WO1998005746A1 - Use of citric acid derivatives in detergents and cleaning agents - Google Patents

Abstract

The use is disclosed of a compound having the general formula (I), as well as its alkali salts, as scaling inhibitors and/or (co)-builders. In the formula (I), R' stands for hydrogen and R and R' independently represent branched or non-branched aliphatic C4-28 radicals which can contain one or several double C-C and/or triple C-C bonds. Radicals R and R' may be interrupted by one or more non-adjacent oxygen atoms, NH groups and/or N-C1-4-alkyl groups, and may be substituted by one or more hydroxyl groups, primary amino groups and/or secondary C1-4-alkylamino groups; or radicals R and R' are hydrogen atoms and radical R' has the above-mentioned meaning; or R' has the meaning given above for R' and R and R' are hydrogen atoms.

Description

 Use of citric acid derivatives in detergents and cleaning agents

The invention relates to the use of citric acid derivatives as incrustation inhibitors in detergents and cleaning agents, and other formulations.

AC ₁₆ substituted citric acid, agaricinic acid, is available both from natural sources and synthetically. Agaricinic acid occurs naturally in the larch sponge, Polyporus officinalis. α-Tetradecyl-citronic acid (Norcaperatic acid) occurs naturally in Polyporus fibrillosus. These citric acid derivatives are synthetically accessible, for example, via the diethyl oxosuccinate, and also by condensation of fatty acid esters and diethyl oxalate. Fermentative processes for the production of agaricic acid are also known.

The use of polycarboxylic acid derivatives in detergents is known. DE-Al 24 11 479 describes a cleaning agent mixture in which the body-forming agents are replaced by the salt of an ester of a carboxylic acid. Reaction products of maleic anhydride with citric acid, tartaric acid, malic acid, and also of citric acid with succinic anhydride or phthalic anhydride are described as usable.

DE-Al 37 22 342 describes a textile conditioning composition that makes the textiles soft and antistatic without impairing cleaning. The composition contains 0.5 to 15% by weight of a multifunctional carboxylic acid complex of a tertiary amine, the carboxylic acid being selected from citric acid and di- and tricarboxylic acid. with 21 to 54 carbon atoms. One example is dimerized oleic acid. Methyl di (hydrogenated) tallow amine is preferably used as the amine.

EP-A1-0 514 992 describes aqueous liquid emulsions which can be used as plasticizers and antistatic agents for washed textiles. A complex of a tertiary amine with a multifunctional carboxylic acid is used, the carboxylic acid being, for example, citric acid. Other acids that can be used are 5 (or 6) carboxy-4-hexyl-2-cyclohexene-1-octanoic acid and dimerized or trimerized oleic acid.

EP-A2-0 402 971 describes bleach booster particles which can be incorporated into detergent formulations. The additive consists of a precursor, a stabilizing agent and a dispersing agent. The precursor is a quaternized ammonium or phosphonium substituted carboxylic acid ester. The stabilizing agent is a solid inorganic acid or a C ₄ - or higher organic acid with at least one carboxyl group. Examples are C 1 to C ₂₂ fatty acids, citric acid, polyacrylic acid, maleic acid, succinic acid. The additive can be used in bleach detergent compositions in addition to a peroxide compound, a builder and a surfactant.

In T. Fuji, J. Jpn. Oil Chem. Soc. 1993, 42, 7, 493-500, studies on the detergent action of sodium salts of agaricinic acid are described. In addition to the surface-active effect of sodium salts of agaricic acid, the calcium binding ability is also examined. The calcium binding capacity of agaricic acid is higher at basic pH values than at acidic pH values.

The object of the present invention is to provide incrustation inhibitors, in particular for washing and cleaning agents. Another object of the present invention is to provide incrustation inhibitors that have builder properties.

Another object of the present invention is to provide cobuilders which, when used with builders, have advantageous effects and significantly reduce the amount of builders required.

Another object of the invention is to provide a builder, cobuilder or incrustation inhibitor which has an improved activity, in particular in comparison with commercially available maleic acid / acrylic acid copolymers (for example Sokalan CP 5 from BASF AG, Ludwigshafen) and citric acid trisodium salt with regard to the fabric deposition and the ash content.

Another object of the invention is to provide a builder, cobuilder or incrustation inhibitor which can be very easily eliminated from water and is very readily biodegradable.

According to the invention, it has been found that compounds of the general formula (I)

where R "is hydrogen and R and R 'are independently branched or unbranched aliphatic C 1-6 radicals which can contain one or more double and / or triple bonds,

the residues can be interrupted by one or more non-adjacent oxygen atoms, NH groups and / or NC _j - ₄ alkyl groups, and the radicals R and R 'can be substituted by one or more hydroxyl groups, primary amino groups and / or secondary C -alkylamino groups,

or where the radicals R and R "are hydrogen atoms and the radical R 'has the above meaning,

or where the radicals R "have the meaning given above for R 'and R and R' are hydrogen atoms,

or whose alkali salts can be used as incrustation inhibitors and / or (co) builders, in particular in detergents and cleaning agents and solve the above problems.

According to one embodiment, R "is a radical as defined for R 'and R and R' are hydrogen atoms. They are therefore ethers of citric acid.

In the following, R "is hydrogen and R and R 'have the meaning given.

According to one embodiment of the invention, one of the radicals R and R 'is a hydrogen atom.

According to one embodiment of the invention R and R 'are independently C ₆ _ ₂ o-, preferably C. _{8 18} radicals which have 0 to 4, preferably 1 to 3 CC double bonds and no CC triple bonds and are preferably unbranched, or the radical R is a hydrogen atom and the radical R 'has the above meaning. R is preferably a hydrogen atom and R 'is a linear, unsubstituted C ₁₆ radical which has a CC double bond in the C 1-6 position. R 'can additionally have one or two further CC double bonds in the C ₁₀ position and optionally also in the C _{13 14} position.

According to one embodiment of the invention, the radicals R and / or R 'are branched or unbranched C 1-6 alkyl radicals, preferably C ₆ . ₂₀ -, particularly preferably C ₈ . ₁₈ -, in particular C ₁₆ alkyl radicals. The radicals R or R 'are preferably unbranched.

According to one embodiment of the invention, at least one of the radicals R and R 'is a C ₄ . ₂₈ -alkyl radical, preferably C ₆ . ₂₀ -alkyl, in particular C ₈ _ ₁₈ alkyl radical, which by one or more nonadjacent oxygen atoms, NH-groups and / or NC _j ^ alkyl group is interrupted. According to an embodiment of the invention, branches are possible within this carbon chain or carbon chains.

According to one embodiment of the invention, at least one of the radicals R or R 'has, as substituents, hydroxyl groups, primary amino groups and / or secondary C -amino groups. At least one of the radicals R or R 'preferably has at least one hydroxyl group, in particular in the C 1 -, C ₇ -, C ₈ - or C ₁₀ -position relative to the radical R or R'.

According to one embodiment of the invention, the radicals R and R 'are free of C-C double and C-C three-bond bonds.

According to one embodiment of the invention, the radicals R and R 'are free of NH bonds. According to one embodiment of the invention, at least one of the radicals R and R 'in the carbon chain is interrupted by an oxygen atom.

If there are branches or alkyl radicals on nitrogen atoms, the shorter radicals in the branch or on the nitrogen atom preferably have 1 to 4 carbon atoms and are in particular methyl, ethyl, n-propyl, i-propyl, n-butyl or tert. -Butyl residues.

According to one embodiment of the invention, the radicals R and / or R 'contain a total of no more than 4 heteroatoms, preferably no more than 2 heteroatoms, such as oxygen or nitrogen atoms.

According to one embodiment of the invention, the radicals R and R 'each have at most one branch.

According to one embodiment of the invention, the radicals R and R 'are identical branched or unbranched C ₄ . ₂₈ residues that may contain one or more double and / or triple bonds.

According to one embodiment of the invention, the total number of carbon atoms in the radicals R and R 'is 4 to 40, preferably 10 to 30, in particular 10 to 20.

According to one embodiment of the invention, the radical R is a hydrogen atom and the radical R 'is a linear, unsubstituted C ₄ . ₂₈ -, preferably Cö- ₂₀ "', particularly preferably C _{8. 18} -, in particular about C ₁₆ -alkyl radical.

The compounds of formula (I) can be used as free acids or as alkali salts, in particular as sodium or potassium salts or mixtures. One, two or all of the acid groups can be in the salt form.

The compounds listed above per se and processes for their preparation per se are known.

The compounds according to the invention show very good activity as an incrustation inhibitor, as a builder and as a cobuilder.

When the compounds according to the invention are used as cobuilders, the amount of builders used can be greatly reduced.

The compounds according to the invention can be used as incrustation inhibitors, builders and / or cobuilders in a large number of formulations.

According to one embodiment of the invention, the compounds according to the invention are preferably used in washing and / or cleaning agents or washing aids, in particular for textile detergents. The compound can be incorporated into a detergent and cleaning agent in an amount of 0.1 to 40% by weight, preferably 0.5 to 30% by weight, in particular 1 to 15% by weight.

The detergents can be powdery or can also be in liquid form. The composition of detergents and cleaning agents can vary widely. Detergent and cleaning agent formulations usually contain 2 to 50% by weight of surfactants and optionally builders. This information applies to both liquid and powder detergents. Detergent and cleaning agent formulations that are common in Europe, the USA and Japan can be found, for example, in Chemical and Engin. News, volume 67, 35 (1989). More information UUmann's Encyclopedia of Technical Chemistry, Verlag Chemie, Weinheim 1983, 4th edition, pages 63 to 160, can be found on the composition of detergents and cleaning agents.

According to a preferred embodiment of the invention, the detergent is reduced in phosphate or free of phosphate.

Reduced phosphate detergents are understood to mean those formulations which contain at most 25% by weight of phosphate, calculated as pentasodium triphosphate. The detergents can be full detergents or special detergents. Both anionic and nonionic surfactants or mixtures of anionic and nonionic surfactants are suitable as surfactants. The surfactant content of the detergents is preferably 8 to 30% by weight.

Suitable anionic surfactants are, for example, fatty alcohol sulfates of fatty alcohols having from 8 to 22, preferably 10 to 18 carbon atoms, for example C ₉ - to C _{ι r} alcohol sulfates, C ₁₂ - stylsulfat to _C13 alcohol sulphates, cetyl sulfate, myristic, palmityl, stearyl and Talgfettalkoholsulfat.

Other suitable anionic surfactants are sulfated, ethoxylated C ₈ to C ₂₂ alcohols or their soluble salts. Compounds of this type are prepared, for example, by first alkoxylating a C ₈ to C ^, preferably a C ₁₀ to C ₈ alcohol and then sulfating the alkoxylation product. Ethylene oxide is preferably used for the alkoxylation, 1 to 50, preferably 2 to 20 mol, particularly preferably 2 to 5 mol of ethylene oxide being used per mol of fatty alcohol. However, the alkoxylation of the alcohols can also be carried out using propylene oxide alone and, if appropriate, butylene oxide. Also suitable are alkoxylated C ₈ -C ₂₂ -alcohols which contain ethylene oxide and pro- contain pylene oxide or ethylene oxide and butylene oxide. The alkoxylated C ₈ to C ₂₂ alcohols can contain the ethylene oxide, propylene oxide and butylene oxide units in the form of blocks or in statistical distribution.

Other suitable anionic surfactants are alkyl sulfonates such as C ₈ to C ₂₄ , preferably C ₁₀ to C ₁₈ alkane sulfonates and soaps, such as the salts of C ₈ to C ₂₄ carboxylic acids.

Other suitable anionic surfactants are C ₉ to C ₂₀ linear alkylbenzenesulfonates (LAS). The compounds according to the invention are preferably used in LAS-poor detergent formulations with less than 4% LAS, particularly preferably in LAS-free formulations.

The anionic surfactants are preferably added to the detergent in the form of salts. Suitable cations in these salts are alkali metal salts such as sodium, potassium, lithium and ammonium salts such as e.g. Hydroxyethylammonium, di (hydroxyethyl) ammonium and tri (hydroxyethyl) ammonium salts.

Examples of suitable nonionic surfactants are alkoxylated, C ₈ -C ₂₂ -alcohols. The alkoxylation can be carried out using ethylene oxide, propylene oxide and / or butylene oxide. All alkoxylated alcohols which contain at least two molecules of an alkylene oxide mentioned above can be used as the surfactant. Here too, block polymers of ethylene oxide, propylene oxide and / or butylene oxide come into consideration or addition products which contain the alkylene oxides mentioned in a statistical distribution. 2 to 50, preferably 3 to 20, moles of at least one alkylene oxide are used per mole of alcohol. Ethylene oxide is preferably used as the alkylene oxide. The alcohols preferably have 10 to 18 carbon atoms. Another class of nonionic surfactants are alkyl polyglucosides with 8 to 22, preferably 10 to 18 carbon atoms in the alkyl chain. These compounds contain 1 to 20, preferably 1.1 to 5, glucoside units. Another class of nonionic surfactants are N-alkyl glucamides of the general structures

where A is a C ₆ to C ₂₂ alkyl, B is an H or C to C ₄ alkyl and D is a polyhydroxyalkanyl radical having 5 to 12 C atoms and at least 3 hydroxyl groups. A is preferably C ₁₀ to C ₁₈ alkyl, B is CH ₃ and D is a C ₅ or C ₆ radical. For example, such compounds are obtained by the acylation of reducing aminated sugars with acid chlorides of C ₁₀ -C ₁₈ carboxylic acids.

Further preferred surfactants are the end group-capped fatty acid amide alkoxylates of the general formula known from WO-A 95/11225

R ¹ -CO-NH- (CH ₂ ) _n -O- (AO) _x -R ² in the

R ¹ denotes a C ₅ to C ₂₁ alkyl or alkenyl radical, R ² denotes a C _r to C alkyl group,

A is C ₂ to C ₄ alkylene, n denotes the number 2 or 3 and x has a value from 1 to 6. Examples of such compounds are the reaction products of n-butyltriglycolamine of the formula H ₂ N- (CH ₂ -CH ₂ -O) ₃ -C ₄ H ₉ with methyl dodecanoate or the reaction products of ethyltetraglycolamine of the formula H ₂ N- ( CH ₂ -CH ₂ -O) ₄ -C ₂ H ₅ with a commercially available mixture of saturated C ₈ - to C ₁₈ -fatty acid methyl esters.

The powdered or granular detergents and optionally also structured liquid detergents can also contain one or more inorganic builders. All conventional inorganic builders such as aluminosilicates, silicates, carbonates and phosphates are suitable as inorganic builder substances.

Suitable inorganic builders are e.g. Alumosilicates with ion exchange properties such as Zeolites. Different types of zeolites are suitable, in particular zeolite A, X, B, P, MAP and HS in their Na form or in forms in which Na is partly replaced by other cations such as Li, K, Ca, Mg or ammonium. Suitable zeolites are described, for example, in EP-A-0 038 591, EP-A-0 021 491, EP-A-0 087 035, US 4,604,224, GB-A-2 013 259, EP-A-0 522 726, EP -A-0 384 070 and WO 94/24251.

Other suitable inorganic builders are e.g. amorphous or crystalline silicates such as e.g. amorphous disilicates, crystalline disilicates such as the layered silicate SKS-6 (manufacturer Hoechst AG). The silicates can be used in the form of their alkali, alkaline earth or ammonium salts. Na, Li and Mg carbonates or bicarbonates, in particular sodium carbonate and / or sodium bicarbonate, are preferably used.

The inorganic builders can be present in the detergents in amounts of 0 to 60% by weight together with any organic ones to be used Cobuilders may be included. The inorganic builders can be incorporated into the detergent either alone or in any combination with one another. In powder or granular detergents, they are added in amounts of 10 to 60% by weight, preferably in amounts of 20 to 50% by weight. In structured (multi-phase) liquid detergents, inorganic builders are added in amounts of up to 40% by weight, preferably up to 20% by weight. They are suspended in the liquid formulation components.

According to one embodiment, organic cobuilders are in powder or granule form and in liquid detergent formulations in amounts of 0.1 to 40% by weight, preferably 0.5 to 30% by weight, in particular in amounts of 1 to 15% by weight. -% together with inorganic builders. The cobuilders are at least partially, preferably completely, the compounds according to the invention.

The powdery or granular heavy-duty detergents can also contain, as other conventional constituents, a bleaching system consisting of at least one bleaching agent, optionally in combination with a bleaching activator and / or a bleaching catalyst.

Suitable bleaching agents are perborates and percarbonate in the form of their alkali, in particular their Na salts. They are contained in the formulations in amounts of 5 to 30% by weight, preferably 10 to 25% by weight. Other suitable bleaching agents are inorganic and organic peracids in the form of their alkali or magnesium salts or in some cases also in the form of the free acids. Examples of suitable organic percarboxylic acids or salts are, for example, Mg monoterephthalate, phthalimidopercaproic acid and dodecane-l, 10-di-peracid. An example of an inorganic peracid salt is potassium peroxomonosulfate (oxone). Suitable bleach activators are, for example:

Acylamines such as tetraacetylethylenediamine, tetraacetylglycoluril, N, N'-diacetyl-N, N'dimethylurea and l, 5-diacety-2,4-diαxohexahydro-l, 3,5-triazine. acylated lactams such as acetylcaprolactam, octanoylcapro-iactam and benzoylcaprolactam substituted phenol esters of carboxylic acids such as e.g. Na acetoxybenzenesulfonate, Na octanoyloxybenzenesulfonate and Na nonaoyloxybenzenesulfonate - acylated sugars such as e.g. Pentaacetyl glucose

Anthranil derivatives such as 2-Methylπthranil or 2-phenylanthranil

Enol esters such as Isopropenyl acetate

Oxime esters such as O-acetylacetone oxime

Carboxylic anhydrides, e.g. Phthalic anhydride or acetic anhydride.

Tetraacetylethylenediamine and Na nonanoyloxybenzenesulfonate are preferably used as bleach activators. The bleach activators are added to heavy-duty detergents in amounts of 0.1 to 15% by weight, preferably in amounts of 1.0 to 8.0% by weight, particularly preferably in amounts of 1.5 to 6.0% by weight .

Suitable bleaching catalysts are quaternized imines and sulfonimines as described in US 5,360,568, US 5,360,569 and EP-A-0 453 003 and Mn complexes, cf. eg WO 94/21777. If bleach catalysts are used in the detergent formulations, they are in amounts of up to 1.5% by weight, preferably up to 0.5% by weight, in the case of the very active manganese complexes in amounts of up to 0.1% by weight. contain. The detergents preferably contain an enzyme system. These are proteases, lipases, amylases and cellulases that are commonly used in detergents. The enzyme system may be limited to a single one of the enzymes or may include a combination of different enzymes. Of the commercially available enzymes, amounts of 0.1 to 1.5% by weight, preferably 0.2 to 1.0% by weight, of the compounded enzyme are generally added to the detergents. Suitable proteases are, for example, Savinase and Esperase (manufacturer Novo Nordisk). A suitable lipase is, for example, lipopolase (manufacturer Novo Nordisk). A suitable cellulase is eg Celluzym (manufacturer Novo Nordisk).

The detergents preferably contain soil release polymers and / or graying inhibitors as other common constituents. This is e.g. polyester from polyethylene oxides with ethylene glycol and / or propylene glycol and aromatic dicarboxylic acids or aromatic and aliphatic dicarboxylic acids. Polyesters made from polyethylene oxides which are end group-capped with di- and / or polyhydric alcohols and dicarboxylic acids. Such polyesters are known, cf. for example US 3,557,039, GB-A-1 154 730, EP-A-0 185 427, EP-A-0 241 984, EP-A-0 241 985, EP-A-0 272 033 and US 5,142,020.

Other suitable soil release polymers are amphiphilic graft or copolymers of vinyl and / or acrylic esters on polyalkylene oxides, cf. US 4,746,456, US 4,846,995, DE-A-3 711 299, US 4,904,408, US 4,846,994 and US 4,849,126 or modified celluloses such as e.g. Methyl cellulose, hydroxypropyl cellulose or carboxymethyl cellulose.

Graying inhibitors and soil release polymers are present in the detergent formulations in an amount of 0 to 2.5% by weight, preferably 0.2 to 1.5% by weight, particularly preferably 0.3 to 1.2% by weight. Preferred used Soil release polymers are the graft polymers known from US Pat. No. 4,746,456 of vinyl acetate on polyethylene oxide with a molecular weight of 2500-8000 in a weight ratio of 1.2: 1 to 3.0: 1, and commercially available polyethylene terephthalate / polyoxyethylene terephthalates with a molecular weight of 3000 to 25000 made of polyethylene oxides the molar mass 750 to 5000 with terephthalic acid and ethylene oxide and a molar ratio of polyethylene terephthalate to polyoxyethylene terephthalate from 8: 1 to 1: 1 and the block polycondensates known from DE-A-44 03 866, the blocks from (a) ester units Contain polyalkylene glycols with a molecular weight of 500 to 7500 and aliphatic dicarboxylic acids and / or monohydroxymonocarboxylic acids and (b) ester units from aromatic dicarboxylic acids and polyhydric alcohols. These amphiphilic block copolymers have molecular weights from 1500 to 25000.

According to one embodiment of the invention, the detergent is a detergent containing

0.1 to 40% by weight of a compound of formula (I), 5 to 30% by weight of at least one anionic and / or nonionic surfactant, 5 to 50% by weight of at least one inorganic builder,

5 to 30% by weight of at least one inorganic bleaching agent, 0.1 to 15% by weight of at least one bleach activator, 0.2 to 2.0% by weight of enzymes,

wherein the total amount of the detergent ingredients is 100% by weight.

A typical powder or granular heavy-duty detergent can have the following composition, for example: 3 to 50, preferably 8 to 30% by weight of at least one anionic and / or nonionic surfactant,

5 to 50, preferably 15 to 42.5% by weight of at least one inorganic builder, 5 to 30, preferably 10 to 25% by weight of an inorganic bleaching agent,

0.1 to 15, preferably 1 to 8% by weight of a bleach activator, 0 to 1, preferably up to at most 0.5% by weight of a bleaching catalyst, 0.05 to 5% by weight, preferably 0.2 to 2.5% by weight of a color transfer inhibitor based on water-soluble homopolymers of N-vinylpyrrolidone or N-vinylimidazole, water-soluble copolymers of N-vinylimidazole and N-vinylpyrrolidone with a particle size of 0.1 to 500, preferably up to 250 μm, these copolymers containing 0.01 to 5, preferably 0.1 to 2% by weight of N, N'-divinylethylene urea as crosslinking agent. Further color transfer inhibitors are water-soluble and also crosslinked polymers of 4-vinylpyridine-N-oxide, which can be obtained by polymerizing 4-vinylpyridine-N-oxide and subsequent oxidation of the polymers, - 0.1 to 40, preferably 0.5 to 30, in particular 1 to 15% by weight of at least one compound of the formula I to be used according to the invention as organic cobuilders or incrustation inhibitors, 0.2 to 1.0% by weight of protease, 0.2 to 1.0% by weight of lipase, 0.3 to 1.5% by weight of a soil realease polymer,

the total amount of ingredients being 100% by weight.

According to one embodiment of the invention, the detergent is a detergent containing 0.1 to 40% by weight of a compound of the formula (I)

3 to 50% by weight of at least one anionic and / or nonionic

Surfactants,

10 to 60% by weight of at least one inorganic builder,

0.05 to 5% by weight of a color transfer inhibitor,

0.2 to 2.0% by weight of enzymes,

wherein the total amount of the detergent ingredients is 100% by weight.

A bleaching system is often completely or partially dispensed with in color-preserving special detergents (for example in so-called color detergents). A typical powder or granular color detergent can have the following composition, for example:

3 to 50, preferably 8 to 30% by weight of at least one anionic and / or nonionic surfactant,

10 to 60, preferably 20 to 55% by weight of at least one inorganic builder, 0 to 15, preferably 0 to 5% by weight of an inorganic bleaching agent,

0.05 to 5% by weight, preferably 0.2 to 2.5% by weight, of a color transfer inhibitor, cf. above, 0.1 to 20, preferably 1 to 15% by weight of at least one compound of the formula I according to the invention as an organic cobuilder,

0.2 to 1.0% by weight of protease, 0.2 to 1.0% by weight of cellulase,

0.2 to 1.5% by weight of a soil release polymer, for example a graft polymer of vinyl acetate on polyethylene glycol, the total amount of ingredients being 100% by weight.

The powdery or granular detergents can contain up to 60% by weight of inorganic adjusting agents as other common constituents. Sodium sulfate is usually used for this. However, the detergents according to the invention are preferably low in adjusting agents and contain up to 20% by weight, particularly preferably up to 8% by weight, of adjusting agents.

The detergents according to the invention can have different bulk densities in the range from 300 to 950 g / l. Modern compact laundry detergents generally have high bulk densities, e.g. 550 to 950 g / 1, and show a granular structure.

According to one embodiment of the invention, the detergent is a liquid detergent containing

0.1 to 40% by weight of a compound of the formula (I) 5 to 60% by weight of at least one anionic and / or nonionic surfactant, 0.05 to 5% by weight of a color transfer inhibitor, the total amount of the ingredients of the Detergent gives 100 wt .-%.

The liquid detergents according to the invention contain, for example

5 to 60, preferably 10 to 40% by weight of at least one anionic and / or nonionic surfactant,

0.05 to 5% by weight, preferably 0.2 to 2.5% by weight, of a color transfer inhibitor (cf. above), 0.1 to 20, preferably 1 to 15% by weight of at least one compound of the formula I according to the invention as a cobuilder, 0 to 1.0% by weight of protease, 0 to 1.0% by weight of cellulase,

0 to 1.5% by weight of a soil release polymer and / or graying inhibitor,

0 to 60% by weight of water,

0 to 10% by weight of alcohols, glycols such as ethylene glycol, diethylene glycol or propylene glycol or glycerin,

the total amount of ingredients being 100% by weight.

The detergents can optionally contain other customary additives. As further additives, e.g. Complexing agents, phosphonates, optical brighteners, dyes, perfume oils, foam dampers and corrosion inhibitors are included.

The percentages in the examples mean% by weight, unless stated otherwise, and give a total of 100% by weight for the ingredients of the finished formulation.

The invention also relates to a method for washing or cleaning articles or textiles, the articles or textiles being treated with an aqueous, preferably 0.2 to 10% by weight washing liquor of a detergent, as described above.

According to one embodiment of the invention, the invention

Compounds used in washing aids. According to one embodiment, they are used in detergent boosters for the treatment of severe localized grease contamination. The washing power boosters are included Products rich in surfactants, the main focus of which is on easy-care textiles, in which certain low washing temperatures should not be exceeded.

According to one embodiment of the invention, the compounds according to the invention are used in soaking agents for heavily soiled laundry. The soaking agents are, for example, strongly alkaline washing aids based on anion / nonionic surfactant mixtures, which loosen stubborn and firmly adhering dirt.

According to one embodiment of the invention, the compounds according to the invention are used in aftertreatment compositions which are used after the actual washing process. Examples of these are finishing agents, tumble aids, form washers, spray starches, ironing aids and other stiffening agents.

According to one embodiment of the invention, the compounds according to the invention are used in the food industry in oil / water / emulsions, such as mayonnaise or sauces or water / oil / emulsions, such as margarine and the like.

According to one embodiment of the invention, the compounds according to the invention are used in agriculture in fertilizers or crop protection formulations. They prevent the formation of agglomerates in fertilizers such as artificial fertilizers and salts, which are available as powders, granules or prills.

According to one embodiment of the invention, the inventive

Compounds used in the textile industry in the manufacture of synthetic fibers. They are used, for example, in pre-treatment agents for Fibers, used in the production of rayon fibers, in spin finishes and in textile smelting, in dyeing aids, finishing agents, water repellents, auxiliaries for printing, antistatic agents and flocking and coating agents.

According to one embodiment of the invention, the compounds according to the invention are used in cosmetics, such as cosmetic care products and cosmetic cleaning agents.

According to one embodiment of the invention, the compounds are used in the pulp and paper industry, for example for resin removal in pulp production and paper production, in pigment dispersion and foam control in the production of paper and paper coating, in paper sizing agents, in agents for cleaning machine nen, sieving and felting, in the regeneration of waste paper, fiber recovery and wet strengthening.

According to one embodiment of the invention, the compounds according to the invention are used in the leather industry in the pretreatment of the leather, the tanning of the leather and the aftertreatment of the wet or dry leather or in the care of the leather.

According to one embodiment of the invention, the compounds according to the invention are used in the photo industry, for example in pouring aids, antistatic agents, lubricants, emulsifiers and dispersants for the preparation of active ingredient emulsions, dispersions and latices and in additions to processing baths.

According to one embodiment of the invention, the compounds according to the invention are used to inhibit corrosion. According to one embodiment of the invention, the compounds according to the invention are used in technical detergent formulations, such as chain lubricants for conveyor belts in bottle filling and cleaning systems, all-purpose cleaners, high-alkaline cleaners, high-pressure cleaners, aqueous cold cleaners, alkaline rust removers, alkaline immersion degreasers, car detergents for brush and high-pressure washing, steam jet cleaners and passivating agents for steel.

The invention is explained in more detail below with the aid of examples.

example 1

Agaricic acid (R = H, R '= C ₁₆ -alkyl radical, linear) has the following properties:

The chemically pure acid melts constantly and smoothly at 142 ° C (uncorrected) and crystallizes from ethanol in large, pearlescent leaves.

Using the cobuilder 1 shown in Table 2, the detergent formulations described in Table 1 were prepared. Compositions A-M are compact detergents, N and O are examples of color detergents and formulation P is a structured liquid detergent. The abbreviations in table 1 have the following meaning:

TAED: tetraacetylethylenediamine

Soil release additive 1: polyethylene terephthalate / polyoxyethylene terephthalate in a molar ratio of 3: 2, molar mass of the condensed polyethylene glycol 4000, molar mass of the polyester 10000 Soil release additive 2: graft polymer of vinyl acetate on polyethylene glycol of molecular weight 8000, molecular weight of graft polymer 24000 O: ethylene oxide

TABLE 1

INGREDIENTS A B C D E F G H I J K L M N O P

Soap 2 2 1 0.5 2 0.5 0.6 1 2 2 2 2 1.5 2

Na metasilicate 2 2 3.5 3 2 2 2 2 x 5.5 H ₂ 0

Na silicate 8 2.5 4 0.5

Mg-SUikat 0.8 0.5

Zeolite A 18 24 36 35 15 30 36.5 25 20 36 24 36 36 55 25

10 zeolite P 18 36

Layered silicate SKS 12 14 12 6 (Hoechst AG) amorphous sodium 12 12 disilicate

15

Sodium carbonate 12 12 12 11 15 10.5 10 8 12 12 12 6

Sodium hydrogen 9 6.5 carboαat

Sodium citrate 5 7 4 -

20th

BESTANDTEILE A B C D E F G H I J K L M N 0 P

INGREDIENTS ABCDEFGHIJKLMN 0 P

opt. Brightener 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2

1 color transfer 1.5 1 inhibitor

| Water 3.5 3.5 0.3 1 1 1 22.5 11 40.6

A detergent of the above formulation C, to which 5% by weight of the trisodium salt of agaricin was added, was used to investigate the cobuilder action and the inhibition effect on incontinence.

The washing conditions were as follows:

WASHING CONDITIONS:

DEVICE: Launder-o-meter from Atlas, Chicago NUMBER OF WASHING CYCLES: 15

WASHING FLEET: 250 ml liquor

WASHING TIME: 30 min at 60 ° C

DETERGENT DOSE: 4.5 g / 1

WATER HARDNESS: 22.4 ° dH (4mmol Ca / 1; Ca: Mg = 4: 1) TEST FABRIC: 20 g cotton-nettle tissue

Examples 2 to 4

No cobuilder was used as reference substance in Example 2, sodium citrate in Example 3 and a copolymer of acrylic acid and maleic acid in a ratio of 70:30 with an average molecular weight of 70,000 in Example 4 (sold by BASF under the name Sokalan CP 5).

The fabrics described above were incinerated. The results of the ash test are summarized in Table 2 below. TABLE 2

BEICOBUILDER CONTENT OF COBUILr ASH (%) GAME OF

IN DETERGENT FORM

MULING (%)

1 Agari5 1.48 cic acid according to the invention

2 without 0 4.53

3 Na citrate 5 2.75 AS / MS 5 2.04

As can be seen from the table above, the ash content is significantly lower when using agaricic acid in the detergent formulation than when using the comparison co-builders or when a cobuilder is not used.

Biodegradability of agaricic acid.

The biodegradability of agaricic acid was investigated with the help of the Zahn-Wellens test (according to EC Directive 88/302 / EEC, OECD 302B, ISO 9888-1991). The degree of DOC elimination is more than 90% after 7 days and 10 to 20% after 3 hours (adsorption), so that agaric acid can be easily eliminated from water.

In the modified storm test (according to 92/69 / EEC, part C. 4-C, OECD 301B, ISO 9439-1990), a degree of degradation of 60 - 70% CO ₂ / ThCO ₂ - is determined after 28 days, the DOC degree of degradation is after 28 days 90 - 100%.

As can be seen from the above results, the compounds of the general formula are very suitable as builders, cobuilders or incrustation inhibitors, particularly in modern textile detergent formulations.

Claims

claims 1. Use of a compound of the general formula (I)

wherein R 'is hydrogen R and R' independently, are branched or unbranched aliphatic C. ₄ residues are _28, which may contain triple bonds CC one or more C-C double and / or, the radicals R and R 'can be interrupted by one or more non-adjacent oxygen atoms, NH groups and / or N-C ^ alkyl groups, and the radicals R and R 'can be substituted by one or more hydroxyl groups, primary amino groups and / or secondary Cι_4-alkylamino groups, or where the radicals R and R "are hydrogen atoms and the radical R 'has the above meaning, or where R "has the meaning given above for R 'and R and R' are hydrogen atoms, or their alkali salts as incrustation inhibitors and / or (co) builders. 2. Use according to claim 1, wherein R "is hydrogen and R and R 'are independently Cg ^ g, preferably C ₈ _ ₁₈ radicals which have 0 to 4 CC double bonds and no CC triple bonds and are preferably unbranched , or wherein the radicals R and R "are hydrogen atoms and the radical R 'has the above meaning. 3. Use according to claim 1, wherein R and R "are hydrogen atoms and R 'is a C ₆ _ ₂₀ -, preferably Cg_ι ₈ alkyl radical, which is preferably unbranched. 4. Use according to one of claims 1 to 3 in detergents or cleaning agents or washing aids, in particular in textile detergents. 5. Use according to one of claims 1 to 3 in cosmetics, crop protection formulations, fertilizers, foods, pretreatment agents for the textile and leather industry, treatment agents for the pulp and paper industry, additives for the photo industry or in anti-corrosion agents. 6. Detergent containing 0.1 to 40% by weight of a compound as defined in one of claims 1 to 3, 5 to 30% by weight of at least one anionic and / or nonionic surfactant, 5 to 50% by weight of at least one inorganic builder, 5 to 30% by weight of at least one inorganic bleaching agent, 0.1 to 15% by weight of at least one bleach activator, 0.2 to 2.0% by weight of enzymes, wherein the total amount of detergent ingredients is 100% by weight. 7. detergent containing 0.1 to 40 wt .-% of a compound as defined in any one of claims 1 to 3, 3 to 50% by weight of at least one anionic and / or nonionic surfactant, 10 to 60% by weight of at least one inorganic builder, 0.05 to 5% by weight of a color transfer inhibitor, 0.2 to 2.0% by weight of enzymes, wherein the total amount of detergent ingredients is 100% by weight. 8. Containing liquid detergent 0.1 to 40% by weight of a compound as defined in one of claims 1 to 3, 5 to 60% by weight of at least one anionic and / or nonionic surfactant, 0.05 to 5% by weight of a color transfer inhibitor, wherein the total amount of detergent ingredients is 100% by weight. Process for washing or cleaning articles or textiles, the articles or textiles being treated with an aqueous, preferably 0.2 to 10% by weight wash liquor of a detergent according to any one of claims 6 to 8.