WO2024251400A1 - New surfactant combinations and washing and cleaning agents containing same - Google Patents

Abstract

The invention relates to surfactant combinations of a first alkylpolyglycol ether of the general formula (Ia) or (Ib) and a second alkylpolyglycol ether of the general formula (IIa) or (IIb) and a rhamnolipid of the general formula (III) or the salt thereof, CH₃(CH₂)_m(-O-R)_n-OH (Ia), formula (Ib), CH₃(CH₂)_m(-O-R)_a-OH (IIa), formula (IIb), formula (II), wherein R is a linear or branched alkyl group with 2 to 4 C atoms, m is a number from 9 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 1 to 5 and a is a number from 2 to 7, and a is greater n by at least 1, 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. These surfactant combinations can be well incorporated into washing and cleaning agents, have excellent use properties and can be produced from renewable raw materials.

Description

New surfactant combination and detergents and cleaning agents containing them

The invention relates to a combination of non-ionic surfactant with anionic surfactant, which can be produced at least partially on the basis of renewable raw materials and which has superior washing performance on oily soiling. The invention also relates to washing or cleaning agents which contain this surfactant combination.

The use of surfactants to reduce the surface tension of water, to form dispersions and to facilitate solubilization has long been common knowledge in the field of detergents and cleaning agents. Although many surfactants are made entirely or partially from renewable raw materials, some powerful and widely used representatives are still petrochemically based. In addition, there is a constant desire to provide surfactants with outstanding application properties in order to achieve high performance even with low surfactant usage.

The object of the present invention is to provide surfactants which have advantageous application properties and can be produced, if possible, on the basis of renewable raw materials. In addition, the surfactants should be well tolerated by the skin and can also be formulated together with other surfactants so that they are particularly suitable for use in washing and cleaning agents.

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 can be esterified with a hydroxyl group of another hydroxyl-containing fatty acid molecule. They are obtained by fermentation of bacteria of the genus Pseudomonas, in particular Pseudomonas aeruginosa, preferably when they grow on hydrophobic substrates such as n-alkanes or vegetable oils. Due to their surface-active behavior and their origin, rhamnolipids belong to the so-called biosurfactants. The 3-(hydroxydecanoyloxy)decanoic acid dirhamnoside, for example, has the formula

Detergents are known from patent specification EP 0 499 434 B1 which contain 1 to 60% by weight of a surfactant which forms a micellar phase at pH 7.0 and 25°C in 1% by weight aqueous solution and a surfactant which forms a lamellar phase at pH 7.0 and 25°C in 1% by weight aqueous solution, where rhamnolipid can be both the surfactant which forms the micellar phase and the surfactant which forms the lamellar phase. European patent specification EP 1 445 302 B1 relates to detergents which contain at least one glycolipid biosurfactant and at least one non-glycolipid surfactant, where these are in a micellar phase. From the international patent application WO 2012/010405 A1, cleaning agents are known which contain at least 1% by weight of biosurfactant and an enzyme of bacterial origin. The European patent application EP 0 605 308 A1 discloses compositions which contain 0.001% by weight to 99.99% by weight of anionic and/or nonionic surfactant and 0.001% by weight to 99.99% by weight of glycolipid, where the glycolipids can include, for example, sophorolipids, rhamnolipids, glucose lipids, trehalose lipids and cellobiose lipids. From the international patent application WO 2012/010406 A1, cleaning agents are known which contain lipase and rhamnolipid, where the rhamnolipid consists of at least 50% by weight of mono-rhamnolipid. Detergents are known from the international patent application WO 2012/010407 A1 which contain glycolipid surfactant and lipase of bacterial origin, wherein the glycolipid surfactant consists of at least 20% by weight of disaccharide acid group-containing glycolipid surfactant. The 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 from 95:5 to 45:55. The 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. From the European patent application EP 2 786 743 A1, rhamnolipid mixtures are known which contain 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 the international patent application WO 2016/096478 A1. The present invention relates, in a first embodiment, to a surfactant combination of a first alkyl polyglycol ether of the general formula (Ia) or (Ib) with a second alkyl polyglycol ether of the general formula (IIa) or (Hb) and with a rhamnolipid of the general formula (III) or its salt,

in denen R für eine lineare oder verzweigte Alkylgruppe mit 2 bis 4 C-Atomen, insbesondere 2 C- Atomen steht, m für eine Zahl von 9 bis 15 steht, x und y unabhängig voneinander für Zahlen von 0 bis 12 stehen, z für eine Zahl von 1 bis 4 steht, wobei die Summe x + y + z im Bereich von 10 bis 16 liegt, n für eine Zahl von 1 bis 5 steht und a für eine Zahl von 2 bis 7 steht, wobei a mindestens um 1 größer als n ist, o für 2, 1 oder 0 steht, p für 0 oder 1 steht, und R¹ und R² unabhängig voneinander für gleiche oder verschiedene organische Reste mit 2 bis 24, insbesondere 5 bis 13 Kohlenstoffatomen, stehen. R¹ und/oder R² sind dabei vorzugsweise Alkyl- oder Alkenylreste, die gegebenenfalls verzweigt und/oder substituiert sein können, insbesondere hydroxy-substituiert, gegebenenfalls einfach, zweifach oder dreifach ungesättigt sein können und dann bevorzugt ausgewählt werden aus der Gruppe bestehend aus Pentenyl, Heptenyl, Nonenyl, Undecenyl und Tridecenyl, und alternativ bevorzugt -(CH2)q-CH3 sind mit q = 1 bis 23, bevorzugt 4 bis 12. CH ₃ (CH ₂ )m(-OR)n-OH (la)

in which R is a linear or branched alkyl group having 2 to 4 C atoms, in particular 2 C atoms, m is a number from 9 to 15, x and y independently of one another are numbers from 0 to 12, z is a number from 1 to 4, where the sum x + y + z is in the range from 10 to 16, n is a number from 1 to 5 and a is a number from 2 to 7, where a is at least 1 greater than n, o is 2, 1 or 0, p is 0 or 1, and R ¹ and R ² independently of one another are identical or different organic radicals having 2 to 24, in particular 5 to 13 carbon atoms. R ¹ and/or R ² 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 (III) or their salts where p = 1, and “mono-rhamnolipids” are understood to mean those of the general formula (III) or their salts where p = 0.

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

Surfactants of the general formula (Ib) or the general formula (IIb) are less preferred than surfactants of the general formula (Ia) or the general formula (Ia), since they are only obtainable from a renewable raw material basis with comparatively great effort. Preferred surfactants of the general formula (Ia) or the general formula (Ila) 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 2 to 4 and/or a is a number in the range from 4 to 7.

Surfactants of the general formula (la), (Ib), (lla) or (llb) can be prepared in a known manner by r T OH L I J z

L Jy herstellen, wobei bei Einsatz von Alkoholmischungen die Indizes m, x, y und z hier und in den Verbindungen der allgemeinen Formel (la), (Ib), (lla) oder (llb) auch nicht-ganzzahlig sein können. Bei der Alkoxylierung wird vorzugsweise Ethylenoxid eingesetzt. Da sich in aller Regel bei der Alkoxylierung der Alkohole Homologengemische bilden, kann auch der durchschnittliche Alkoxylierungsgrad n oder a in den Verbindungen der allgemeinen Formel (la), (Ib), (lla) oder (llb) nicht-ganzzahlig sein. Der Alkohol CH3(CH₂)m-OH ist vorzugsweise ein Fettalkohol und stammt damit ebenfalls aus einer nachwachsenden Rohstoffbasis. Zu den besonders bevorzugten Tensiden der allgemeinen Formel (la) gehören der lineare Ci2-Alkohol mit 3 Ethylenoxidgruppen und der lineare Cu-Alkohol mit 4 Ethylenoxidgruppen sowie die technischen Alkoxylate, die durch Umsetzung von 1 Molequivalent linearem Ci2-Alkohol oder linearem Cu-Alkohol mit 2, 3 oder 4 Molequivalenten Ethylenoxid entstehen. Zu den besonders bevorzugten Tensiden der allgemeinen Formel (lla) gehören der lineare Ci2-Alkohol mit 5 Ethylenoxidgruppen und der lineare Cu-Alkohol mit 7 Ethylenoxidgruppen sowie die technischen Alkoxylate, die durch Umsetzung von 1 Molequivalent linearem Ci2-Alkohol oder linearem Cu-Alkohol mit 5, 6 oder ? Molequivalenten Ethylenoxid entstehen Alkoxylation of alcohols CH3(CH2)m-OH or

L Jy, where when alcohol mixtures are used the indices m, x, y and z here and in the compounds of the general formula (la), (Ib), (lla) or (llb) can also be non-integer. Ethylene oxide is preferably used for the alkoxylation. Since homolog mixtures are generally formed during the alkoxylation of the alcohols, the average degree of alkoxylation n or a in the compounds of the general formula (la), (Ib), (lla) or (llb) can also be non-integer. The alcohol CH3(CH ₂ )m-OH is preferably a fatty alcohol and thus also comes from a renewable raw material base. The particularly preferred surfactants of the general formula (la) include the linear Ci2 alcohol with 3 ethylene oxide groups and the linear Cu alcohol with 4 ethylene oxide groups as well as the technical alkoxylates which are formed by reacting 1 molar equivalent of linear Ci2 alcohol or linear Cu alcohol with 2, 3 or 4 molar equivalents of ethylene oxide. The particularly preferred surfactants of the general formula (lla) include the linear Ci2-alcohol with 5 ethylene oxide groups and the linear Cu-alcohol with 7 ethylene oxide groups as well as the technical alkoxylates which are formed by reacting 1 mole equivalent of linear Ci2-alcohol or linear Cu-alcohol with 5, 6 or ? mole equivalents of ethylene oxide

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 alkyl polyglycol ethers of the general formula (IIa) and/or (Ib) with those of the general formula (III), 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 weight proportions than those of the general formula (Ib). If the surfactant combinations contain mixtures of compounds of the general formula (IIa) and the general formula (IIb), those of the general formula (IIa) are preferably present in larger proportions by weight than those of the general formula (IIb). The weight ratio of the sum of the proportions of surfactants of the general formula (Ia) and (Ib) to the sum of the proportions of surfactants of the general formula (IIa) and (IIb) is preferably in the range from 5:95 to 95:5, in particular in the range from 20:80 to 80:20, more preferably from 30:70 to 70:30, even more preferably from 40:60 to 60:40.

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

Particularly good results are achieved when they are used in washing and cleaning agents, so that further objects of the present invention are 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 which contain a surfactant combination defined above.

Because the surfactant combination essential to the invention develops its advantageous effect even at low temperatures, it or an agent containing it is preferably used in processes for washing laundry or for cleaning hard surfaces which are carried out at temperatures in the range from 20 °C to 40 °C, in particular up to a maximum of 30 °C. A washing or cleaning agent according to the invention preferably contains 5% to 70% by weight, in particular 10% to 50% by weight and particularly preferably 12% to 40% by weight of the surfactant combination defined above.

In addition to the surfactant combination, the washing or cleaning agent can contain other ingredients which further improve the application and/or aesthetic properties of the agent. In the context of the present invention, the agent preferably additionally contains one or more substances from the group of non-ionic surfactants, anionic surfactants, builders, bleaches, bleach activators, enzymes, electrolytes, pH adjusters, perfumes, perfume carriers, fluorescent agents, dyes, hydrotopes, foam inhibitors, anti-redeposition agents, graying inhibitors, shrinkage inhibitors, anti-crease agents, color transfer inhibitors, antimicrobial agents, non-aqueous solvents, germicides, fungicides, antioxidants, preservatives, corrosion inhibitors, antistatic agents, bitter agents, ironing aids, phobic and impregnating agents, skin care agents, swelling and anti-slip agents, softening components and UV absorbers.

A washing or cleaning agent according to the invention can contain up to 30% by weight of 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 in addition to the surfactant combination essential to the invention.

The agent according to the invention can 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 can also be used as further nonionic surfactants, in which R ⁷ corresponds to a primary straight-chain or methyl-branched, in particular methyl-branched in the 2-position, aliphatic radical with 8 to 22, preferably 12 to 18 C atoms and G is the symbol which stands for a glycose unit with 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 between 1.2 and 1.4.

Another class of nonionic surfactants, which are used either as the sole additional nonionic surfactant or in combination with other additional nonionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain. 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.

in der R für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen, R¹ für Wasserstoff, einen Alkyl- oder Hydroxyalkylrest mit 1 bis 4 Kohlenstoffatomen und [Z] für einen linearen oder verzweigten Polyhydroxyalkylrest mit 3 bis 10 Kohlenstoffatomen und 3 bis 10 Hydroxylgruppen steht. Bei den Polyhydroxyfettsäureamiden handelt es sich um bekannte Stoffe, die üblicherweise durch reduktive Aminierung eines reduzierenden Zuckers mit Ammoniak, einem Alkylamin oder einem Alkanolamin und nachfolgender Acylierung mit einer Fettsäure, einem Fettsäurealkylester oder einem Fettsäurechlorid erhalten werden können. Zur Gruppe der Polyhydroxyfettsäureamide gehören auch Verbindungen der Formel

in der R für einen linearen oder verzweigten Alkyl- oder Alkenylrest mit 7 bis 12 Kohlenstoffatomen, R¹ für einen linearen, verzweigten oder zyklischen Alkylrest oder einen Arylrest mit 2 bis 8 Kohlenstoffatomen und R² für einen linearen, verzweigten oder zyklischen Alkylrest oder einen Arylrest oder einen Oxy-Alkylrest mit 1 bis 8 Kohlenstoffatomen steht, wobei CwAlkyl- oder Phenylreste bevorzugt sind und [Z] für einen linearen Polyhydroxyalkylrest steht, dessen Alkylkette mit mindestens zwei Hydroxylgruppen substituiert ist, oder alkoxylierte, vorzugsweise ethoxylierte oder propoxylierte Derivate dieses Restes. [Z] wird vorzugsweise durch reduktive Aminierung eines reduzierten Zuckers erhalten, beispielsweise Glucose, Fructose, Maltose, Lactose, Galactose, Mannose oder Xylose. Die N-Alkoxy- oder N-Aryloxy-substituierten Verbindungen können durch Umsetzung mit Fettsäuremethylestern in Gegenwart eines Alkoxids als Katalysator in die gewünschten Polyhydroxyfettsäureamide überführt werden. Other surfactants that may be suitable if desired are polyhydroxy fatty acid amides of the formula,

in which R is an aliphatic acyl radical having 6 to 22 carbon atoms, R ¹ is hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl radical having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups. Polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride. The group of polyhydroxy fatty acid amides also includes compounds of the formula

in which R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ¹ is a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R ² is 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] is 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, methyl glycinediacetic 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 of these, which may also contain small amounts of polymerizable substances without carboxylic acid functionality polymerized in. The relative average molecular mass of the homopolymers of unsaturated carboxylic acids is generally between 5,000 g/mol and 200,000 g/mol, 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, although 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 which contain 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 Cs-Cs-carboxylic acid and 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 monomeric unit is in this case formed from vinyl alcohol and/or preferably an esterified vinyl alcohol. Vinyl alcohol derivatives which are an ester of short-chain carboxylic acids, for example of Ci-C4-carboxylic acids, with vinyl alcohol are particularly preferred. Preferred polymers contain 60% by weight to 95% by weight, in particular 70% by weight to 90% by weight of (meth)acrylic acid or (meth)acrylate, particularly preferably acrylic acid or acrylate, and maleic acid or maleate, as well as 5% by weight to 40% by weight, preferably 10% by weight to 30% by weight, 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 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 which is substituted in the 2-position with an alkyl radical, preferably with a Ci-C4-alkyl radical, or an aromatic radical, which is 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 be, for example, a mono-, di-, oligo- or polysaccharide, with mono-, di- or oligosaccharides being preferred. Sucrose is particularly preferred. The use of the third monomer presumably builds predetermined breaking points into the polymer, which are responsible for the good biodegradability of the polymer. These terpolymers generally have a relative average molecular mass of 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, particularly for the production of liquid agents, in the form of aqueous solutions, preferably in the form of 30 to 50 percent by weight aqueous solutions. All of the acids mentioned are generally used in the form of their water-soluble salts, particularly their alkali salts.

Such organic builder substances can, if desired, be present in amounts of up to 40% by weight, in particular up to 25% by weight and preferably from 1% by weight to 8% by weight. Amounts in the upper half of the ranges mentioned are preferably used in paste-like or liquid, in particular water-containing, agents.

Polyphosphates, preferably sodium triphosphate, are particularly suitable as water-soluble inorganic builder materials. Crystalline or amorphous, water-dispersible alkali aluminosilicates are particularly used as water-insoluble inorganic builder materials, in amounts of not more than 25% by weight, preferably from 3% by weight to 20% by weight and in particular in amounts of from 5% by weight to 15% by weight. Among these, crystalline sodium aluminosilicates in detergent quality, in particular zeolite A, zeolite P and zeolite MAP and optionally zeolite X, are preferred. Amounts close to the upper limit mentioned are preferably used in solid, particulate agents. Suitable aluminosilicates in particular do not have any particles with a grain size of more than 30 pm and preferably consist of at least 80% by weight of particles with a size of less than 10 pm. Their calcium binding capacity is generally in the range from 100 to 200 mg CaO per gram.

In addition to or as an alternative to the water-insoluble aluminosilicate and alkali carbonate mentioned, other water-soluble inorganic builder materials can be included. In addition to polyphosphates such as sodium triphosphate, these include in particular the water-soluble crystalline and/or amorphous alkali silicate builders. Such water-soluble inorganic builder materials are preferably included in the agents in amounts of 1 wt.% to 20 wt.%, in particular 5 wt.% to 15 wt.% The alkali silicates that can be used as builder materials preferably have a molar ratio of alkali oxide to SiO2 of less than 0.95, in particular 1:1.1 to 1:12, and can be amorphous or crystalline. Preferred alkali silicates are the sodium silicates, in particular the amorphous sodium silicates, with a molar ratio Na2O:SiC>2 of 1:2 to 1:2.8. As crystalline silicates, which can be present alone or in a mixture with amorphous silicates, preferably crystalline layered silicates of the general formula Na2Si _x C>2x+iy H2O are used, 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 assumes the values 2 or 3. In particular, both ß- and 5-sodium disilicates (Na2Si2Os y H2O) are preferred. Virtually anhydrous crystalline alkali silicates made from amorphous alkali silicates 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 layer silicate with a modulus of 2 to 3 is used, as can be made from sand and soda. Sodium silicates with a modulus in the range of 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, as is commercially available, for example, under the name Nabion® 15.

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 which release hydrogen peroxide under the conditions of use, such as alkali perborate, alkali percarbonate and/or alkali persilicate, and hydrogen peroxide inclusion compounds such as H2C>2-urea adducts, as well as mixtures of these. Hydrogen peroxide can also be produced with the aid of an enzymatic system, i.e. an oxidase and its substrate. If solid peroxygen compounds are to be used, these can be used in the form of powders or granules, which can also be coated in a manner known in principle. Alkali percarbonate, alkali perborate monohydrate or hydrogen peroxide are particularly preferred. A detergent that can be used in the context of the invention contains peroxidic bleach in amounts of preferably up to 60% by weight, in particular from 5% by weight to 50% by weight and particularly preferably from 15% by weight to 30% by weight or alternatively from 2.5% by weight to 20% by weight, with hydrogen peroxide being the particularly preferred peroxidic bleach in liquid agents and sodium percarbonate being the particularly preferred peroxidic bleach in solid agents. Peroxidic bleach 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 to 4.9 g/cm ³ , in particular from 0.91 g/cm ³ to 2.7 g/cm ³ .

As bleach-activating compounds which yield peroxocarboxylic acid under perhydrolysis conditions, it is possible to use in particular compounds which yield optionally substituted perbenzoic acid and/or aliphatic peroxocarboxylic acids having 1 to 12 C atoms, in particular 2 to 4 C atoms, alone or in mixtures. Suitable bleaching agents are activators which carry O- and/or N-acyl groups, in particular of the stated number of C atoms and/or optionally substituted benzoyl groups. Preference is given to 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.

in der R¹ für -H, -CH3, einen C2-24-Alkyl- oder -Alkenylrest, einen substituierten Ci-24-Alkyl- oder C2- 24-Alkenylrest mit mindestens einem Substituenten aus der Gruppe -CI, -Br, -OH, -NH2, -CN und - N⁽⁺⁾-CH2-CN, einen Alkyl- oder Alkenylarylrest mit einer Ci-24-Alkylgruppe, oder für einen substituierten Alkyl- oder Alkenylarylrest mit mindestens einer, vorzugsweise zwei, gegebenenfalls substituierten Ci-24-Alkylgruppe(n) und gegebenenfalls weiteren Substituenten am aromatischen Ring steht, R² und R³ unabhängig voneinander ausgewählt sind aus -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 mit n = 1 , 2, 3, 4, 5 oder 6, R⁴ und R⁵ unabhängig voneinander eine voranstehend für R¹, R² oder R³ angegebene Bedeutung haben, wobei mindestens 2 der genannten Reste, insbesondere R² und R³, auch unter Einschluss des Stickstoffatoms und gegebenenfalls weiterer Heteroatome ringschließend miteinander verknüpft sein können und dann vorzugsweise einen Morpholino-Ring ausbilden, und X ein ladungsausgleichendes Anion, vorzugsweise ausgewählt aus Benzolsulfonat, Toluolsulfonat, Cumolsulfonat, den Cg-is-Alkylbenzolsulfonaten, den Ci-20-Alkylsulfaten, den C8-22-Carbonsäure-methylestersulfonaten, Sulfat, Hydrogensulfat und deren Gemischen, ist, können eingesetzt werden. Unter Perhydrolysebedingungen Peroxocarbon- säuren oder Perimidsäuren bildende Bleichaktivatoren sind vorzugsweise in Mengen bis zu 25 Gew.- %, insbesondere 0,1 Gew.-% bis 10 Gew.-% in erfindungsgemäßen Mitteln vorhanden. Vorzugsweise weisen Bleichaktivator-Partikel eine Teilchengröße im Bereich von 10 pm bis 5000 pm, insbesondere von 50 pm bis 1000 pm und/oder eine Dichte von 0,85 g/cm³ bis 4,9 g/cm³, insbesondere von 0,91 g/cm³ bis 2,7 g/cm³ auf. In addition to the compounds which form peroxocarboxylic acids under perhydrolysis conditions, or in their place, 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 which R ¹ is -H, -CH3, a C2-24-alkyl or -alkenyl radical, a substituted Ci-24-alkyl or C2-24-alkenyl radical with at least one substituent from the group -CI, -Br, -OH, -NH2, -CN and - N ⁽⁺⁾ -CH2-CN, an alkyl or alkenylaryl radical with a Ci-24-alkyl group, or a substituted alkyl or alkenylaryl radical with at least one, preferably two, optionally substituted Ci-24-alkyl group(s) and optionally further substituents on the aromatic ring, R ² and R ³ are independently selected from -CH2-CN, -CH3, -CH2-CH3, CH2-CH2-CH3, - CH(CH ₃ )-CH3,-CH2-OH, -CH2-CH2-OH, -CH(OH)-CH ₃ , -CH2-CH2-CH2-OH, -CH ₂ -CH(OH)-CH3, - CH(OH)-CH2-CH3, -(CH ₂ CH2-O)nH with n = 1, 2, 3, 4, 5 or 6, R ⁴ and R ⁵ independently of one another have a meaning given above for R ¹ , R ² or R ³ , where at least 2 of the radicals mentioned, in particular R ² and R ³ , can also be linked to one another in a ring-closing manner including the nitrogen atom and optionally further heteroatoms and then preferably form a morpholino ring, and X is a charge-balancing anion, preferably selected from benzenesulfonate, toluenesulfonate, cumenesulfonate, the C 8-13 alkylbenzenesulfonates, the C 1-20 alkyl sulfates, the C 8-22 carboxylic acid methyl ester sulfonates, sulfate, hydrogen sulfate and or 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 to 4.9 g/cm ³ , in particular from 0.91 g/cm ³ to 2.7 g/cm ³ .

The presence of bleach-catalyzing transition metal complexes, in addition to or instead of the bleach activators mentioned, is possible. These are preferably selected from among the cobalt, iron, copper, titanium, vanadium, manganese and ruthenium complexes. Both inorganic and organic compounds can be used as ligands in such transition metal complexes, which include, in addition to carboxylates, 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 the halides such as fluoride, chloride, bromide and iodide, and the (NO2) group, i.e. a nitro ligand or a nitrito ligand. The (NO2) group can also be bound to a transition metal in a chelating manner or it can bridge two transition metal atoms asymmetrically or pl-O. In addition to the ligands mentioned, the transition metal complexes can also carry other, usually simpler ligands, in particular mono- or polyvalent anion ligands. Examples of possible ligands are 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 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 have a bridging effect, so that multinuclear complexes are formed. In the case of bridged, binuclear 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 also possible. If anion ligands are missing or the presence of anion ligands does not lead to charge balance in the grain plex, 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, the 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-diamino-cyclohexane]-manganese-(III) chloride, [N,N'-bis[(2-hydroxy-5-nitrophenyl)-methylene]-1,2-diamino-cyclohexane]-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-sulfonato-phenyl)-methylene]-1,2-diaminoethane]-manganese-(III) chloride, manganese oxalato complexes, nitropentammine-cobalt(III) chloride, nitritopentammine-cobalt(III) chloride, hexamminecobalt(III) chloride, chloropentammine-cobalt(III) chloride and the peroxo complex [(NH3)5Co-0-0-Co(NH3)s]Cl4.

Enzymes that can be used in the agents are those from the class of proteases, amylases, lipases, cutinases, pullulanases, hemicellulases, cellulases, oxidases, laccases and peroxidases and mixtures thereof. Enzymatic active substances 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 on carriers and/or embedded in coating substances in order to protect them against premature inactivation. They are preferably contained in the washing 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 from about 100 PE/g to about 10,000 PE/g, in particular 300 PE/g to 8,000 PE/g. If several 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 prepared separately in a known manner or by two or more enzymes prepared together in a granulate.

To set a desired pH value that does not arise automatically from the mixture 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% by weight to 17% by weight. The purpose of graying inhibitors is to keep the dirt detached from the textile fiber suspended in the liquor. Water-soluble colloids, usually of an organic nature, are suitable for this purpose, for example starch, glue, gelatin, salts of ethercarboxylic acids or ethersulfonic 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. Cellulose ethers such as carboxymethylcellulose (Na salt), methylcellulose, hydroxyalkylcellulose and mixed ethers such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof are preferred, for example in amounts of 0.1 to 5% by weight based on the agent.

If desired, the agents can contain a conventional color 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. Both polyvinylpyrrolidones with molecular weights of 15,000 g/mol to 50,000 g/mol and 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 can be used. Enzymatic systems comprising a peroxidase and hydrogen peroxide or a substance that provides 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 in addition. Polyvinylpyrrolidone preferably has an average molecular weight in the range from 10,000 g/mol to 60,000 g/mol, in particular in the range from 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 molecular weight in the range from 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.

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 are salts of 4,4'-bis(2-anilino-4-morpholino-1,3,5-triazinyl-6-amino)stilbene-2,2'-disulfonic acid or similarly structured compounds which carry a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group instead of the morpholino group. Brighteners can also be lers of the substituted diphenylstyryl type may be present, for example the alkali 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 above-mentioned optical brighteners can also be used.

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 have a high proportion of cis-C24 fatty acids. Suitable non-surfactant-type foam inhibitors include, for example, organopolysiloxanes and mixtures thereof with microfine, optionally silanized silica, as well as paraffins, waxes, microcrystalline waxes and mixtures thereof with silanized silica or bis-fatty acid alkylenediamides. Mixtures of different foam inhibitors are also advantageously used, for example those made from silicones, paraffins or waxes. The foam inhibitors, in particular silicone and/or paraffin-containing foam inhibitors, are preferably bound to a granular, water-soluble or water-dispersible carrier substance. Mixtures of paraffins and bis-stearylethylenediamide are particularly preferred.

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.%.

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 with 1 to 4 carbon atoms, in particular methanol, ethanol, isopropanol and tert-butanol, diols and triols with 2 to 4 carbon atoms, in particular ethylene glycol, propylene glycol and glycerin, as well as mixtures thereof and the ethers derivable from the above-mentioned classes of compounds. 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.

In a further preferred embodiment, the agent according to the invention is portioned ready for individual dosing in a chamber made of water-soluble material; 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 in which the product to be dosed is contained. A chamber is a space delimited by walls (for example by a film) which can also be filled without the product to be dosed (if necessary with changes in the its shape). A surface coating or a layer of a surface coating is therefore not a wall according to the present invention.

The walls of the chamber 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 pm) fixed in a square frame (edge length on the inside: 20 mm) according to the following measurement protocol. The framed film in question is immersed in 800 ml of distilled water tempered to 20 °C in a 1 liter beaker with a circular bottom surface (Schott, Mainz, beaker 1000 ml, low form) so that the surface of the clamped film is arranged at a right angle to the bottom surface of the beaker, the upper edge of the frame is 1 cm below the water surface and the lower edge of the frame is aligned parallel to the bottom surface of the beaker in such a way that the lower edge of the frame runs along the radius of the bottom surface of the beaker and the center of the lower edge of the frame is arranged above the center of the radius of the bottom of the beaker. The material dissolves within 600 seconds when stirred (magnetic stirrer speed 300 rpm, stirring rod: 5 cm long) to such an extent that no individual solid particles are visible to the naked eye.

The walls of the chambers and thus the water-soluble casings of the detergents according to the invention are preferably formed by a water-soluble film material. Such water-soluble packaging can be produced either by vertical form-fill-seal processes or by thermoforming processes.

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.

The water-soluble film material is preferably selected from polymers or polymer mixtures. The casing can be formed from one or from 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 coating contains polyvinyl alcohol or a polyvinyl alcohol copolymer; more preferably it consists of polyvinyl alcohol or polyvinyl alcohol copolymer. 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 from 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 in particular from 40,000 to 80,000 gmol ^-1 .

Polyvinyl alcohol is usually 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 in particular 82 to 88 mol%.

Polymers selected from the group comprising acrylic acid-containing polymers, polyacrylamides, oxazoline polymers, polystyrene sulfonates, polyurethanes, polyesters, polyethers, polylactic acid, and/or mixtures of the above polymers can additionally be added to a film material suitable for producing the water-soluble coating. The copolymerization of monomers underlying such polymers, individually or in mixtures of two or more, with vinyl acetate is also possible.

In addition to vinyl alcohol, preferred polyvinyl alcohol copolymers comprise an ethylenically unsaturated carboxylic acid, its salt or its ester. In addition to vinyl alcohol, such polyvinyl alcohol copolymers particularly preferably contain 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 are, for example, itaconic acid, maleic acid, fumaric acid and mixtures thereof, with itaconic acid being particularly preferred.

Suitable water-soluble films for use in the wrappers of the water-soluble packaging according to the invention are films sold by MonoSol LLC, for example under the designation M8630, C8400 or M8900. Other suitable films include films with the designation Solublon® PT, Solublon® GA, Solublon® KC or Solublon® KL from Aicello Chemical Europe GmbH or the VF-HP films from Kuraray.

The washing or cleaning agent portion, comprising the washing or cleaning agent and the water-soluble casing, can have one or more chambers. The water-soluble casings with a 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 casing.

In a preferred embodiment, the water-soluble casing has two chambers. In this embodiment, both chambers can each contain a solid partial composition or each contain a liquid partial composition, or the first chamber contains a liquid partial composition and the second chamber contains a solid partial composition.

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. Preferably, however, the agents in a water-soluble casing with at least two chambers have partial compositions that differ in at least one ingredient and/or in the content of at least one ingredient. Preferably, a partial composition of such agents according to the invention comprises enzyme and/or bleach activator and a separate further partial composition comprises peroxidic bleaching agent, in which case the first-mentioned partial composition in particular comprises no peroxidic bleaching agent and the second-mentioned partial composition in particular comprises no enzyme and no bleach activator.

By packaging the portions in a water-soluble coating, the user is able to put one or, if desired, several, preferably one, portions into the washing machine or dishwasher, in particular into the detergent compartment 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 adding water, the coating material dissolves so that the ingredients are released and can develop their effect in the bath. A water-soluble coated portion preferably weighs 10 g to 35 g, in particular 12 g to 28 g and particularly preferably 12 g to 15 g, with the proportion of the water-soluble coating included in the weight specification accounting for 0.3 g to 2.5 g, in particular 0.7 g to 1.2 g.

The production of solid agents 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. To produce agents with increased bulk density, in particular in the range from 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. examples

Example 1: Washing performance

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 given in Table 1 below (which had the weight ratio of the individual surfactants given in brackets) were used at 30 °C to wash cotton test fabrics with 9 different standardized oily soilings and the sum of the Y values across the 9 test fabrics was determined after drying. The values also given in Table 1 were the mean values of 3 tests. A clear superiority of the surfactant mixtures E1, E2 and E3 according to the invention is observed in comparison to another surfactant system commonly used in commercial detergents (V1; consisting of linear alkylbenzenesulfonate, Ci2/14 ether sulfate and a nonionic surfactant Ci2/18-7EO) and (V2) the mixture of rhamnolipid with only one surfactant of the general formula (Ha).

Table 1

Example 2: Phase behavior of microemulsions with n-decane at 30 °C

The amount of surfactants at the X-point is given in Table 2.

Table 2

Example 3 Diffusion coefficient

Table 3 shows the effective diffusion coefficients from dynamic surface tension measurements (maximum bubble pressure) at room temperature; the surfactant mixtures were used in amounts of 1 g/L each in citrate buffer at pH 8, and the effective diffusion coefficients were obtained by fitting the first data points with the Ward-Tordai equation.

Table 3: Diffusion coefficients

Example 4: Dynamic surface tension

In spinning drop tests with n-decane as oil against the citrate buffer at pH 8, each surfactant mixture given in Table 4 was measured for 1 hour at 6000 revolutions per minute. These data were fitted with the Rosen equation including the constants n and t*. t* is here is a measure of the rate of reduction of the interfacial tension, n is a scaling parameter for the slope.

Table 4: Fit constants n and t*

Claims

patent claims 1. Surfactant combination of a first alkyl polyglycol ether of the general formula (la) or (lb) with a second alkyl polyglycol ether of the general formula (Ha) or (llb) and with a rhamnolipid of the general formula (III) or its salt, CH ₃ (CH ₂ )m(-OR)n-OH (la)

in which R is a linear or branched alkyl group having 2 to 4 C atoms, in particular 2 C atoms, m is a number from 9 to 15, x and y independently of one another are numbers from 0 to 12, z is a number from 1 to 4, the sum of x + y + z being in the range from 10 to 16, n is a number from 1 to 5 and a is a number from 2 to 7, where a is at least 1 greater than n, o is 2, 1 or 0, p is 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. 2. Washing or cleaning agent containing a surfactant combination of a first alkyl polyglycol ether of the general formula (Ia) or (Ib) with a second alkyl polyglycol ether of the general formula (Ha) or (IIb) and with a rhamnolipid of the general formula (III) or its salt, CH ₃ (CH ₂ )m(-OR)n-OH (la)

in which R is a linear or branched alkyl group having 2 to 4 C atoms, in particular 2 C atoms, m is a number from 9 to 15, x and y independently of one another are numbers from 0 to 12, z is a number from 1 to 4, where the sum x + y + z is in the range from 10 to 16, n is a number from 1 to 5 and a is a number from 2 to 7, where a is at least 1 greater than n, o is 2, 1 or 0, p is 0 or 1, and R ¹ and R ² independently of one another are identical or different organic radicals having 2 to 24, in particular 5 to 13 carbon atoms. 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 builder, 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 portioned ready for individual dosing in a chamber made of water-soluble material and contains less than 15% by weight, in particular in the range of 1% by weight to 12% by weight, of water. 7. Use of a surfactant combination of a first alkylpolyglycol ether of the general formula (la) or (Ib) with a second alkylpolyglycol ether of the general formula (lla) or (llb) and with a rhamnolipid of the general formula (III) or its salt, CH ₃ (CH2)m(-OR)n-OH (la) (Ib) (Ha) (Hb)

in which R is a linear or branched alkyl group having 2 to 4 C atoms, in particular 2 C atoms, m is a number from 9 to 15, x and y independently of one another are numbers from 0 to 12, z is a number from 1 to 4, where the sum x + y + z is in the range from 10 to 16, n is a number from 1 to 5 and a is a number from 2 to 7, where a is at least 1 greater than n, o is 2, 1 or 0, p is 0 or 1, and R ¹ and R ² independently of one another are identical or different organic radicals having 2 to 24, in particular 5 to 13 carbon atoms, for increasing the performance of washing or cleaning agents when washing laundry or cleaning hard surfaces. 8. Use of a surfactant combination of a first alkylpolyglycol ether of the general formula (la) or (Ib) with a second alkylpolyglycol ether of the general formula (lla) or (I Ib) and with a rhamnolipid of the general formula (III) or its salt, CH ₃ (CH ₂ )m(-OR)n-OH (la)

CH ₃ (CH ₂ )m(-OR)a-OH (Ha)

in which R is a linear or branched alkyl group having 2 to 4 C atoms, in particular 2 C atoms, m is a number from 9 to 15, x and y independently of one another are numbers from 0 to 12, z is a number from 1 to 4, the sum of x + y + z being in the range from 10 to 16, n is a number from 1 to 5 and a is a number from 2 to 7, a being at least 1 greater than n, o is 2, 1 or 0, p is 0 or 1, and R ¹ and R ² independently of one another are identical or different organic radicals having 2 to 24, in particular 5 to 13 carbon atoms, for the production of washing or cleaning agents. 9. A method for washing laundry or cleaning hard surfaces, characterized in that a surfactant combination of a first alkyl polyglycol ether of the general formula (la) or (Ib) with a second alkyl polyglycol ether of the general formula (lla) or (llb) and with a rhamnolipid of the general formula (III) or its salt, CH ₃ (CH2)m(-OR)n-OH (la)

in which R is a linear or branched alkyl group having 2 to 4 C atoms, in particular 2 C atoms, m is a number from 9 to 15, x and y independently of one another are numbers from 0 to 12, z is a number from 1 to 4, where the sum x + y + z is in the range from 10 to 16, n is a number from 1 to 5 and a is a number from 2 to 7, where a is at least 1 greater than n, o is 2, 1 or 0, p is 0 or 1, and R ¹ and R ² independently of one another are identical or different organic radicals having 2 to 24, in particular 5 to 13 carbon atoms, or an agent containing them is used and it is carried 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 method 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) or the general formula (Ha) m is a number in the range from 11 to 15 and/or n is a number in the range from 2 to 4 and/or a is a number in the range from 4 to 7; and/or that the salts of the compounds of the general formula (III) are those in which the carboxyl H atom is replaced by an alkali metal cation or the grouping N ⁺ R ³ R ⁴ R ⁵ R ^e , in which R ³ , R ⁴ , R ⁵ and R ^e independently of one another represent hydrogen, an alkyl group having 1 to 6 C atoms or a hydroxyalkyl group having 2 to 6 C atoms, and the carboxylic acid group is present as a carboxylate anion.