New surfactant combination and detergents and cleaning agents containing same

Abstract

The invention relates to surfactant combinations of: an alkyl polyglcol ether of the general formula (Ia) or (Ib) and a rhamnolipid of the general formula (III) or the salt thereof, CH3(CH2)m(-O-R)n-OH, formulae (Ia), (Ib), (II), wherein R is a linear or branched alkyl group with 2 to 4 C atoms, m is a number from 7 to 15, x and y independently of each other are numbers from 0 to 12, z is a number from 1 to 4, with the sum of x + y + z being in the range of 10 to 16, n is a number from 2 to 10, o is 2, 1 or 0, p is 0 or 1, and R1 and R2 independently of each other are the same or different organic groups with 2 to 24 carbon atoms, in particular 5 to 13 carbon atoms; and another anion surfactant that is different from the rhamnolipid. These surfactant combinations can be well incorporated into detergents and cleaning agents, have excellent use properties and can be produced from renewable raw materials at least to some extent.

Description

[0001] New surfactant combination and detergents and cleaning agents containing them

[0002] The invention relates to a combination of nonionic surfactant with two different anionic surfactants, which can be produced at least partially from renewable raw materials and which exhibits superior washing performance on oily soils. The invention also relates to detergents or cleaning agents containing this surfactant combination.

[0003] The use of surfactants to reduce the surface tension of water, to form dispersions, and to promote solubility has long been well known in the field of detergents and cleaning agents. Although many surfactants are made entirely or partially from renewable raw materials, some high-performance and widely used surfactants are still petrochemically based. Furthermore, there is a constant desire to provide surfactants with outstanding application properties in order to achieve high performance even with low surfactant usage.

[0004] The object of the present invention is to provide surfactants that exhibit advantageous application properties and can, if possible, be produced from renewable raw materials. Furthermore, the surfactants should be well tolerated by the skin and can also be formulated together with other surfactants, making them particularly suitable for use in detergents and cleaning agents.

[0005] Rhamnolipids are compounds in which a mono- or dirhamnose unit is glycosidically linked to the hydroxyl group of a ß-hydroxyl-containing fatty acid, whereby the fatty acid may be esterified with a hydroxyl group of another hydroxyl-containing fatty acid molecule. They are obtained by fermentation of bacteria of the genus Pseudomonas, particularly Pseudomonas aeruginosa, preferably during their growth on hydrophobic substrates such as n-alkanes or vegetable oils. Due to their surface-active properties and their origin, rhamnolipids belong to the so-called biosurfactants. 3-(hydroxydecanoyloxy)decanoic acid dirhamnoside, for example, has the formula

[0006]

[0007] Patent EP 0 499 434 B1 discloses detergents containing 1 to 60 wt. % of a surfactant forming a micellar phase at pH 7.0 and 25°C in a 1 wt. % aqueous solution, and a surfactant forming a lamellar phase at pH 7.0 and 25°C in a 1 wt. % aqueous solution. Rhamnolipid can be either the surfactant forming the micellar phase or the surfactant forming the lamellar phase. European patent EP 1 445 302 B1 relates to detergents containing at least one glycolipid biosurfactant and at least one non-glycolipid surfactant, which are in a micellar phase. International patent application WO 2012 / 010405 A1 discloses cleaning agents containing at least 1% by weight of biosurfactant and an enzyme of bacterial origin. European patent application EP 0 605 308 A1 discloses compositions containing 0.001% to 99.99% by weight of anionic and / or nonionic surfactant and 0.001% to 99.99% by weight of ammonium bicarbonate.-% glycolipid, where the glycolipids can include, for example, sophorolipids, rhamnolipids, glucose lipids, trehalose lipids, and cellobiose lipids. International patent application WO 2012 / 010406 ​​A1 discloses detergents containing lipase and rhamnolipid, where the rhamnolipid consists of at least 50% by weight mono-rhamnolipid. International patent application WO 2012 / 010407 A1 discloses detergents containing glycolipid surfactant and lipase of bacterial origin, where the glycolipid surfactant consists of at least 20% by weight of a disaccharide acid-containing glycolipid surfactant. European patent application EP 2 410 049 A1 discloses mono- and dirhamnolipid-containing cleaning agents in which the weight ratio of monorhamnolipid to dirhamnolipid is in the range of 95:5 to 45:55.European patent application EP 2 787 065 A1 discloses mono- and dirhamnolipid-containing textile detergents in which the weight ratio of dirhamnolipid to monorhamnolipid is greater than 51:49. European patent application EP 2 786 743 A1 discloses rhamnolipid mixtures containing 51 wt.% to 95 wt.% of a specific dirhamnolipid and 0.5 wt.% to 9 wt.% of a specific monorhamnolipid, in which the weight ratio of dirhamnolipid to monorhamnolipid is greater than 91:9. Washing or cleaning agents containing rhamnolipid and N-containing polymer are known from international patent application WO 2016 / 096478 A1. The present invention relates, in a first embodiment, to a surfactant combination of an alkyl polyglycol ether of the general formula (Ia) or (Ib) with a rhamnolipid of the general formula (II) or its salt.

[0008] CH3(CH2)m(-OR)n-OH (la) in which R represents a linear or branched alkyl group having 2 to 4 C atoms, in particular 2 C atoms, m represents a number from 7 to 15, x and y independently represent numbers from 0 to 12, z represents a number from 1 to 4, the sum x + y + z being in the range from 10 to 16, n represents a number from 2 to 10, o represents 2, 1 or 0, p represents 0 or 1, and R 1 and R 2 independently of one another represent identical or different organic radicals having 2 to 24, in particular 5 to 13, carbon atoms, and a further anionic surfactant which is different from the rhamnolipid (hereinafter referred to as “further anionic surfactant” or “further anionic surfactant”). R 1 and / or R 2in formula (II) are preferably alkyl or alkenyl radicals, which may optionally be branched and / or substituted, in particular hydroxy-substituted, may optionally be mono-, di- or triunsaturated and are then preferably selected from the group consisting of pentenyl, heptenyl, nonenyl, undecenyl and tridecenyl, and alternatively preferably -(CH2)q-CH3 with q = 1 to 23, preferably 4 to 12. “Di-rhamnolipids” are understood to mean compounds of the general formula (II) or salts thereof in which p = 1, and “mono-rhamnolipids” are understood to mean those of the general formula (II) or salts thereof in which p = 0.

[0009] The salts of the compounds of general formula (II) in question here are preferably those in which the carboxyl H atom is replaced by an alkali metal cation or the group N + R 3 R 4 R 5 R 6 , in the R 3 , R 4 , R 5 and R6 independently of one another represent hydrogen, an alkyl group with 1 to 6 C atoms or a hydroxyalkyl group with 2 to 6 C atoms, i.e. the carboxylic acid group is present as a carboxylate anion.

[0010] Surfactants of general formula (Ib) are less preferred than surfactants of general formula (Ia) because they are relatively difficult to obtain from a renewable raw material base. Preferred surfactants of general formula (Ia) are those in which m is a number in the range from 11 to 15 and / or n is a number in the range from 4 to 7.

[0011] Surfactants of the general formula (Ia) or (Ib) can be prepared in a known manner by alkoxylation of alcohols CH3(CH2)m-OH or produce, whereby when using

[0012] In alcohol mixtures, the indices m, x, y, and z here and in the compounds of general formula (Ia) or (Ib) may also be non-integer. Ethylene oxide is preferably used for the alkoxylation. Since homologous mixtures generally form during the alkoxylation of alcohols, the average degree of alkoxylation n in the compounds of general formula (Ia) or (Ib) may also be non-integer. The alcohol CH3(CH2)m-OH is preferably a fatty alcohol and thus also originates from a renewable raw material source. The particularly preferred surfactants of the general formula (Ia) include the linear C12 alcohol with 3 ethylene oxide groups and the linear C14 alcohol with 4 ethylene oxide groups as well as the technical alkoxylates which are formed by reacting 1 molar equivalent of linear C12 alcohol or linear C14 alcohol with 2, 3 or 4 molar equivalents of ethylene oxide.

[0013] Other suitable anionic surfactants include, in particular, soaps and those containing sulfate or sulfonate groups. Preferred sulfonate-type surfactants are C9-C13 alkylbenzenesulfonates, olefinsulfonates, i.e., mixtures of alkene and hydroxyalkanesulfonates, and disulfonates, such as those obtained, for example, from C12-C18 monoolefins with a terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products. Also suitable are alkanesulfonates obtained from C12-C18 alkanes, for example, by sulfochlorination or sulfoxidation followed by hydrolysis or neutralization.Also suitable are the esters of α-sulfofatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel, or tallow fatty acids, which are produced by α-sulfonation of the methyl esters of fatty acids of plant and / or animal origin with 8 to 20 C atoms in the fatty acid molecule and subsequent neutralization to water-soluble monosalts. These are preferably the α-sulfonated esters of hydrogenated coconut, palm, palm kernel, or tallow fatty acids, although sulfonation products of unsaturated fatty acids, for example oleic acid, may also be present in small amounts, preferably in amounts not exceeding about 2 to 3 wt.%. Particularly preferred are α-sulfofatty acid alkyl esters which have an alkyl chain with no more than 4 C atoms in the ester group, for example methyl esters, ethyl esters, propyl esters, and butyl esters.The methyl esters of α-sulfofatty acids (MES), as well as their saponified disalts, are particularly advantageously used. Other suitable anionic surfactants include sulfated fatty acid glycerol esters, which are mono-, di-, and triesters, as well as mixtures thereof, as obtained by esterification of a monoglycerol with 1 to 3 mol of fatty acid or by transesterification of triglycerides with 0.3 to 2 mol of glycerol. Preferred alk(en)yl sulfates are the alkali metal salts and, in particular, the sodium salts of the sulfuric acid monoesters of C12-C18 fatty alcohols, for example, coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl, or stearyl alcohol, or of C10-C20 oxo alcohols, and those monoesters of secondary alcohols of this chain length.Also preferred are alk(en)yl sulfates of the stated chain length, which contain a synthetic, petrochemically produced, straight-chain alkyl radical, which exhibit degradation behavior similar to that of the corresponding compounds based on oleochemical raw materials. For washing purposes, C12-C16 alkyl sulfates and C12-C15 alkyl sulfates, as well as C14-C15 alkyl sulfates, are particularly preferred. Also suitable are the sulfuric acid monoesters of straight-chain or branched C7-C21 alcohols ethoxylated with 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C8-C18 alcohols with an average of 3.5 mol of ethylene oxide (EO) or C12-C18 fatty alcohols with 1 to 4 EO.Other preferred anionic surfactants include the salts of alkyl sulfosuccinic acid, also known as sulfosuccinates or sulfosuccinic acid esters, and the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols. Preferred sulfosuccinates contain Cs to Cs fatty alcohol residues or mixtures thereof. Particularly preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty alcohols, which, considered individually, are nonionic surfactants. Sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution are particularly preferred. It is also possible to use alk(en)ylsuccinic acid, preferably with 8 to 18 carbon atoms in the alk(en)yl chain, or salts thereof.Other suitable anionic surfactants include fatty acid derivatives of amino acids, for example N-methyltaurine (taurides) and / or N-methylglycine (sarcosides). Sarcosides and sarcosinates are particularly preferred, especially sarcosinates of higher and optionally mono- or polyunsaturated fatty acids such as oleyl sarcosinate. Other suitable anionic surfactants include, in particular, soaps. Particularly suitable are saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid, and behenic acid, as well as soap mixtures derived from natural fatty acids, for example coconut, palm kernel, or tallow fatty acids. The well-known alkenylsuccinic acid salts can also be used together with these soaps or as soap substitutes.

[0014] The other anionic surfactants, including soaps, can be present in the form of their sodium, potassium, or ammonium salts, as well as soluble salts of organic bases, such as mono-, di-, or triethanolamine. They are preferably present in the form of their sodium or potassium salts, especially in the form of the sodium salts. The other anionic surfactants are present in detergents in amounts of normally 0.1% to 70% by weight, in particular 1% to 20% by weight.

[0015] In the surfactant combinations according to the invention, which consist of mixtures of alkyl polyglycol ethers of the general formula (Ia) and / or (Ib) with the surfactants of the general formula (II) and the further anionic surfactant, the weight ratio of alkyl polyglycol ether to rhamnolipid is preferably in the range from 50:50 to 99:1, in particular from 70:30 to 95:5 and particularly preferably from 80:20 to 90:10. If the surfactant combinations contain mixtures of compounds of the general formula (Ia) and the general formula (Ib), those of the general formula (Ia) are preferably present in larger proportions by weight than those of the general formula (Ib).

[0016] The surfactant combinations according to the invention are outstandingly suitable as ingredients in washing and cleaning agents, cosmetics such as shampoos, toothpastes, and for other fields of application in which anionic surfactants have traditionally been used, such as in the food industry, geosciences, tertiary oil production, plastics technology, metalworking, photography, paper recycling, tool cleaning, and firefighting.

[0017] Particularly good results are achieved when used in washing and cleaning agents, so that the present invention further relates to the use of the surfactant combination defined above for producing washing or cleaning agents, the use of the surfactant combination defined above for increasing the performance of washing or cleaning agents when washing laundry or cleaning hard surfaces, and the washing or cleaning agents containing a surfactant combination defined above. Because the surfactant combination essential to the invention exerts its advantageous effect even at low temperatures, it or an agent containing it is preferably used in processes for washing laundry or cleaning hard surfaces that are carried out at temperatures in the range from 20°C to 40°C, in particular up to a maximum of 30°C.

[0018] A washing or cleaning agent according to the invention preferably contains 5% by weight to 70% by weight, in particular 10% by weight to 50% by weight and particularly preferably 12% by weight to 40% by weight of the surfactant combination defined above.

[0019] In addition to the surfactant combination, the washing or cleaning agent may contain other ingredients that further improve the performance and / or aesthetic properties of the agent. Within the scope of the present invention, the agent preferably additionally contains one or more substances from the group of nonionic surfactants, anionic surfactants, builders, bleaching agents, bleach activators, enzymes, electrolytes, pH adjusters, perfumes, perfume carriers, fluorescent agents, dyes, hydrotopes, foam inhibitors, anti-redeposition agents, graying inhibitors, shrinkage inhibitors, crease inhibitors, dye transfer inhibitors, antimicrobial agents, non-aqueous solvents, germicides, fungicides, antioxidants, preservatives, corrosion inhibitors, antistatic agents, bittering agents, ironing aids, anti-staining and waterproofing agents, skin-care agents, swelling and slip-resistant agents, softening components, and UV absorbers.

[0020] A washing or cleaning agent according to the invention may contain up to 30 wt.% additional surfactant in addition to the surfactant combination essential to the invention, with the additional surfactants preferably being obtainable from renewable raw materials. In particular embodiments of the invention, no additional surfactant is present besides the surfactant combination essential to the invention.

[0021] The agent according to the invention may contain additional nonionic surfactants. Suitable nonionic surfactants include alkoxylated fatty acid alkyl esters, fatty acid amides, alkoxylated fatty acid amides, polyhydroxy fatty acid amides, alkylphenol polyglycol ethers, amine oxides, alkyl polyglucosides, and mixtures thereof. In addition, alkyl glycosides of the general formula R 7 O(G) q be used in the R 7a primary straight-chain or methyl-branched, in particular 2-methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, C atoms, and G is the symbol that stands for a glycose unit having 5 or 6 C atoms, preferably glucose. The degree of oligomerization q, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably q is 1.2 to 1.4. Another class of non-ionic surfactants, which are used either as the sole additional non-ionic surfactant or in combination with other additional non-ionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the alkyl chain.

[0022] Non-ionic surfactants of the amine oxide type, for example N-cocoalkyl-N,N-dimethylamine oxide and N-tallowalkyl-N,N-dihydroxyethylamine oxide, and fatty acid alkanolamides can also be used.

[0023] Other suitable surfactants are polyhydroxy fatty acid amides of the formula, in which R is an aliphatic acyl radical having 6 to 22 carbon atoms, R 1represents hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z] represents a linear or branched polyhydroxyalkyl radical having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups. Polyhydroxy fatty acid amides are known substances that can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride. The group of polyhydroxy fatty acid amides also includes compounds of the formula in which R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R 1 represents a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R 2represents a linear, branched, or cyclic alkyl radical, or an aryl radical, or an oxyalkyl radical having 1 to 8 carbon atoms, with C 1-4 alkyl or phenyl radicals being preferred, and [Z] represents a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this radical. [Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose, or xylose. The N-alkoxy- or N-aryloxy-substituted compounds can be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as a catalyst. An agent according to the invention preferably contains at least one water-soluble and / or water-insoluble, organic and / or inorganic builder.The water-soluble organic builder substances include polycarboxylic acids, in particular citric acid and sugar acids, monomeric and polymeric aminopolycarboxylic acids, in particular glycinediacetic acid, methylglycinediacetic acid, nitrilotriacetic acid, iminodisuccinates such as ethylenediamine-N,N'-disuccinic acid and hydroxyiminodisuccinates, ethylenediaminetetraacetic acid and polyaspartic acid, polyphosphonic acids, in particular aminotris(methylenephosphonic acid), ethylenediaminetetrakis(methylenephosphonic acid), lysinetetra(methylenephosphonic acid) and 1-hydroxyethane-1,1-diphosphonic acid, polymeric hydroxy compounds such as dextrin and polymeric (poly)carboxylic acids, in particular polycarboxylates accessible by oxidation of polysaccharides, polymeric acrylic acids, methacrylic acids, maleic acids and copolymers thereof, which also contain small amounts of polymerizable substances without may contain polymerized carboxylic acid functionality.The relative average molecular mass of the homopolymers of unsaturated carboxylic acids is generally between 5,000 g / mol and 200,000 g / mol, and that of the copolymers between 2,000 g / mol and 200,000 g / mol, preferably 50,000 g / mol to 120,000 g / mol, in each case based on the free acid. A particularly preferred acrylic acid-maleic acid copolymer has a relative average molecular mass of 50,000 to 100,000. Suitable, albeit less preferred, compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinyl methyl ethers, vinyl esters, ethylene, propylene, and styrene, in which the proportion of acid is at least 50% by weight. Terpolymers containing two unsaturated acids and / or their salts as monomers and vinyl alcohol and / or a vinyl alcohol derivative or a carbohydrate as the third monomer can also be used as water-soluble organic builder substances.The first acidic monomer or its salt is derived from a monoethylenically unsaturated C8-C8 carboxylic acid, preferably from a C3-C4 monocarboxylic acid, in particular from (meth)acrylic acid. The second acidic monomer or its salt can be a derivative of a C4-C8 dicarboxylic acid, with maleic acid being particularly preferred. The third monomer unit is formed in this case from vinyl alcohol and / or preferably from an esterified vinyl alcohol. Vinyl alcohol derivatives that represent an ester of short-chain carboxylic acids, for example, C1-C4 carboxylic acids, with vinyl alcohol are particularly preferred. Preferred polymers contain 60 wt.% to 95 wt.%, in particular 70 wt.% to 90 wt.% of (meth)acrylic acid or (meth)acrylate, particularly preferably acrylic acid or acrylate, and maleic acid or maleate and 5 wt.% to 40 wt.%, preferably 10 wt.% to 30 wt.% of vinyl alcohol and / or vinyl acetate.Very particular preference is given to polymers in which the weight ratio of (meth)acrylic acid or (meth)acrylate to maleic acid or maleate is between 1:1 and 4:1, preferably between 2:1 and 3:1, and in particular between 2:1 and 2.5:1. Both the amounts and the weight ratios are based on the acids. The second acidic monomer or its salt can also be a derivative of an allylsulfonic acid substituted in the 2-position by an alkyl radical, preferably a C1-C4-alkyl radical, or an aromatic radical, preferably derived from benzene or benzene derivatives. Preferred terpolymers contain 40 wt.% to 60 wt.%, in particular 45 to 55 wt.% (meth)acrylic acid or (meth)acrylate, particularly preferably acrylic acid or acrylate, 10 wt.% to 30 wt.%, preferably 15 wt.% to 25 wt.% methallylsulfonic acid or methallylsulfonate and as a third monomer 15 wt.% to 40 wt.-%, preferably 20 wt.% to 40 wt.% of a carbohydrate. This carbohydrate can, for example, be a mono-, di-, oligo- or polysaccharide, with mono-, di- or oligosaccharides being preferred. Sucrose is particularly preferred. The use of the third monomer presumably creates predetermined breaking points in the polymer, which are responsible for the polymer's good biodegradability. These terpolymers generally have a relative average molecular weight between 1,000 g / mol and 200,000 g / mol, preferably between 200 g / mol and 50,000 g / mol. Other preferred copolymers are those which have acrolein and acrylic acid / acrylic acid salts or vinyl acetate as monomers. The organic builder substances can be used in the form of aqueous solutions, preferably in the form of 30 to 50 wt.% aqueous solutions, in particular for the production of liquid agents.All of the acids mentioned are generally used in the form of their water-soluble salts, especially their alkali salts.

[0024] Such organic builder substances can, if desired, be present in amounts of up to 40 wt.%, in particular up to 25 wt.%, and preferably from 1 wt.% to 8 wt.%. Amounts in the upper half of the above-mentioned ranges are preferably used in paste-like or liquid, especially water-based, compositions.

[0025] Polyphosphates, preferably sodium triphosphate, are particularly suitable as water-soluble inorganic builder materials. Crystalline or amorphous, water-dispersible alkali aluminosilicates are particularly suitable as water-insoluble inorganic builder materials, in amounts not exceeding 25 wt.%, preferably from 3 wt.% to 20 wt.%, and especially in amounts from 5 wt.% to 15 wt.%. Among these, crystalline sodium aluminosilicates of detergent quality, in particular zeolite A, zeolite P, zeolite MAP, and optionally zeolite X, are preferred. Amounts close to the stated upper limit are preferably used in solid, particulate compositions. Suitable aluminosilicates, in particular, have no particles with a grain size exceeding 30 μm and preferably consist of at least 80 wt.% particles with a size below 10 μm. Their calcium-binding capacity is generally in the range of 100 to 200 mg CaO per gram.

[0026] In addition to or as an alternative to the aforementioned water-insoluble aluminosilicate and alkali metal carbonate, other water-soluble inorganic builder materials may be present. These include, in particular, polyphosphates such as sodium triphosphate, water-soluble crystalline and / or amorphous alkali metal silicate builders. Such water-soluble inorganic builder materials are preferably present in the agents in amounts of 1 wt.% to 20 wt.%, in particular 5 wt.% to 15 wt.%. The alkali metal silicates usable as builder materials preferably have a molar ratio of alkali metal oxide to SiO2 of less than 0.95, in particular of 1:1.1 to 1:12, and can be amorphous or crystalline. Preferred alkali metal silicates are sodium silicates, in particular amorphous sodium silicates, with a molar Na2O:SiO2 ratio of 1:2 to 1:2.8.Crystalline silicates, which can be present alone or in a mixture with amorphous silicates, are preferably crystalline layered silicates of the general formula Na2Si. xO2x+iy H2O, in which x, the so-called modulus, is a number from 1.9 to 4 and y is a number from 0 to 20, and preferred values ​​for x are 2, 3, or 4. Preferred crystalline layered silicates are those in which x in the general formula mentioned is 2 or 3. In particular, both β- and β-sodium disilicates (Na2Si2O5·y H2O) are preferred. Virtually anhydrous crystalline alkali silicates produced from amorphous alkali silicates and of the above general formula, in which x is a number from 1.9 to 2.1, can also be used in the agents. In a further preferred embodiment, a crystalline sodium layered silicate with a modulus of 2 to 3 is used, such as can be produced from sand and soda. Sodium silicates with a modulus in the range from 1.9 to 3.5 are used in a further embodiment.In a preferred embodiment of such agents, a granular compound of alkali silicate and alkali carbonate is used, such as that commercially available under the name Nabion® 15.

[0027] Suitable peroxidic bleaching agents include, in particular, organic peracids or peracidic salts of organic acids, such as phthalimidopercaproic acid, perbenzoic acid, monoperoxyphthalic acid, and diperdodecanedioic acid, as well as their salts such as magnesium monoperoxyphthalate, diacyl peroxides, hydrogen peroxide, and inorganic salts that release hydrogen peroxide under the conditions of use, such as alkali metal perborate, alkali metal percarbonate, and / or alkali metal persilicate, and hydrogen peroxide inclusion compounds such as H2G2-urea adducts, as well as mixtures thereof. Hydrogen peroxide can also be generated with the aid of an enzymatic system, i.e., an oxidase and its substrate. If solid peroxygen compounds are to be used, they can be used in the form of powders or granules, which can also be coated in a manner known in principle. Particular preference is given to using alkali metal percarbonate, alkali metal perborate monohydrate, or hydrogen peroxide.A detergent usable within the scope of the invention contains peroxidic bleaching agent in amounts of preferably up to 60 wt.%, in particular from 5 wt.% to 50 wt.%, and particularly preferably from 15 wt.% to 30 wt.%, or alternatively from 2.5 wt.% to 20 wt.%, with hydrogen peroxide being the particularly preferred peroxidic bleaching agent in liquid detergents and sodium percarbonate being the particularly preferred peroxidic bleaching agent in solid detergents. Peroxidic bleaching agent particles preferably have a particle size in the range of 10 μm to 5000 μm, in particular from 50 μm to 1000 μm, and / or a density of 0.85 g / cm. 3 up to 4.9 g / cm 3 , in particular 0.91 g / cm 3 up to 2.7 g / cm 3As bleach-activating compounds that yield peroxocarboxylic acid under perhydrolysis conditions, compounds that yield optionally substituted perbenzoic acid and / or aliphatic peroxocarboxylic acids having 1 to 12 carbon atoms, in particular 2 to 4 carbon atoms, under perhydrolysis conditions, can be used, alone or in mixtures. Suitable bleach activators are those that carry O- and / or N-acyl groups, in particular of the stated number of carbon atoms, and / or optionally substituted benzoyl groups. Preferred are multiply acylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates or carboxylates or the sulfonic or carboxylic acids thereof,in particular nonanoyl or isononanoyl or lauroyloxybenzenesulfonate (NOBS or iso-NOBS or LOBS) or decanoyloxybenzoate (DOBA), their formal carbonic acid ester derivatives such as 4-(2-decanoyloxyethoxycarbonyloxy)benzenesulfonate (DECOBS), acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2,5-di-acetoxy-2,5-dihydrofuran as well as acetylated sorbitol and mannitol and mixtures thereof (SORMAN), acylated sugar derivatives, in particular pentaacetylglucose (PAG), pentaacetylfructose, tetraacetylxylose and octaacetyllactose, acetylated, optionally N-alkylated glucamine and gluconolactone, and / or N-acylated lactams, for example N-benzoylcaprolactam.

[0028] In addition to the compounds that form peroxocarboxylic acids under perhydrolysis conditions, or instead of them, other bleach-activating compounds, such as nitriles, from which perimidic acids are formed under perhydrolysis conditions, may be present. These include, in particular, aminoacetonitrile derivatives with a quaternized nitrogen atom according to the formula in the R 1 represents -H, -CH3, a C2-24 alkyl or alkenyl radical, a substituted C2-24 alkyl or C2-24 alkenyl radical having at least one substituent from the group consisting of -Cl, -Br, -OH, -NH2, -CN and -N (+) -CH2-CN, an alkyl or alkenylaryl radical having a Ci-24 alkyl group, or a substituted alkyl or alkenylaryl radical having at least one, preferably two, optionally substituted Ci-24 alkyl group(s) and optionally further substituents on the aromatic ring, R 2 and R 3are independently selected from -CH2-CN, -CH3, -CH2-CH3, CH2-CH2-CH3, - CH(CH3)-CH3, -CH2-OH, -CH2-CH2-OH, -CH(OH)-CH3, -CH2-CH2-CH2-OH, -CH2-CH(OH)-CH3, - CH(OH)-CH2-CH3, -(CH2CH2-O)nH with n = 1, 2, 3, 4, 5 or 6, R 4 and R 5 independently of each other a preceding for R 1 , R 2 or R 3 have the meaning given, where at least 2 of the radicals mentioned, in particular R 2 and R 3, including the nitrogen atom and optionally further heteroatoms, can be linked to one another in a ring-closing manner and then preferably form a morpholino ring, and X is a charge-balancing anion, preferably selected from benzenesulfonate, toluenesulfonate, cumenesulfonate, the C8-15 alkylbenzenesulfonates, the C1-20 alkyl sulfates, the C8-22 carboxylic acid methyl ester sulfonates, sulfate, hydrogen sulfate, and mixtures thereof. Bleach activators which form peroxocarboxylic acids or perimidic acids under perhydrolysis conditions are preferably present in amounts of up to 25% by weight, in particular 0.1% by weight to 10% by weight, in agents according to the invention. Bleach activator particles preferably have a particle size in the range from 10 pm to 5000 pm, in particular from 50 pm to 1000 pm and / or a density of 0.85 g / cm 3 up to 4.9 g / cm 3 , in particular 0.91 g / cm 3 up to 2.7 g / cm 3 on.

[0029] The presence of bleach-catalyzing transition metal complexes, in addition to or instead of the aforementioned bleach activators, is possible. These are preferably selected from cobalt, iron, copper, titanium, vanadium, manganese, and ruthenium complexes. Both inorganic and organic compounds can be considered as ligands in such transition metal complexes, including carboxylates and in particular compounds with primary, secondary and / or tertiary amine and / or alcohol functions, such as pyridine, pyridazine, pyrimidine, pyrazine, imidazole, pyrazole, triazole, 2,2'-bispyridylamine, tris-(2-pyridylmethyl)amine, 1,4,7-triazacyclononane, 1,4,7-trimethyl-1,4,7-triazacyclononane, 1,5,9-trimethyl-1,5,9-triazacyclododecane, (bis-((1-methylimidazol-2-yl)-methyl))-(2-pyridylmethyl)-amine, N,N'-(bis-(1-methylimidazol-2-yl)-methyl)-ethylenediamine, N-Bis-(2-benzimidazolylmethyl)-aminoethanol, 2,6-bis-(bis-(2-benzimidazolylmethyl)aminomethyl)-4-methylphenol, N,N,N',N'-Tetrakis-(2-benzimidazolylmethyl)-2-hydroxy-1,3-diaminopropane, 2,6-bis-(bis-(2-pyridylmethyl)aminomethyl)-4-methylphenol, 1,3-bis-(bis-(2-benzimidazolylmethyl)aminomethyl)benzene, sorbitol, mannitol, erythritol, adonitol, inositol, lactose, and optionally substituted salens, porphines, and porphyrins. The inorganic neutral ligands include, in particular, ammonia and water. If not all coordination sites of the transition metal central atom are occupied by neutral ligands, the complex contains further, preferably anionic, and among these, in particular mono- or bidentate ligands. These include, in particular, halides such as fluoride, chloride, bromide, and iodide, and the (NO2) group.This means a nitro ligand or a nitrito ligand. The (NO2) group can also be chelated to a transition metal, or it can bridge two transition metal atoms asymmetrically or in a p-O bond. In addition to the ligands mentioned, the transition metal complexes can also bear other, generally simpler ligands, particularly monovalent or polyvalent anion ligands. Examples include nitrate, acetate, trifluoroacetate, formate, carbonate, citrate, oxalate, perchlorate, and complex anions such as hexafluorophosphate. The anion ligands are intended to ensure charge balance between the transition metal's central atom and the ligand system. The presence of oxo ligands, peroxo ligands, and imino ligands is also possible. Such ligands, in particular, can also act as bridging ligands, forming polynuclear complexes. In the case of bridged, dinuclear complexes, both metal atoms in the complex do not have to be the same. The use of binuclear complexes,in which the two transition metal central atoms have different oxidation numbers is possible. If anion ligands are absent or the presence of anion ligands does not lead to charge balance in the complex, anionic counterions are present in the transition metal complex compounds to be used according to the invention, which neutralize the cationic transition metal complex. These anionic counterions include, in particular, nitrate, hydroxide, hexafluorophosphate, sulfate, chlorate, perchlorate, halides such as chloride, or the anions of carboxylic acids such as formate, acetate, oxalate, benzoate, or citrate. Examples of usable transition metal complex compounds are [N,N'-bis[(2-hydroxy-5-vinylphenyl)methylene]-1,2-diaminocyclohexane]-manganese-(III) chloride, [N,N'-bis[(2-hydroxy-5-nitrophenyl)methylene]-1,2-diaminocyclohexane]-manganese-(III) acetate, [N,N'-bis[(2-hydroxyphenyl)methylene]-1,2-phenylenediamine]-manganese-(III) acetate, [N,N'-bis[(2-hydroxyphenyl)methylene]-1,2-diaminocyclohexane]-manganese-(III) chloride, [N,N'-bis[(2-hydroxyphenyl)methylene]-1,2-diaminoethane]-manganese-(III) chloride, [N,N'-bis[(2-hydroxy-5-sulfonatophenyl)methylene]-1,2-diaminoethane]-manganese-(III) chloride, manganese oxalato complexes, nitropentammine-cobalt(III) chloride, nitritopentammine-cobalt(III) chloride, hexa-ammine-cobalt(III) chloride, chloropentammine-cobalt(III) chloride and the peroxo complex [(NH3)5Co-O-O-Co(NH3)5]Cl4.

[0030] Suitable enzymes for use in the detergents include those from the class of proteases, amylases, lipases, cutinases, pullulanases, hemicellulases, cellulases, oxidases, laccases, and peroxidases, as well as mixtures thereof. Enzymatic active ingredients obtained from fungi or bacteria, such as Bacillus subtilis, Bacillus licheniformis, Bacillus lentus, Streptomyces griseus, Humicola lanuginosa, Humicola insolens, Pseudomonas pseudoalcaligenes, Pseudomonas cepacia, or Coprinus cinereus, are particularly suitable. The enzymes can be adsorbed onto carriers and / or embedded in coating substances to protect them against premature inactivation. They are preferably present in the detergents or cleaning agents according to the invention in amounts of up to 5% by weight, in particular from 0.002% by weight to 4% by weight.If the agent according to the invention contains protease, it preferably has a proteolytic activity in the range of about 100 PE / g to about 10,000 PE / g, in particular 300 PE / g to 8,000 PE / g. If multiple enzymes are to be used in the agent according to the invention, this can be done by incorporating two or more separate enzymes or enzymes formulated separately in a known manner, or by two or more enzymes formulated together in one granulate.

[0031] To adjust a desired pH value that does not arise automatically from the mixing of the other components, the agents according to the invention can contain system- and environmentally compatible acids, in particular citric acid, acetic acid, tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid, and / or adipic acid, but also mineral acids, in particular sulfuric acid, or bases, in particular ammonium or alkali hydroxides. Such pH regulators are contained in the agents according to the invention in amounts of preferably not more than 20% by weight, in particular from 1.2% to 17% by weight.

[0032] The purpose of graying inhibitors is to keep the dirt detached from the textile fibers suspended in the liquor. Suitable for this purpose are water-soluble colloids, usually of an organic nature, such as starch, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose, or salts of acidic sulfuric acid esters of cellulose or starch. Water-soluble polyamides containing acidic groups are also suitable for this purpose. Starch derivatives other than those mentioned above can also be used, for example, aldehyde starches. Preference is given to cellulose ethers, such as carboxymethylcellulose (sodium salt), methylcellulose, hydroxyalkylcellulose, and mixed ethers, such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose, and mixtures thereof, for example in amounts of 0.1 to 5% by weight, based on the agent.

[0033] If desired, the agents may contain a conventional dye transfer inhibitor, preferably in amounts of up to 2% by weight, in particular 0.1% by weight to 1% by weight, which in a preferred embodiment is selected from the polymers of vinylpyrrolidone, vinylimidazole, vinylpyridine-N-oxide or the copolymers thereof. Useful are polyvinylpyrrolidones with molecular weights of 15,000 g / mol to 50,000 g / mol as well as polyvinylpyrrolidones with higher molecular weights of, for example, up to over 1,000,000 g / mol, in particular from 1,500,000 g / mol to 4,000,000 g / mol, N-vinylimidazole / N-vinylpyrrolidone copolymers, polyvinyloxazolidones, copolymers based on vinyl monomers and carboxamides, polyesters and polyamides containing pyrrolidone groups, grafted polyamidoamines and polyethyleneimines, polyamine N-oxide polymers and polyvinyl alcohols.Enzymatic systems comprising a peroxidase and hydrogen peroxide or a substance that releases hydrogen peroxide in water can also be used. The addition of a mediator compound for the peroxidase, for example, an acetosyringone, a phenol derivative, or a phenotiazine or phenoxazine, is preferred in this case, although the above-mentioned polymeric dye transfer inhibitor active ingredients can also be used. Polyvinylpyrrolidone preferably has an average molecular weight in the range of 10,000 g / mol to 60,000 g / mol, in particular in the range of 25,000 g / mol to 50,000 g / mol. Among the copolymers, those of vinylpyrrolidone and vinylimidazole in a molar ratio of 5:1 to 1:1 with an average molar mass in the range of 5,000 g / mol to 50,000 g / mol, in particular 10,000 g / mol to 20,000 g / mol, are preferred.In preferred embodiments of the invention, however, the detergents are free of such additional dye transfer inhibitors.

[0034] Detergents can contain, for example, derivatives of diaminostilbenedisulfonic acid or its alkali metal salts as optical brighteners, although they are preferably free of optical brighteners for use as color detergents. Suitable examples include salts of 4,4'-bis(2-anilino-4-morpholino-1,3,5-triazinyl-6-amino)stilbene-2,2'-disulfonic acid or similarly structured compounds that carry a diethanolamino group, a methylamino group, an anilino group, or a 2-methoxyethylamino group instead of the morpholino group. Furthermore, brighteners of the substituted diphenylstyryl type may be present, for example, the alkali metal salts of 4,4'-bis(2-sulfostyryl)-diphenyl, 4,4'-bis(4-chloro-3-sulfostyryl)-diphenyl, or 4-(4-chlorostyryl)-4'-(2-sulfostyryl)-diphenyl. Mixtures of the aforementioned optical brighteners can also be used.

[0035] Particularly when used in mechanical processes, it can be advantageous to add conventional foam inhibitors to the agents. Suitable foam inhibitors include, for example, soaps of natural or synthetic origin that contain a high proportion of C1a-C24 fatty acids. Suitable non-surfactant foam inhibitors include, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica, as well as paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica or bisfatty acid alkylenediamides. Mixtures of different foam inhibitors, for example, those made of silicones, paraffins, or waxes, are also advantageously used. The foam inhibitors, especially silicone- and / or paraffin-containing foam inhibitors, are preferably bound to a granular, water-soluble or water-dispersible carrier substance. Mixtures of paraffins and bistearylethylenediamide are particularly preferred.

[0036] In a preferred embodiment, the agent according to the invention is particulate and contains, in addition to the surfactant essential to the invention, builder, in particular in an amount in the range of 1 wt.% to 60 wt.%.

[0037] In a further preferred embodiment, an agent according to the invention is liquid and contains up to 90% by weight, in particular 10% by weight to 85% by weight, preferably 25% by weight to 75% by weight, and particularly preferably 35% by weight to 65% by weight of water, water-miscible solvent or a mixture of water and water-miscible solvent. Water-miscible solvents include, for example, monohydric alcohols having 1 to 4 C atoms, in particular methanol, ethanol, isopropanol and tert-butanol, diols and triols having 2 to 4 C atoms, in particular ethylene glycol, propylene glycol and glycerol, as well as mixtures thereof and the ethers derivable from the aforementioned classes of compound. Such water-miscible solvents are preferably present in the agents according to the invention in amounts not exceeding 30% by weight, in particular from 2% by weight to 20% by weight.

[0038] In a further preferred embodiment, the agent according to the invention is present in a chamber made of water-soluble material in a ready-to-dose portion; the agent then preferably contains less than 15% by weight, in particular in the range of 1% by weight to 12% by weight, of water. A portion is an independent dosing unit with at least one chamber containing the product to be dosed. A chamber is a space delimited by walls (for example, by a film), which can also exist without the product to be dosed (optionally with a change in its shape). A surface coating or a layer of a surface coating is therefore not a wall according to the present invention.

[0039] The chamber walls are made of a water-soluble material. The water solubility of the material can be determined using a square film of the material in question (film: 22 x 22 mm with a thickness of 76 μm) fixed in a square frame (inner edge length: 20 mm) according to the following measurement protocol. The framed film is placed in 800 ml of distilled water at 20 °C in a 1-liter beaker with a circular bottom (made by Co.Schott, Mainz, 1000 ml beaker, low form) so that the surface of the clamped film is positioned at a right angle to the bottom of the beaker, the top edge of the frame is 1 cm below the water surface, and the bottom edge of the frame is aligned parallel to the bottom of the beaker such that the bottom edge of the frame runs along the radius of the beaker bottom and the center of the bottom edge of the frame is positioned above the center of the radius of the beaker bottom. The material dissolves within 600 seconds with stirring (magnetic stirrer speed 300 rpm, stirring bar: 5 cm long) to such an extent that no individual solid particles are visible to the naked eye.

[0040] The walls of the chambers, and thus the water-soluble enclosures of the detergents according to the invention, are preferably formed from a water-soluble film material. Such water-soluble packages can be produced either by vertical form-fill-seal processes or by thermoforming processes.

[0041] The thermoforming process generally includes forming a first layer of a water-soluble film material to form recesses for receiving a composition therein, filling the composition into the recesses, covering the composition-filled recesses with a second layer of a water-soluble film material, and sealing the first and second layers together at least around the recesses.

[0042] The water-soluble film material is preferably selected from polymers or polymer blends. The wrapper can be formed from one or two or more layers of water-soluble film material. The water-soluble film materials of the first layer and the further layers, if present, can be the same or different. It is preferred that the water-soluble wrapper contains polyvinyl alcohol or a polyvinyl alcohol copolymer; more preferably, it consists of polyvinyl alcohol or a polyvinyl alcohol copolymer.

[0043] Water-soluble films for producing the water-soluble coating are preferably based on a polyvinyl alcohol or a polyvinyl alcohol copolymer whose molecular weight is in the range of 10,000 to 1,000,000 gmol -1 , preferably from 20,000 to 500,000 gmol -1 , particularly preferably from 30,000 to 100,000 gmol -1 and especially from 40,000 to 80,000 gmol -1 lies.

[0044] Polyvinyl alcohol is typically produced by hydrolysis of polyvinyl acetate, since the direct synthesis route is not possible. The same applies to polyvinyl alcohol copolymers, which are produced from polyvinyl acetate copolymers. It is preferred if at least one layer of the water-soluble coating comprises a polyvinyl alcohol whose degree of hydrolysis is 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol%, and especially 82 to 88 mol%.

[0045] A film material suitable for producing the water-soluble wrapping may additionally contain polymers selected from the group comprising acrylic acid-containing polymers, polyacrylamides, oxazoline polymers, polystyrenesulfonates, polyurethanes, polyesters, polyethers, polylactic acid, and / or mixtures of the above polymers. Copolymerization of the monomers underlying such polymers, individually or in mixtures of two or more, with vinyl acetate is also possible.

[0046] Preferred polyvinyl alcohol copolymers comprise, in addition to vinyl alcohol, an ethylenically unsaturated carboxylic acid, its salt, or its ester. Particularly preferably, such polyvinyl alcohol copolymers contain, in addition to vinyl alcohol, acrylic acid, methacrylic acid, acrylic acid esters, methacrylic acid esters, or mixtures thereof; among the esters, C 1-4 alkyl esters or hydroxyalkyl esters are preferred. Likewise preferred polyvinyl alcohol copolymers comprise, in addition to vinyl alcohol, ethylenically unsaturated dicarboxylic acids as further monomers. Suitable dicarboxylic acids include, for example, itaconic acid, maleic acid, fumaric acid, and mixtures thereof, with itaconic acid being particularly preferred.

[0047] Suitable water-soluble films for use in the wrappings of the water-soluble packages according to the invention are films marketed by MonoSol LLC, for example, under the designation M8630, C8400, or M8900. Other suitable films include films called Solublon® PT, Solublon® GA, Solublon® KC, or Solublon® KL from Aicello Chemical Europe GmbH, or the VF-HP films from Kuraray. The detergent or cleaning agent portion, comprising the detergent or cleaning agent and the water-soluble wrapping, can have one or more chambers. The water-soluble wrappings with one chamber can have a substantially dimensionally stable spherical, spherical ellipsoidal, cube-shaped, cuboid-shaped, or pillow-shaped configuration with a circular, elliptical, square, or rectangular basic shape. The agent can be contained in one or more chambers, if present, of the water-soluble wrapping.

[0048] In a preferred embodiment, the water-soluble coating has two chambers. In this embodiment, each chamber can contain a solid partial composition or a liquid partial composition, or the first chamber can contain a liquid partial composition and the second chamber a solid partial composition.

[0049] The proportions of the agents contained in the different chambers of a water-soluble casing with two or more chambers can have the same composition. However, the agents in a water-soluble casing with at least two chambers preferably have partial compositions that differ in at least one ingredient and / or in the content of at least one ingredient. Preferably, one partial composition of such agents according to the invention comprises an enzyme and / or bleach activator, and a further partial composition present separately comprises a peroxidic bleaching agent, wherein the first-mentioned partial composition then comprises, in particular, no peroxidic bleaching agent, and the second-mentioned partial composition then comprises, in particular, no enzyme and no bleach activator.

[0050] By packaging the portions in a water-soluble casing, the user is able to put one or, if desired, several, preferably one, of the portions into the washing machine or dishwasher, in particular into the detergent drawer of a washing machine, or into a container for carrying out a manual washing or cleaning process. Such portion packs meet the consumer's desire for simplified dosing. After water is added, the casing material dissolves, so that the ingredients are released and can develop their effect in the liquor. A water-soluble casing preferably weighs 10 g to 35 g, in particular 12 g to 28 g and particularly preferably 12 g to 15 g, wherein the proportion of the water-soluble casing contained in the weight specification accounts for 0.3 g to 2.5 g, in particular 0.7 g to 1.2 g.

[0051] The production of solid compositions according to the invention presents no difficulties and can be carried out in a known manner, for example by spray drying or granulation, with enzymes and any other thermally sensitive ingredients, such as bleaching agents, being added separately later if necessary. For the production of compositions with increased bulk density, particularly in the range of 650 g / l to 950 g / l, a process comprising an extrusion step is preferred. Liquid or pasty compositions according to the invention in the form of solutions containing water and conventional solvents are generally prepared by simply mixing the ingredients, which can be added in bulk or as a solution to an automatic mixer.

[0052] Examples

[0053] Example 1: Washing performance

[0054] The washing performance of surfactant combinations according to the invention was determined in comparison to conventional surfactant mixtures in a miniaturized washing device. For this purpose, aqueous solutions of 1 g / l each of the mixtures listed in Table 1 below (which had the weight ratio of the individual surfactants given in parentheses) were used to wash cotton test fabrics with standardized oily soils at 30 °C, and the sum of the Y values ​​across all test fabrics was determined after drying. The values ​​also given in Table 1 were obtained. A clear superiority of the surfactant mixtures E1 to E5 according to the invention was observed compared to the individual surfactants or other surfactant mixtures (V1 to V5).

[0055] Table 1 Example 2: Zeta potential

Claims

Patent claims 1. Surfactant combination of an alkyl polyglycol ether of the general formula (Ia) or (Ib) with a rhamnolipid of the general formula (II) or its salt, CH3(CH2)m(-OR)n-OH (la) in which R represents a linear or branched alkyl group having 2 to 4 C atoms, in particular 2 C atoms, m represents a number from 7 to 15, x and y independently represent numbers from 0 to 12, z represents a number from 1 to 4, the sum x + y + z being in the range from 10 to 16, n represents a number from 2 to 10, o represents 2, 1 or 0, p represents 0 or 1, and R 1 and R 2 independently of one another represent identical or different organic radicals having 2 to 24, in particular 5 to 13 carbon atoms, and a further anionic surfactant which is different from the rhamnolipid.

2. Washing or cleaning agents containing a surfactant combination of an alkyl polyglycol ether of the general formula (Ia) or (Ib) with a rhamnolipid of the general formula (II) or its salt, CH3(CH2)m(-OR)n-OH (la) in which R represents a linear or branched alkyl group having 2 to 4 C atoms, in particular 2 C atoms, m represents a number from 7 to 15, x and y independently represent numbers from 0 to 12, z represents a number from 1 to 4, the sum x + y + z being in the range from 10 to 16, n represents a number from 2 to 10, o represents 2, 1 or 0, p represents 0 or 1, and R 1 and R 2 independently of one another represent identical or different organic radicals having 2 to 24, in particular 5 to 13 carbon atoms, and a further anionic surfactant which is different from the rhamnolipid.

3. Agent according to claim 2, characterized in that it contains 5 wt.% to 70 wt.%, in particular 10 wt.% to 50 wt.% of the surfactant combination.

4. Agent according to claim 2 or 3, characterized in that it additionally contains up to 30 wt.% of further surfactant.

5. Agent according to one of claims 2 to 4, characterized in that it is particulate and contains builders, in particular in an amount in the range of 1 wt.% to 60 wt.%, or that it is liquid and contains up to 90 wt.%, in particular 10 wt.% to 85 wt.% water, water-miscible solvent or a mixture of water and water-miscible solvent.

6. Agent according to one of claims 2 to 5, characterized in that it is present in individually dosed portions in a chamber formed from water-soluble material and contains less than 15% by weight, in particular in the range from 1% by weight to 12% by weight, of water.

7. Use of a surfactant combination of an alkyl polyglycol ether of the general formula (Ia) or (Ib) with a rhamnolipid of the general formula (II) or its salt, CH3(CH2)m(-OR)n-OH (la) in which R represents a linear or branched alkyl group having 2 to 4 C atoms, in particular 2 C atoms, m represents a number from 7 to 15, x and y independently represent numbers from 0 to 12, z represents a number from 1 to 4, the sum x + y + z being in the range from 10 to 16, n represents a number from 2 to 10, o represents 2, 1 or 0, p represents 0 or 1, and R 1 and R 2 independently of one another represent identical or different organic radicals having 2 to 24, in particular 5 to 13 carbon atoms, and a further anionic surfactant which is different from the rhamnolipid, to increase the performance of detergents or cleaning agents when washing laundry or cleaning hard surfaces.

8. Use of a surfactant combination of an alkyl polyglycol ether of the general formula (Ia) or (Ib) with a rhamnolipid of the general formula (II) or its salt, CH3(CH2)m(-OR)n-OH (la) in which R represents a linear or branched alkyl group having 2 to 4 C atoms, in particular 2 C atoms, m represents a number from 7 to 15, x and y independently represent numbers from 0 to 12, z represents a number from 1 to 4, the sum x + y + z being in the range from 10 to 16, n represents a number from 2 to 10, o represents 2, 1 or 0, p represents 0 or 1, and R 1 and R 2 independently of one another represent identical or different organic radicals having 2 to 24, in particular 5 to 13 carbon atoms, and a further anionic surfactant which is different from the rhamnolipid, for the production of washing or cleaning agents.

9. A process for washing laundry or cleaning hard surfaces, characterized in that a surfactant combination of an alkyl polyglycol ether of the general formula (Ia) or (Ib) with a rhamnolipid of the general formula (II) or its salt, CH3(CH2)m(-OR)n-OH (la) in which R represents a linear or branched alkyl group having 2 to 4 C atoms, in particular 2 C atoms, m represents a number from 7 to 15, x and y independently represent numbers from 0 to 12, z represents a number from 1 to 4, the sum x + y + z being in the range from 10 to 16, n represents a number from 2 to 10, o represents 2, 1 or 0, p represents 0 or 1, and R 1 and R 2independently of one another represent identical or different organic radicals having 2 to 24, in particular 5 to 13 carbon atoms, and a further anionic surfactant which is different from the rhamnolipid, or an agent which contains them, and carrying it out at temperatures in the range from 20 °C to 40 °C, in particular up to a maximum of 30 °C.

10. Surfactant combination according to claim 1, agent according to one of claims 2 to 6, use according to claim 7 or 8, or process according to claim 9, characterized in that the weight ratio of alkyl polyglycol ether to rhamnolipid is in the range from 50:50 to 99:1, in particular from 70:30 to 95:5; and / or that in the general formula (Ia) m is a number in the range from 11 to 15 and / or n is a number in the range from 4 to 7; and / or that the salts of the compounds of the general formula (II) are those in which the carboxyl H atom is replaced by an alkali metal cation or the group N + R3 R 4 R 5 R 6 , in the R 3 , R 4 , R 5 and R 6 independently of each other represent hydrogen, an alkyl group with 1 to 6 C atoms or a Hydroxyalkyl group with 2 to 6 C atoms, is replaced and the carboxylic acid group is present as a carboxylate anion.

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