be used. The product can be obtained by the simultaneous action of ethylene oxide and propylene oxide on fatty alcohols.

In addition, the additional nonionic surfactants used may also be alkyl glycosides of the formula (I):

R ^a O (G) _y (1)

[Wherein R ^a is ^a linear or methyl-branched, in particular 2-methyl-branched, aliphatic radical having 8 to 22 carbon atoms, preferably 12 to 18 carbon atoms, and G is a glycoside having 5 or 6 carbon atoms Unit, preferably glucose]. Degree of oligomerization y representing the distribution of monoglycosides and oligoglycosides is any number from 1 to 10; y is preferably 1.2 to 1.4.

A further class of suitable nonionic surfactants which can be used as sole nonionic surfactants or in combination with other nonionic surfactants is preferably alkoxylation, preferably ethoxy having 1 to 4 carbon atoms in the alkyl chain. Fatty acid methyl prepared by the method of oxidization or ethoxylation and propoxylation, fatty acid alkyl esters, in particular in Japanese patent application JP 58/217598, or preferably in international patent application WO-A-90 / 13533 Of esters.

Amine oxide types such as N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and nonionic surfactants of fatty acid alkanolamide type are also May be suitable. The amount of such nonionic surfactants is preferably up to the amount of ethoxylated fatty alcohols, in particular up to half thereof.

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

[Wherein R ^b C (═O) is 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 3 to 10 carbon atoms Linear or branched polyhydroxyalkyl radical having 3 to 10 hydroxyl groups. Polyhydroxy fatty acid amides are typically known materials that can be obtained by reductive amination of reducing sugars with ammonia, alkylamines or alkanolamines, and subsequent acylation with fatty acids, fatty acid alkyl esters or fatty acid chlorides.

The group of polyhydroxy fatty acid amides also includes compounds of formula (3):

[Wherein R ^e is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, and 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 R ^g is a linear, branched or cyclic alkyl radical or aryl radical or oxyalkyl radical having 1 to 8 carbon atoms, preferably a C ₁ -C ₄ -alkyl or phenyl radical, [Z] ¹ is a linear polyhydride Oxyalkyl radicals, the alkyl chains of which are substituted with two or more hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of such radicals. [Z] ¹ is preferably obtained by reductive amination of sugars such as glucose, fructose, maltose, lactose, galactose, mannose or xylose. N-alkoxy- or N-aryloxy-substituted compounds can then be converted to the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of alkoxides as catalysts, for example according to WO-A-95 / 07331. have.

Suitable anionic surfactants are for example of the sulfonate and sulfate types. Useful surfactants of the sulfonate type are preferably C ₉ -C ₁₃ -alkylbenzenesulfonates, olefinsulfonates, ie sulfonation with, for example, gaseous sulfur trioxide and then alkaline or acidic hydrolysis of the sulfonated product. A mixture of alkene- and hydroxyalkanesulfonates and disulfonates obtained by C ₁₂ -C ₁₈ -monoolefins having terminal or internal double bonds. Also suitable are alkanesulfonates obtained from C ₁₂ -C ₁₈ -alkanes, for example by sulfochlorination or sulfoxylation and subsequent hydrolysis or neutralization. Equally suitable are also esters of the α-sulfo fatty acids (ester sulfonates), for example α-sulfonated methyl esters of hydrogenated coconut fatty acids, palm kernel fatty acids or uji acids.

Further suitable anionic surfactants are sulfonated fatty acid glyceryl esters. Fatty acid glyceryl esters are obtained from the mono-, di- and triesters obtained at the time of preparation by esterification of monoglycerol with 1 to 3 mol of fatty acid or by transesterification of triglyceride with 0.3 to 2 mol of glycerol and mixtures thereof. It is understood to mean. Preferred sulfonated fatty acid glyceryl esters are sulfonated saturated fatty acids having 6 to 22 carbon atoms, such as caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid. Product.

Preferred al (ken) yl sulfates are alkali metal salts, in particular C ₁₂ -C _18. Fatty alcohols such as coconut fatty alcohol, tallow alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol or stearyl alcohol, or C ₁₀ -C ₂₀ Sulfuric acid monoesters of oxo alcohols, and alkali metal salts, in particular sodium salts, of monoesters of such chain length secondary alcohols. Further preferred are al (ken) yl sulfates of the mentioned chain length, which are prepared on a petrochemical basis and comprise synthetic straight chain alkyl radicals having the same degradation behavior as equivalent compounds based on fatty chemical raw materials. In view of washing, C ₁₂ -C ₁₆ -alkyl sulfates and C ₁₂ -C ₁₅ -alkyl sulfates, and also C ₁₄ -C ₁₅ -alkyl sulfates, are preferred. Also suitable are anionic surfactants, for example 2,3-alkyl sulfates prepared according to US Pat. No. 3,234,258 or 5,075,041 and obtainable as commercially available products from Shell Oil Company under the name DAN®.

Straight or branched C ₇ -C ₂₁ -alcohols ethoxylated by 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C ₉ -C ₁₁ -alcohols with an average of 3.5 mol of ethylene oxide (EO), Or sulfuric acid monoesters of C ₁₂ -C ₁₈ fatty alcohols having 1 to 4 EO are also suitable. Due to their high foaming level, they are used in cleaning compositions only in relatively small amounts, for example in amounts of 1 to 5% by weight.

Further suitable anionic surfactants are also salts of alkylsulfosuccinic acids, which are also represented as sulfosuccinates or sulfosuccinic esters, which are monoesters of sulfosuccinic acid with alcohols, preferably fatty alcohols, in particular ethoxylated fatty alcohols and And / or diesters. Preferred sulfosuccinates include C ₈ -C ₁₈ fatty alcohol radicals or mixtures thereof. Particularly preferred sulfosuccinates comprise fatty alcohol radicals derived from ethoxylated fatty alcohols. Particular preference is given to sulfosuccinates which in turn derive from ethoxylated fatty alcohols having a narrow homology distribution of fatty alcohol radicals. It is likewise possible to use al (ken) yl succinic acids, or salts thereof, preferably with 8 to 18 carbon atoms in the al (ken) yl chain.

Suitable anionic surfactants are also soaps. Saturated and unsaturated fatty acid soaps such as lauric acid, myristic acid, palmitic acid, stearic acid, salts of (hydrogenated) erucic acid and behenic acid, especially natural fatty acids such as coconut fatty acids, palm kernel fatty acids, olive oil Soap mixtures derived from fatty acids or Uji acid are suitable.

Anionic surfactants, including soaps, can be present in the form of sodium, potassium or ammonium salts, or as soluble salts of organic bases such as mono-, di- or triethanolamine. Anionic surfactants are preferably in the form of their sodium or potassium salts, in particular in the form of sodium salts.

Cationic surfactants are for example ammonium salts such as C ₈ -C ₁₆ -dialkyldimethylammonium halides, dialkoxydimethylammonium halides or imidazolinium salts with long chain alkyl radicals.

Amphoteric surfactants are, for example, derivatives of secondary or tertiary amines, for example C ₆ -C ₁₈ -alkyl betaines or C ₆ -C ₁₅ -alkyl sulfobetaines or amine oxides such as alkyldimethylamine oxides.

The solvent present in component e) is for example derived from the group of monohydric or polyhydric alcohols, alkanolamines or glycol ethers. It is preferably ethanol, n- or isopropanol, butanol, glycol, propane- or butanediol, glycerol, diglycol, propyl- or butyldiglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether , Ethylene glycol mono-n-butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, propylene glycol methyl, ethyl or propyl ether, dipropylene glycol monomethyl or monoethyl ether, diisopropylene glycol monomethyl or monoethyl Ether, methoxy-, ethoxy- or butoxytriglycol, isobutoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, propylene glycol tertbutyl ether and mixtures of these solvents.

Useful foam inhibitors or antifoams of component e) can be, for example, soaps, paraffins or silicone oils, which may optionally be applied to the carrier material.

Suitable bases of component e) are the carbonates mentioned above in particular with respect to builders.

In an alternatively preferred embodiment of the invention, the cleaning and cleaning compositions of the invention are in gel form. Washing and cleaning composition gels are preferably dishwashing composition gels, of which mechanical dishwashing composition gels are particularly preferred. More particularly, it is a dishwashing composition gel with a rinse aid function, preferably a machine dishwashing composition gel.

Washing and Cleaning Compositions Gels are understood to mean fluid compositions that have a viscosity that exceeds the viscosity of water at room temperature (20 ° C.) but can still be administered without any problem with conventional dosing aids. The cleaning and cleaning composition gels of the invention preferably have a viscosity at 20 ° C. of 0.5 to 100, more preferably 0.5 to 50, in particular 1 to 30 Pa · s.

The dishwashing composition gel of the invention preferably comprises the following components:

a) at least one compound of formula (I);

b) one or more builders (also known as metal ion sequestrants, structural materials, complexing agents, chelators, chelating agents or emollients);

c) optionally one or more enzymes;

d) optionally one or more bleaches;

e1) water;

e2) one or more thickeners; And

e3) at least one additional additive, preferably selected from surfactants, bases, corrosion inhibitors, antifoams, dyes, flavors, fillers, solubilizers and organic solvents other than a).

Such ingredients are preferably present in the dishwashing composition gels of the present invention in the following proportions:

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

b) one or more builders: 5 to 80 weight percent;

c) one or more enzymes: 0 to 8% by weight;

d) at least one bleach: 0-30% by weight;

e1) water: 10-90 weight percent;

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

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

Weight percent is based on the total weight of the dishwashing composition. The weight of a) to e3) is 100% by weight in total.

The dishwashing composition of the present invention more preferably comprises one or more enzymes.

The aforementioned components are more preferably present in the dishwashing composition of the present invention in the following proportions:

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

b) one or more builders: 5 to 60 weight percent;

c) one or more enzymes: 0.1 to 6 weight percent;

d) at least one bleach: 0-30% by weight; And

e1) water: 10-90 weight percent;

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

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

Weight percent is based on the total weight of the dishwashing composition. The weight of a) to e3) is 100% by weight in total.

The aforementioned components are even more preferably present in the dishwashing composition gel of the invention in the following proportions:

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

b) one or more builders: 5 to 40 weight percent;

c) one or more enzymes: 0.1 to 6 weight percent;

d) at least one bleach: 0-25% by weight; And

e1) water: 20-80 wt%;

e2) at least one thickener: 0.3-50% by weight; And

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

Weight percent is based on the total weight of the dishwashing composition. The weight of a) to e3) is 100% by weight in total.

The thickener serves to impart the desired viscosity to the dishwashing composition of the present invention.

Any known thickener (fluid modifier) is theoretically suitable, provided it does not adversely affect the efficacy of the dishwashing composition. Suitable thickeners may be of natural origin or of synthetic nature.

Examples of thickeners of natural origin are xanthan, carob flour, guar flour, carrageenan, agar, tragacanth, gum arabic, alginate, modified starch such as hydroxyethyl starch, starch phosphate ester Or starch acetate, dextrin, pectin and cellulose derivatives such as carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, methyl cellulose and the like.

Thickeners of natural origin are also the silicates mentioned for inorganic thickeners such as polysilic acid and clay minerals such as sheet silicates, and also builders.

Examples of synthetic thickeners are polyacrylic and polymethacrylic compounds, such as acrylic acid crosslinked with (partly) crosslinked homopolymers of acrylic acid, such as allyl ethers of pentaerythritol or sucrose or crosslinked with propylene (carbomer). Homopolymers, for example Carbopol® from BF Goodrich (for example Carbopol® 676, 940, 941, 934, etc.) or trade name Polygel® (for example Polygel® DA) from 3V Sigma, ethylenically unsaturated mono- Or terpolymers of (meth) acrylates derived from copolymers of dicarboxylic acids, for example acrylic acid, methacrylic acid or maleic acid with methyl acrylate or ethyl acrylate and long chain ethoxylated alcohols, for example Rohm & Haas trade name, manufactured by Acusol® (e.g. Acusol® 820 or 1206A), acrylic acid, methacrylic acid and its C ₁ -C ₄ - two or more selected from alkyl esters Copolymers of monomers, for example methacrylic acid, butyl acrylate and methyl methacrylate or copolymers of butyl acrylate and methyl methacrylate, for example the trade names Aculyn® and Acusol® from Rohm & Haas Aculyn® 22, 28 or 33 and Acusol® 810, 823 and 830), or crosslinked high molecular weight acrylic acid copolymers such as C ₁₀ -C ₃₀ -alkyl acrylates and acrylic acid, methacrylic acid and C _1- Copolymers with one or more comonomers selected from C ₄ -alkyl esters (the copolymers are crosslinked with pentaerythritol or allyl ethers of sucrose) (eg Carbopol® ETD 2623, Carbopol® from Rohm & Haas) 1382 or Carbopol® AQUA 30).

Examples of synthetic thickeners are also reaction products of maleic acid polymers with ethoxylated long chain alcohols, for example Texaco Chemical Co. Surfonic L series manufactured by Gantrez AN-119, manufactured by ISP; Polyethylene glycols, polyamides, polyimines and polycarboxylic acids.

Also suitable are mixtures of the abovementioned thickeners.

Preferred thickeners are xanthan and the aforementioned polyacrylic and polymethacrylic compounds.

With regard to suitable and preferred components a) to d) and e3), reference is made to the abovementioned contents.

Compounds I used according to the invention are notable for their high melting point compared to conventional prior art surfactants, which allow their use as solid cleaning and cleaning compositions. It does not tend to be strong even though it tends to form a foam, which has a good deposition-inhibiting action, especially with regard to dishes washed with it in connection with stains, which is not hydrolytically unstable.

The present application is now further described by the following non-limiting examples.

Example

1. Synthetic Example

General method

1.1 Preparation of Alkyloxy Ethylene Glycol Dodecyl Mercaptoethanol

1.1.1 Preparation of Alcohol Ethoxylates:

In a 2 L autoclave from Mettler, the alcohol to be alkoxylated (isotridecanol, 2-propylheptanol or C ₁₂ / C ₁₄ -alcohol; 1.0 eq) is mixed with an aqueous KOH solution containing 50% by weight of KOH It was. The amount of KOH is 0.2% by weight of the product to be prepared. While stirring, the mixture was dehydrated at 100 ° C. and 20 mbar for 2 hours. After the three purged with N ₂ after therefore, was to establish the initial pressure of N ₂ to approximately 1.3 bar, the temperature was raised to 120 ℃. Ethylene oxide (n equimolar) was weighed so that the temperature was maintained at 125 to 135 ° C. It was then stirred for an additional 5 hours at 125 ° C., purged with N ₂ , cooled to 70 ° C. and the reactor was emptied. The crude product was degassed in a rotary evaporator at 100 ° C. (<20 mbar) for 2 hours. This basic crude product can be deionized with commercial magnesium silicate, which is then filtered off. Alternatively, neutralization with acetic acid can also be carried out. ¹ H NMR spectra in CDCl ₃ and gel permeation chromatography, and also OH number determination, characterized the light colored product and the yield was determined (> 98%).

1.1.2 Reaction with dodecyl mercaptoethanol

A 500 ml device with a water trap was first charged with alkoxylate (1 equimolar), para-toluenesulfonic acid (0.005 equimolar) and toluene from Example 1.1.1. The reaction mixture was heated to reflux. Dodecyl mercaptoethanol (x equimolar) was added dropwise. Water formed was removed by water trap overnight. The reaction mixture was cooled down, neutralized with sodium carbonate (0.005 equimolar), filtered and the solvent was completely removed at 100 ° C. and 6 mbar. This yielded a white solid product. The structure was measured by TAI NMR (% OH group converted). The residual amount of toluene (always <0.5%) and the residual amount of dodecylmercaptoethanol were measured by GC.

* According to TAI NMR

** According to quantitative GC

iC ₁₃ = "isotridecanol"; Mixtures of Different Tridecanol Isomers

EO = ethylene oxide

PO = propylene oxide

2PH = 2-propylheptanol

1.2 Oxidation of Product C to Corresponding Sulphoxide D

In a 250 mL flask introduced into water and heated to 70 ° C., 71.6 g (40 mmol, 1 equimolar) of the product C described above were melted. Hydrogen peroxide (50%) (4.1 g, 60 mmol, 1.5 equimoles) was added dropwise. The reaction mixture was stirred for 2 h at 70 ° C, then cooled and concentrated at 100 ° C and 6 mbar. This yielded 69.2 g (96% yield) of solid yellow product. Absence of hydrogen peroxide was confirmed by IR, and conversion (100%) was measured by ¹ H NMR.

Explain how to TAI NMR:

^In order to be able to measure (quantitatively) the signals of superimposed primary and / or secondary alcohols in the ¹ H NMR spectrum, samples in CDCl ₃ were mixed with excess TAI (trichloroacetyl isocyanate). Isocyanates immediately reacted with alcohol groups to produce carbamate. OCH ₂ R or _{Cl 3 CC (O) NHC (} O) - - The present compound _{Cl 3 CC (O) NHC (} O) OCH that -RR 'is OCH ₂ and OCHRR in ¹ H NMR spectrum, different with respect to, and typically Have a move.

Typical shift ranges for "primary carbamate" are 4.0 to 4.5 ppm, while typical shift range for "secondary carbamate" is 5.0 to 5.3 ppm.

2. Example

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

PO = propylene oxide

EO = ethylene oxide

DeO = 1,2-decane oxide

iC ₁₃ = "isotridecanol"; Mixtures of Different Tridecanol Isomers

2PH = 2-propylheptanol

2.1 Melting Point Measurement

Melting point was measured by DSC (color difference scanning calorimeter).

2.2 Foam Volumes in Mechanical Dishwashers

The foam volume was indirectly measured by measuring the foam formation through the speed of the spray arm of the mechanical dishwasher. For this purpose, 10 ml of broken eggs, 19 g of base dishwashing composition (48 parts of sodium metasilicate x 5H ₂ O, 45 parts sodium triphosphate, 5 parts sodium carbonate) and 1 g of surfactant (AF) are dishwasher (Miele Desinfektor G 7735 CD MCU; Programmable Controller MCU Version S04.01). At different temperatures, the number of revolutions of the spray arm was then measured. Spray arms are slowed down at high foam levels; It can be operated at the highest possible speed (about 125 rpm) at low foam levels. The maximum speed of the dishwasher is typically about 125 rpm when no foam is present. In order to obtain a wider range that allows for a better difference in the product, the maximum speed in the machine dishwasher in the test of the present invention was artificially set (by the hole in the spray arm, the position of the nozzle).

The rotation speeds were measured at 40, 50 and 60 ° C. The table below lists the revolutions at rpm at different temperatures.

2.3 Rinse Aid Test

All examples were performed using base formulations of the following composition:

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

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

3 parts by weight of surfactant

10 parts by weight of polyacrylic acid (Sokalan® PA 25 Cl) with a molar mass of 4000 g / mol

10.5 parts by weight sodium percarbonate

4 parts by weight of tetraacetylethylenediamine

2 parts by weight sodium disilicate (Britesil® H265 LC)

18.8 parts by weight sodium carbonate

33 parts by weight of sodium citrate dihydrate

15 parts by weight of methylglycinediacetic acid trisodium salt (Trilon® M)

0.5 parts by weight of 1-hydroxyethane- (1,1-diphosphonic acid) (HEDP; Cublen® K8514 GR)

Ovozyme® and Stainzyme® are trade names of Novozymes, Sokalan® and Trilon® are trade names of BASF SE, and Britesil® is PQ Corp. Cublen® is a trade name of Zschimmer & Schwarz Mohsdorf GmbH & Co KG.

All rinse aid tests were performed in a Miele mechanical dishwasher (G1222 SCL). The program at 50 ° C. (R time 2) was selected for the wash cycle and the program at 65 ° C. for the rinse cycle. The test was performed using hardened water with a water hardness of 21 ° dH (Ca / Mg): HCO ₃ (3: 1): 1.35. No separate rinse aid was added and the incorporated softeners (ion exchangers) were not regenerated with regenerating salts. The formulations mentioned above were used in each case at a dosage of 21 g. For each rinse cycle, 100 g of ballast soil consisting of fat, protein and starch were added. The test dishes in each cleaning cycle were Cromargan knives, blue melamine dishes, glass and magnetic dishes. Between rinse cycles, in each case there was an hour of congestion, with 10 minutes closed and 50 minutes open.

After the six rinse cycles have ended, the dishes are visually inspected in the dark under light behind an exposed aperture plate, and 1 (= severe residue) to 10 (= No residue).

2.4 Stability Tests Over Range of Use

The test was similar to 2.2. Rotational speed was measured at the maximum temperature (57 ° C.-70 ° C.) over a period of 2 hours. In the table below, the rotational speeds are listed in rpm. Under the speed of rotation, the exact temperature is listed in square brackets.

Claims (30)

Use of a compound of formula (I) in a cleaning or cleaning composition:

[Wherein,
R is C ₈ -C ₂₄ -alkyl;
R 'is C ₆ -C ₁₈ -alkyl;
R ¹ and R ² are each independently at each occurrence C ₁ -C ₅ -alkyl;
m is 10 to 100;
l and n are each independently 0-15;
x is 0, 1 or 2]. The use of claim 1, wherein the cleaning and cleaning composition is selected from the dishwashing compositions. 3. Use according to claim 2, wherein the cleaning and cleaning composition is selected from mechanical dishwashing compositions. 4. Use according to claim 2 or 3, wherein the cleaning and cleaning composition is selected from dishwashing compositions having a rinse aid function. The use according to any one of claims 1 to 4, wherein the cleaning and cleaning composition is a solid. The use according to any one of claims 1 to 4, wherein the cleaning and cleaning composition is in the form of a gel. The use according to any one of claims 1 to 6, wherein compound I is used as a surfactant. 8. Use according to any one of claims 1 to 7, wherein compound I is used as a rinse aid surfactant. The use according to any one of claims 1 to 8, wherein R is C ₁₀ -C ₁₅ -alkyl. 10. Use according to any of the preceding claims, wherein R 'is C ₁₀ -C ₁₄ -alkyl, preferably C ₁₂ -alkyl. Use according to any of the preceding claims, wherein R ¹ and R ² are each independently methyl in each case. The use according to any one of claims 1 to 11, wherein m is 25 to 50. 13. Use according to any of the preceding claims, wherein l and n are each zero. 14. Use according to any one of the preceding claims, wherein x is 0 or 1. The use according to any one of claims 1 to 14, wherein the melting point of compound I is at least 35 ° C, preferably at least 38 ° C. A cleaning or cleaning composition comprising at least one compound of formula (I) as defined in any one of claims 1 and 9-15. The cleaning or cleaning composition of claim 16, wherein the cleaning or cleaning composition is a dishwashing composition. 18. The cleaning or cleaning composition of claim 17, wherein the cleaning or cleaning composition is a mechanical dishwashing composition. 19. The cleaning or cleaning composition of claim 17 or 18, which is a dishwashing composition having a rinse aid function. 20. The cleaning or cleaning composition of any of claims 16 to 19, wherein the cleaning or cleaning composition is solid at room temperature. The cleaning or cleaning composition of claim 18 comprising the following components:
a) at least one compound of formula (I);
b) one or more builders;
c) optionally one or more enzymes;
d) optionally one or more bleaches; And
e) one or more additional additives optionally selected from surfactants, bases, corrosion inhibitors, antifoams, dyes, flavors, fillers, tableting aids, disintegrants, thickeners, solubilizers, organic solvents and water other than a). The cleaning or cleaning composition of claim 21 comprising the following components based on the total weight of the cleaning or cleaning composition:
a) at least one compound of formula I: 0.1-20% by weight;
b) one or more builders: 5 to 80 weight percent;
c) one or more enzymes: 0 to 8% by weight;
d) at least one bleach: 0-30% by weight; And
e) at least one further additive: 0-50% by weight. 23. The cleaning or cleaning composition of claim 21 or 22 comprising the following ingredients based on the total weight of the cleaning or cleaning composition:
a) at least one compound of formula I: 0.1 to 10% by weight;
b) one or more builders: 20 to 80% by weight;
c) one or more enzymes: 0.1 to 6 weight percent;
d) at least one bleach: 0-30% by weight; And
e) at least one further additive: 0-50% by weight. 24. A cleaning or cleaning composition according to any of claims 21 to 23, comprising the following components based on the total weight of the cleaning or cleaning composition:
a) at least one compound of formula I: 0.1 to 10% by weight;
b) one or more builders: 20 to 80% by weight;
c) one or more enzymes: 0.1 to 6 weight percent;
d) at least one bleach: 5-25% by weight; And
e) at least one further additive: 0-50% by weight. The cleaning or cleaning composition according to any of claims 21 to 24, wherein component b) used is a mixture of different builders comprising two or more of the following components: one or more carbonates, one or more silicates, carboxyl One or more polymeric compounds containing acid groups, or one or more polymeric compounds, containing one or more (poly) hydroxycarboxylic acids or salts thereof, all or part of which are present in neutralized form Acids or salts thereof, one or more phosphonic acids, one or more phosphates. 26. The cleaning or cleaning composition of any of claims 16 to 19 or 21 to 25 in the form of a gel at room temperature. The cleaning or cleaning composition of claim 26 comprising the following components:
a) at least one compound of formula (I);
b) one or more builders;
c) optionally one or more enzymes;
d) optionally one or more bleaches;
e1) water;
e2) one or more thickeners; And
e3) at least one additional additive optionally selected from surfactants, bases, corrosion inhibitors, antifoams, dyes, perfumes, fillers, solubilizers and organic solvents other than a). The cleaning or cleaning composition of claim 27 comprising the following components based on the total weight of the cleaning or cleaning composition:
a) at least one compound of formula I: 0.1-20% by weight;
b) one or more builders: 5 to 80 weight percent;
c) one or more enzymes: 0 to 8% by weight;
d) at least one bleach: 0-30% by weight;
e1) water: 10-90 weight percent;
e2) at least one thickener: 0.1 to 8% by weight; And
e3) at least one further additive: 0-25% by weight. 29. The cleaning or cleaning composition of claim 27 or 28 comprising the following ingredients based on the total weight of the cleaning or cleaning composition:
a) at least one compound of formula I: 0.1 to 10% by weight;
b) one or more builders: 5 to 60 weight percent;
c) one or more enzymes: 0.1 to 6 weight percent;
d) at least one bleach: 0-30% by weight; And
e1) water: 10-90 weight percent;
e2) at least one thickener: 0.1 to 6% by weight; And
e3) at least one further additive: 0-25% by weight. 30. The cleaning or cleaning composition of any of claims 27 to 29 comprising the following ingredients based on the total weight of the cleaning or cleaning composition:
a) at least one compound of formula I: 0.1 to 10% by weight;
b) one or more builders: 5 to 40 weight percent;
c) one or more enzymes: 0.1 to 6 weight percent;
d) at least one bleach: 0-25% by weight; And
e1) water: 20-80 wt%;
e2) at least one thickener: 0.3-50% by weight; And
e3) at least one further additive: 0-25% by weight.