EP3234085B1 - Detergents and cleaning agents - Google Patents

Description

The present invention relates to detergents and cleaners containing rhamnolipids and certain polymers.

Modern detergents, which are often used in liquid form, are often used at low temperatures down to room temperature or below. Above all, the surfactant system contained in them serves to remove, in particular, greasy stains. Typical surfactants used are petrochemically based linear alkylbenzenesulfonate, oleochemically or petrochemically based alcohol ether sulfate and petro- or oleochemically derived nonionic surfactants such as alcohol ethoxylates. It is challenging to develop a powerful detergent that contains ingredients based on alternative sources of raw materials and that has a performance spectrum that can compete with a detergent based on such conventional surfactant ingredients. For some years, biosurfactants, which can be obtained, for example, from sugar or other carbohydrate sources, are commercially available. However, the performance profile of biosurfactants in some cases does not readily meet the demands made of a modern detergent.

Rhamnolipids are compounds in which a mono- or dirhamnose unit is glycosidically linked to the hydroxyl group of a fatty acid containing β-hydroxyl groups, it being possible for the fatty acid to 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 in their growth on hydrophobic substrates such as n-alkanes or vegetable oils. Rhamnolipids belong to the so-called biosurfactants because of their surface-active behavior and their origin. The 3- (hydroxydecanoyloxy) decanedioirirrazine, for example, has the formula

From the patent EP 0 499 434 B1 detergents containing 1 to 60% by weight of a micellar phase forming surfactant at pH 7.0 and 25 ° C. in 1% strength by weight aqueous solution and a lamellar at pH 7.0 and 25 ° C. in 1% strength by weight aqueous solution are known Phase-forming surfactant, wherein rhamnolipid may be both the micellar phase and the lamellar phase forming surfactant. The European patent EP 1 445 302 B1 relates to laundry detergents containing at least one glycolipid biosurfactant and at least one non-glycolipid surfactant, which are in a micellar phase. From the international patent application WO 2012/010405 A1 detergents containing at least 1% by weight of biosurfactant and an enzyme of bacterial origin are known. The 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 glycolipid, of which glycolipids include, for example, sophorolipids, rhamnolipids, Glucoselipide, trehaloselipids and cellobioselipids. From the international patent application WO 2012/010406 A1 Detergents are known which contain lipase and rhamnolipid, the rhamnolipid consisting of at least 50% by weight of mono-rhamnolipid. From the international patent application WO 2012/010407 A1 detergents are known 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 detergents in which the weight ratio of monorhamnolipid to dirhamnolipid ranges from 95: 5 to 45:55. The European patent application EP 2 787 065 A1 discloses mono- and dirhamnolipid-containing laundry 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 Rhamnolipidmischungen are known which contain 51 wt .-% to 95 wt .-% of a certain Dirhamnolipids and 0.5 wt .-% to 9 wt .-% of a certain Monorhamnolipids in which the weight ratio of Dirhamnolipid to Monorhamnolipid greater than 91: 9 is.

Surprisingly, it has been found that rhamnolipids in combination with certain polymers lead to a washing performance which exceeds the expected from the sum of the performance of the individual components washing performance.

The invention therefore provides a washing or cleaning agent containing rhamnolipid and N-containing polymer according to claim 1.

A washing or cleaning agent preferably contains 0.01% by weight to 75% by weight, in particular 0.05% by weight to 35% by weight of rhamnolipid and 0.01% by weight to 50% by weight. , in particular 0.05 wt .-% to 30 wt .-% N-containing polymer.

Hydrous mixtures of rhamnolipid and N-containing polymer show a reduced relative to rhamnolipid cmc (critical micelle concentration) and reduced interfacial tension. Hydrous blends of rhamnolipid and N-free, polyester-based polymers, such as Texcare® SRN 170 or Texcare® SRA 300, show no interaction between the blend components. Without wishing to be bound by this theory, it is conceivable that the reduced interfacial tension below the rhamnolipid cmc in the mixtures essential to the invention therefore leads to an increase in the washing performance of an aqueous washing or cleaning liquor containing rhamnolipid and N-containing polymer, since then a better soil-carrying capacity , an improved stabilization of oil-in-water emulsions and a better absorption on hydrophobic stains is effected.

Further objects of the invention are therefore the use of N-containing polymer to increase the washing or cleaning performance of rhamnolipidhaltigen detergents or cleaners, and the use of combinations of rhamnolipid and N-containing polymer to increase the washing or cleaning performance of washing or cleaning detergents. The use according to the invention can be carried out, for example, by adding the N-containing polymer or its combination with rhamnolipid to a washing or cleaning agent-containing liquor or introducing it into the liquor as a constituent of a washing or cleaning agent, the use of the N-containing polymer alone requires the use of a rhamnolipidhaltigen detergent, and brings to washing or cleaning items in the fleet.

in der

• m für 0, 1 oder 2 steht,
• n für 0 oder 1 steht,
• R¹ und R² unabhängig voneinander für gleiche oder verschiedene Kohlenwasserstoffreste mit 2 bis 24, insbesondere 5 bis 13 C-Atomen stehen. Rhamnolipide sind üblicherweise keine Einzelverbindungen, sondern treten als Gemische verschiedener Verbindungen der allgemeinen Formel (I) auf.

The rhamnolipid preferably has the general formula (I)

in the

• m is 0, 1 or 2,
• n is 0 or 1,
• R ¹ and R ² independently of one another represent identical or different hydrocarbon radicals having 2 to 24, in particular 5 to 13, C atoms. Rhamnolipids are usually not individual compounds but occur as mixtures of various compounds of general formula (I).

The radicals R ¹ and R ² in the compounds of the formula (I) can be straight-chain or branched and can be saturated or mono- or polysubstituted, for example difunctional or trisubstituted, ethylenically unsaturated and / or optionally substituted, with hydroxy substituents being particularly preferred. Instead of the terminal carboxylic acid function, the compound of general formula (I) may also carry a carboxylate function; In this case, charge-balancing cations, especially sodium, potassium, ammonium, alkylammonium and / or hydroxyalkylammonium ions, are present. In one embodiment of the invention, the rhamnolipid is a mixture of monorhamnolipids and dirhamnolipids in which the weight ratio of dirhamnolipid to monorhamnolipid is greater than 51:49, preferably greater than 91: 9, preferably greater than 97: 3 and in particular greater than 98: 2 ,

The N-containing polymer is selected from the group consisting of alkoxylated polyamine and those produced by polymerization of N-vinylcaprolactam, N-vinylpyrrolidone, N-vinylimidazole, N-vinylpiperidone, N-vinylsuccinimide, N-vinylglutarimide, N-vinylacetamide, N-alkyl N-vinylacetamide, N-vinylformamide, N-alkyl-N-vinylformamide and / or mixtures of at least 2 of these monomers accessible polymers and mixtures thereof.

The polyalkoxylated polyamine is a polymer having an N-atom containing backbone bearing polyalkoxy groups on the N atoms. The polyamine has primary ends Aminofunktionen and inside preferably both secondary and tertiary amino functions on; if appropriate, it may also have only secondary amino functions on the inside, so that the result is not a branched-chain but a linear polyamine. The ratio of primary to secondary amino groups in the polyamine is preferably in the range from 1: 0.5 to 1: 1.5, in particular in the range from 1: 0.7 to 1: 1. The ratio of primary to tertiary amino groups in the polyamine is preferably in the range from 1: 0.2 to 1: 1, in particular in the range from 1: 0.5 to 1: 0.8. Preferably, the polyamine has an average molecular weight in the range of 500 g / mol to 50,000 g / mol, in particular from 550 g / mol to 2000 g / mol. The average molar masses given here are weight-average molar masses M _w , which can in principle be determined by means of gel permeation chromatography with the aid of an RI detector, the measurement being expediently carried out against an external standard. The N atoms in the polyamine are preferably separated from one another by alkylene groups having 2 to 12 C atoms, in particular 2 to 6 C atoms, wherein not all alkylene groups must have the same C atom number. Particularly preferred are ethylene groups, 1,2-propylene groups, 1,3-propylene groups, and mixtures thereof. The primary amino functions in the polyamine can carry 1 or 2 polyalkoxy groups and the secondary amino functions 1 polyalkoxy group, although not every amino function must be alkoxy group substituted. The average number of alkoxy groups per primary and secondary amino function in the polyalkoxylated polyamine is preferably 5 to 100, in particular 10 to 50. The alkoxy groups in the polyalkoxylated polyamine are preferably ethoxy, propoxy or butoxy groups or mixtures thereof. The polyalkoxylated polyamines are accessible by reacting the polyamines with the epoxides corresponding to the alkoxy groups. If desired, the terminal OH function of at least some of the polyalkoxy substituents can be replaced by an alkyl ether function having 1 to 10, in particular 1 to 3, C atoms.

Copolymers composed of N-vinylcaprolactam and another of the mentioned ethylenically unsaturated monomers, in particular N-vinylpyrrolidone, or of N-vinylpyrrolidone and N-vinylimidazole are particularly preferred. The N-vinylcaprolactam polymers or copolymers which can be used according to the invention are preferably not crosslinked. If the polymers are copolymers obtainable from 2 ethylenically unsaturated monomers, they have the two monomers, one of which is preferably N-vinylcaprolactam, preferably in a weight ratio of from 99: 1 to 1:99, in particular from 97: 3 to 50 : 50 and most preferably from 95: 5 to 70:30, wherein in N-vinylcaprolactam-containing copolymers, this is preferably present in deficit.

The N-containing polymeric active ingredient preferably has an average molecular weight (here: number average) in the range of 1000 g / mol to 500000 g / mol, in particular from 1100 g / mol to 150000 g / mol.

Detergents and cleaners, which may be in the form of homogeneous solutions or suspensions in particular as pulverulent solids, in densified particle form, may contain, in addition to rhamnolipid and N-containing polymer, all known ingredients customary in such agents. The agents may in particular be builders, surfactants, water-miscible organic solvents, enzymes, sequestering agents, electrolytes, pH regulators, special effect polymers such as soil release polymers, dye transfer inhibitors, grayness inhibitors, wrinkle reducing and formaldehyde polymeric actives, and other adjuvants such as optical brighteners , Foam regulators, dyes and fragrances. The polymers present in addition to the N-containing polymers which are essential to the invention are preferably used in amounts of up to 10% by weight, in particular from 1 to 5% by weight.

The agents may contain one or more surfactants, in particular anionic surfactants, nonionic surfactants and mixtures thereof, but also cationic and / or amphoteric surfactants may be included.

As nonionic surfactants, it is possible to use all nonionic surfactants known to the person skilled in the art. The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as they are usually present in Oxoalkoholresten. In particular, however, alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 moles of EO per mole of alcohol are preferred. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 EO or 4 EO, C _9-11 alcohols with 7 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C _12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C _12-14 -alcohol with 3 EO and C _12-18 -alcohol with 5 EO. The stated degrees of ethoxylation represent statistical averages, which may correspond to a particular product of an integer or a fractional number. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).

Alternatively or in addition to these nonionic surfactants, it is also possible to use fatty alcohols with more than 12 EO. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO. In addition, other nonionic surfactants which can also be employed are alkylglycosides of the general formula R ⁵ O (G) _x , in which R ^{5 is} a primary straight-chain or methyl-branched, especially methyl-branched, 2-position aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms. Corresponds to atoms and G is the symbol which represents a glycose unit having 5 or 6 C atoms, preferably glucose. The degree of oligomerization x, which determines the distribution of Specifying monoglycosides and oligoglycosides is any number between 1 and 10; preferably x is 1.2 to 1.4.

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

Nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides 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 C_1-4-Alkyl- 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.Further suitable surfactants are polyhydroxy fatty acid amides of the formula

wherein 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. The polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride. The group of polyhydroxy fatty acid amides also includes compounds of the formula

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] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated Derivatives of this residue. [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 catalyst.

As anionic surfactants, for example, those of the sulfonate type and sulfates are used. Preferred surfactants of the sulfonate type are C _9-13 -alkylbenzenesulfonates, olefinsulfonates, that is to say mixtures of alkene and hydroxyalkanesulfonates and also disulfonates, as are obtained, for example, from C _12-18 -monoolefins having terminal or internal double bonds by sulfonation with gaseous Sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation obtained. Also suitable are alkanesulfonates which are obtained from C _12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. Likewise suitable are the esters of α-sulfo fatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.

Further suitable anionic surfactants are sulfated fatty acid glycerol esters. Fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and mixtures thereof, as obtained in the preparation by esterification of glycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol. Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.

Further suitable anionic surfactants are alkyl sulfates and ether sulfates. By an alkyl sulfate is meant a salt of a sulfuric acid half-ester of an alcohol having a linear, branched or cyclic saturated hydrocarbon radical of 10 to 22 carbon atoms. For charge neutralization of the sulfuric acid half-ester, a counter cation is present, in particular a sodium or potassium ion or an ammonium, alkylammonium or hydroxyalkylammonium ion. Preferred alcohol radicals are derived from native C ₁₂ -C ₁₈ fatty alcohols, such as coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or the C ₁₀ -C ₂₀ oxo alcohols or secondary alcohols of these chain lengths. Also preferred are alkyl sulfates of said chain length, which contain a synthetic, straight-chain alkyl radical produced on a petrochemical basis, which have an analogous degradation behavior as the adequate compounds based on oleochemical raw materials. C ₁₂ -C ₁₆ -alkyl sulfates, C ₁₂ -C ₁₅ -alkyl sulfates and C ₁₄ -C ₁₅ -alkyl sulfates are particularly preferred. Ether sulfates are analogous to the alkyl sulfates of sulfuric monoesters of alkoxylated alcohols, the average number of alkoxy groups per alcohol function being generally from 1 to 10, preferably from 3 to 7. Preferred alkoxy groups are the ethoxy group, the propoxy group and mixtures thereof. Also the Sulfuric acid monoesters of ethoxylated with 1 to 6 moles of ethylene oxide straight-chain or branched C _7-21 alcohols, such as 2-methyl-branched C _9-11 alcohols having an average of 3.5 moles of ethylene oxide (EO) or C _12-18 fatty alcohols 1 to 4 EO, are suitable.

Further suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contain C _8-18 fatty alcohol residues or mixtures of these. Particularly preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty alcohols, which by themselves are nonionic surfactants. Sulfosuccinates, whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are again particularly preferred. Likewise, it is also possible to use alk (en) ylsuccinic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.

As further anionic surfactants are particularly soaps into consideration. 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, and in particular of natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.

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

Instead of the surfactants mentioned or in conjunction with them, it is also possible to use cationic and / or amphoteric surfactants.

worin jede Gruppe R¹ unabhängig voneinander ausgewählt ist aus C_1-6-Alkyl-, -Alkenyl- oder -Hydroxyalkylgruppen; jede Gruppe R² unabhängig voneinander ausgewählt ist aus C_8-28-Alkyl- oder -Alkenylgruppen; R³ = R¹ oder (CH₂)_n-T-R²; R⁴ = R¹ oder R² oder (CH₂)_n-T-R²; T = -CH₂-, -O-CO- oder -CO-O- und n eine ganze Zahl von 0 bis 5 ist.As cationic active substances, for example, cationic compounds of the following formulas can be used:

wherein each R ^{1 group is} independently selected from C _1-6 alkyl, alkenyl or hydroxyalkyl groups; each R ^{2 group is} independently selected from C _8-28 alkyl or alkenyl groups; R ³ = R ¹ or (CH ₂ ) _n -TR ² ; R ⁴ = R ¹ or R ² or (CH ₂ ) _n -TR ² ; T = -CH ₂ -, -O-CO- or -CO-O- and n is an integer from 0 to 5.

Such surfactants which can be used in addition to rhamnolipid are present in agents according to the invention in amounts of preferably from 5% by weight to 50% by weight, in particular from 10% by weight to 30% by weight, but may also be completely absent if desired.

Textile softening compounds can be used to care for the textiles and to improve the textile properties such as a softer "touch" (avivage) and reduced electrostatic charge (increased wearing comfort). The active ingredients of these formulations are quaternary ammonium compounds having two hydrophobic groups, such as the Disteraryldimethylammoniumchlorid, but which is increasingly replaced because of its insufficient biodegradability by quaternary ammonium compounds containing ester groups in their hydrophobic residues as predetermined breaking points for biodegradation.

Such "esterquats" with improved biodegradability are obtainable, for example, by esterifying mixtures of methyldiethanolamine and / or triethanolamine with fatty acids and then quaternizing the reaction products in a manner known per se with alkylating agents. Suitable as a finishing agent is dimethylolethyleneurea.

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 methylglycinediacetic acid, nitrilotriacetic acid and ethylenediaminetetraacetic acid and polyaspartic acid, polyphosphonic acids, in particular aminotris (methylenephosphonic acid), ethylenediaminetetrakis (methylenephosphonic acid) and 1-hydroxyethane-1,1-diphosphonic acid, polymeric hydroxy compounds such as dextrin and polymeric (poly) carboxylic acids, especially by oxidation of polysaccharides or dextrins accessible polycarboxylates, and / or polymeric acrylic acids, methacrylic acids, maleic acids and copolymers thereof, which also small Particles of polymerizable substances without carboxylic acid functionality may contain polymerized. The molecular weight of the homopolymers of unsaturated carboxylic acids is generally between 5,000 and 200,000, of the copolymers between 2,000 and 200,000, preferably 50,000 to 120,000, each based on the free acid. A particularly preferred acrylic acid-maleic acid copolymer has a molecular weight of 50,000 to 100,000. Suitable, although less preferred, compounds of this class are copolymers of acrylic or methacrylic acid with vinyl ethers, such as vinylmethyl ethers, vinyl esters, ethylene, propylene and styrene, in which the acid content is at least 50% by weight. It is also possible to use terpolymers which contain two unsaturated acids and / or salts thereof as monomers and also vinyl alcohol and / or an esterified vinyl alcohol or a carbohydrate as the third monomer as water-soluble organic builder substances. The first acidic monomer or its salt is derived from a monoethylenically unsaturated C ₃ -C ₈ -carboxylic acid and preferably from a C ₃ -C ₄ -monocarboxylic acid, in particular from (meth) -acrylic acid. The second acidic monomer or its salt may be a derivative of a C ₄ -C ₈ -dicarboxylic acid, with maleic acid being particularly preferred, and / or a derivative of an allylsulfonic acid which is substituted in the 2-position by an alkyl or aryl radical. Such polymers generally have a molecular weight between 1,000 and 200,000. Further preferred copolymers are those which have as monomers acrolein and acrylic acid / acrylic acid salts or vinyl acetate. The organic builder substances can be used, in particular for the preparation 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, in particular their alkali metal salts.

If desired, such organic builder substances may 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. Quantities in the upper half of said ranges are preferably used in pasty or liquid, in particular water-containing agents.

Suitable water-soluble inorganic builder materials are, in particular, polymeric alkali metal phosphates, which may be in the form of their alkaline neutral or acidic sodium or potassium salts. Examples of these are tetrasodium diphosphate, disodium dihydrogen diphosphate, pentasodium triphosphate, so-called sodium hexametaphosphate and the corresponding potassium salts or mixtures of sodium and potassium salts. As water-insoluble, water-dispersible inorganic builder materials are in particular crystalline or amorphous Alkalialumosilikate, in amounts of up to 50 wt .-%, preferably not more than 40 wt .-% and in liquid agents, in particular from 1 wt .-% to 5 wt .-%, used. Among these, preferred are the detergent grade crystalline sodium aluminosilicates, especially zeolite A, P and optionally X. Amounts near the above upper limit are preferably used in solid, particulate agents. In particular, suitable aluminosilicates have no particles with a particle size greater than 30 .mu.m and preferably consist of at least 80% by weight of particles having a size of less than 10 .mu.m. Their calcium binding capacity is generally in the range of 100 mg to 200 mg CaO per gram.

Suitable substitutes or partial substitutes for the said aluminosilicate are crystalline alkali silicates which may be present alone or in a mixture with amorphous silicates. The alkali metal silicates useful as builders preferably have a molar ratio of alkali metal oxide to SiO ₂ below 0.95, in particular from 1: 1.1 to 1:12, and may be present in amorphous or crystalline form. Preferred alkali metal silicates are the sodium silicates, in particular the amorphous sodium silicates, with a molar ratio of Na ₂ O: SiO ₂ of 1: 2 to 1: 2.8. The crystalline silicates which may be present alone or in admixture with amorphous silicates, are crystalline layer silicates with the general formula Na ₂ Si _x O _{2x + 1} · are used yH ₂ O, in which x, the so-called module, 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 phyllosilicates are those in which x in the abovementioned general formula assumes the values 2 or 3. In particular, both β- and δ-Natriumdisitikate (Na ₂ Si ₂ O ₅ · y H ₂ O) is preferred. Also prepared from amorphous alkali metal silicates, practically anhydrous crystalline alkali metal silicates of the abovementioned general formula in which x is a number from 1.9 to 2.1, can be used. In a further preferred embodiment, a crystalline sodium layer silicate with a modulus of 2 to 3 is used, as can be prepared from sand and soda. Crystalline sodium silicates with a modulus in the range 1.9 to 3.5 are used in a further preferred embodiment. In a preferred embodiment, a granular compound of alkali metal silicate and alkali metal carbonate is used, as it is commercially available, for example, under the name Nabion® 15. If alkali metal aluminosilicate, in particular zeolite, is also present as an additional builder substance, the weight ratio of aluminosilicate to silicate, based in each case on anhydrous active substances, is preferably 1:10 to 10: 1. In agents containing both amorphous and crystalline alkali metal silicates, the weight ratio of amorphous alkali metal silicate to crystalline alkali metal silicate is preferably 1: 2 to 2: 1 and especially 1: 1 to 2: 1.

Builder substances are preferably contained in detergents in amounts of up to 60% by weight, in particular from 5% by weight to 40% by weight.

1. a) 5 Gew.-% bis 35 Gew.-% Citronensäure, Alkalicitrat und/oder Alkalicarbonat, welches auch zumindest anteilig durch Alkalihydrogencarbonat ersetzt sein kann,
2. b) bis zu 10 Gew.-% Alkalisilikat mit einem Modul im Bereich von 1,8 bis 2,5,
3. c) bis zu 2 Gew.-% Phosphonsäure und/oder Alkaliphosphonat,
4. d) bis zu 50 Gew.-% Alkaliphosphat, und
5. e) bis zu 10 Gew.-% polymerem Polycarboxylat,

wobei die Mengenangaben sich auf das gesamte Waschmittel beziehen. Dies gilt auch für alle folgenden Mengenangaben, sofern nicht ausdrücklich anders angegeben.In a preferred embodiment, the agent comprises a water-soluble builder block. By using the term "builder block" it is intended to express that the agents contain no further builder substances than those which are water-soluble, that is to say all in the builder contained in the composition are summarized in the so-characterized "block", which at most the amounts of substances are excluded, which may be contained as impurities or stabilizing additives in small amounts in the remaining ingredients of the means commercially available manner. The term "water-soluble" is to be understood as meaning that the builder block dissolves without leaving a residue at the concentration which results from the use amount of the agent containing it in the customary conditions. Preferably, at least 15% by weight and up to 55% by weight, in particular 25% by weight to 50% by weight, of water-soluble builder block are contained in the compositions. This is preferably composed of the components

1. a) 5% by weight to 35% by weight of citric acid, alkali citrate and / or alkali metal carbonate, which may also be replaced at least proportionally by alkali metal bicarbonate,
2. b) up to 10% by weight of alkali silicate having a modulus in the range of 1.8 to 2.5,
3. c) up to 2% by weight of phosphonic acid and / or alkali phosphonate,
4. d) up to 50% by weight of alkali metal phosphate, and
5. e) up to 10% by weight of polymeric polycarboxylate,

wherein the quantities are based on the total detergent. This also applies to all following quantities, unless expressly stated otherwise.

In a preferred embodiment, the water-soluble builder block contains at least 2 of the components b), c), d) and e) in amounts greater than 0 wt .-%.

With regard to component a), in a preferred embodiment, 15% by weight to 25% by weight of alkali carbonate, which may be replaced at least proportionally by alkali metal bicarbonate, and up to 5% by weight, in particular 0.5% by weight, bis 2.5% by weight of citric acid and / or alkali citrate. In an alternative embodiment, as component a) 5 wt .-% to 25 wt .-%, in particular 5 wt .-% to 15 wt .-% citric acid and / or alkali citrate and up to 5 wt .-%, in particular 1 wt .-% to 5 wt .-% alkali carbonate, which may be at least partially replaced by alkali metal bicarbonate included. If both alkali metal carbonate and alkali metal bicarbonate are present, the component a) alkali carbonate and alkali metal bicarbonate preferably in a weight ratio of 10: 1 to 1: 1.

With regard to component b), in a preferred embodiment, 1 wt .-% to 5 wt .-% alkali silicate with a modulus in the range of 1.8 to 2.5 are included.

With regard to component c), in a preferred embodiment, from 0.05% by weight to 1% by weight of phosphonic acid and / or alkali metal phosphonate is contained. Phosphonic acids are also understood as meaning optionally substituted alkylphosphonic acids, which may also have a plurality of phosphonic acid groups (so-called polyphosphonic acids). They are preferably selected from the hydroxy and / or aminoalkylphosphonic acids and / or their Alkali metal salts, such as dimethylaminomethane diphosphonic acid, 3-aminopropane-1-hydroxy-1,1-diphosphonic acid, 1-amino-1-phenylmethane diphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid, amino tris (methylenephosphonic acid), N, N, N ', N'-ethylenediamine tetrakis (methylenephosphonic acid) and acylated derivatives of phosphorous acid, which can also be used in any mixtures.

With regard to component d), in a preferred embodiment, 15% by weight to 35% by weight of alkali metal phosphate, in particular trisodium polyphosphate, is contained. Alkali phosphate is the summary term for the alkali metal (especially sodium and potassium) salts of the various phosphoric acids, in which one can distinguish metaphosphoric acids (HPO ₃ ) _n and orthophosphoric H ₃ PO _{4 in} addition to high molecular weight representatives. The phosphates combine several advantages: they act as alkali carriers, prevent lime deposits on machine parts or lime incrustations in fabrics and also contribute to the cleaning performance. Sodium dihydrogen phosphate, NaH ₂ PO ₄ , exists as a dihydrate (density 1.91 gcm ^-3 , melting point 60 °) and as a monohydrate (density 2.04 gcm ^-3 ). Both salts are white powders which are very soluble in water and which lose their water of crystallization when heated and at 200 ° C into the weak acid diphosphate (disodium hydrogen diphosphate, Na ₂ H ₂ P ₂ O ₇ ), at higher temperature in sodium trimetaphosphate (Na ₃ P ₃ O ₉ ) and pass on Madrell's salt. NaH ₂ PO _{4 is} acidic; It arises when phosphoric acid is adjusted to a pH of 4.5 with sodium hydroxide solution and the mash is sprayed. Potassium dihydrogen phosphate (potassium phosphate primary or monobasic potassium, potassium biphosphate, KDP), KH ₂ PO ₄ , is a white salt of density 2.33 gcm ^-3 , has a melting point of 253 ° (decomposition to form (KPO ₃ ) _x , potassium polyphosphate) and is slightly soluble in water. Disodium hydrogen phosphate (secondary sodium phosphate), Na ₂ HPO ₄ , is a colorless, very slightly water-soluble crystalline salt. It exists anhydrous and with 2 moles (density 2.066 gcm ^-3 , water loss at 95 °), 7 moles (density 1.68 gcm ^-3 , melting point 48 ° with loss of 5 H ₂ O) and 12 moles of water (density 1, 52 gcm ^-3 , melting point 35 ° with loss of 5 H ₂ O), becomes anhydrous at 100 ° C. and, on vigorous heating, passes into the diphosphate Na ₄ P ₂ O ₇ . Disodium hydrogen phosphate is prepared by neutralization of phosphoric acid with soda solution using phenolphthalein as an indicator. Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K ₂ HPO ₄ , is an amorphous, white salt that is readily soluble in water. Trisodium phosphate, tertiary sodium phosphate, Na ₃ PO ₄ , are colorless crystals which have a density of 1.62 gcm ^-3 as dodecahydrate and a melting point of 73-76 ° C (decomposition), as decahydrate (corresponding to 19-20% P ₂ O ₅ ) have a melting point of 100 ° C and in anhydrous form (corresponding to 39-40% P ₂ O ₅ ) have a density of 2.536 gcm ^-3 . Trisodium phosphate is readily soluble in water under alkaline reaction and is prepared by evaporating a solution of exactly 1 mole of disodium phosphate and 1 mole of NaOH. Tripotassium phosphate (tertiary or tribasic potassium phosphate), K ₃ PO ₄ , is a white, deliquescent, granular powder of density 2.56 gcm ^-3 , has a melting point of 1340 ° and is readily soluble in water with an alkaline reaction. It arises, for example, when heating Thomasschlacke with coal and potassium sulfate. Despite the higher The more soluble, therefore highly effective, potassium phosphates are often preferred over corresponding sodium compounds. Tetrasodium diphosphate (sodium pyrophosphate), Na ₄ P ₂ O ₇ , exists in anhydrous form (density 2.534 gcm ^-3 , melting point 988 °, also indicated 880 °) and as decahydrate (density 1.815-1.836 gcm ^-3 , melting point 94 ° with loss of water) , For substances are colorless, in water with alkaline reaction soluble crystals. Na ₄ P ₂ O ₇ is formed on heating of disodium phosphate to> 200 ° or by reacting phosphoric acid with soda in a stoichiometric ratio and dewatering the solution by spraying. The decahydrate complexes heavy metal salts and hardness agents and therefore reduces the hardness of the water. Potassium diphosphate (potassium pyrophosphate), K ₄ P ₂ O ₇ , exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33 gcm ^-3 , which is soluble in water, the pH being 1% Solution at 25 ° 10.4. Condensation of the NaH ₂ PO ₄ or the KH ₂ PO ₄ results in higher molecular weight sodium and potassium phosphates, in which one can distinguish cyclic representatives, the sodium or potassium metaphosphates and chain types, the sodium or potassium polyphosphates. In particular, for the latter are a variety of names in use: melting or annealing phosphates, Graham's salt, Kurrolsches and Madrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates. The technically important pentasodium triphosphate, Na ₅ P ₃ O ₁₀ (sodium tripolyphosphate), is an anhydrous or with 6 H ₂ O crystallizing, non-hygroscopic, white, water-soluble salt of the general formula NaO- [P (O) (ONa) -O] _n -Na with n = 3. In 100 g of water dissolve at room temperature about 17 g, at 60 ° about 20 g, at 100 ° around 32 g of the salt water-free salt; after two hours of heating the solution to 100 ° caused by hydrolysis about 8% orthophosphate and 15% diphosphate. In the preparation of pentasodium triphosphate, phosphoric acid is reacted with soda solution or sodium hydroxide solution in a stoichiometric ratio and the solution. drained by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentakaliumtriphosphat, K ₅ P ₃ O ₁₀ (potassium tripolyphosphate), for example, in the form of a 50 wt .-% solution (> 23% P ₂ O ₅ , 25% K ₂ O) in the trade. There are also sodium potassium tripolyphosphates which can also be used in the context of the present invention. These arise, for example, when hydrolyzed sodium trimetaphosphate with KOH:

(NaPO ₃ ) ₃ + 2 KOH → Na ₃ K ₂ P ₃ O ₁₀ + H ₂ O

These are just like sodium tripolyphosphate, potassium tripolyphosphate or mixtures of these two applicable; It is also possible to use mixtures of sodium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of potassium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of sodium tripolyphosphate and potassium tripolyphosphate and sodium potassium tripolyphosphate.

With regard to component e), in a preferred embodiment, the composition contains 1.5% by weight to 5% by weight of polymeric polycarboxylate, in particular selected from the polymerization or copolymerization products of acrylic acid, methacrylic acid and / or maleic acid. Among these, particularly preferred are the homopolymers of acrylic acid and, among these, those having an average molecular weight in the range from 5,000 D to 15,000 D (PA standard).

Suitable enzymes which can be used in the compositions are those from the class of lipases, cutinases, amylases, pullulanases, mannanases, cellulases, hemicellulases, xylanases and peroxidases and mixtures thereof, for example amylases such as Termamyl®, Amylase-LT®, Maxamyl®, Duramyl ® and / or Purafect® OxAm, lipases such as Lipolase®, Lipomax®, Lumafast®, Lipozym® and / or Lipex®, cellulases such as Celluzyme® and / or Carezyme®. Particularly suitable are from fungi or bacteria, such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus, Humicola lanuginosa, Humicola insolens, Pseudomonas pseudoalcaligenes or Pseudomonas cepacia derived enzymatic agents. The optionally used enzymes may be adsorbed to carriers and / or embedded in encapsulants to protect against premature inactivation. They are preferably present in the compositions in amounts of up to 5% by weight, in particular from 0.5% by weight to 2% by weight.

A preferred solvent in liquid agents of the invention is water. Among the organic solvents which can be used in the compositions, in particular if they are in liquid or pasty form, are alcohols having 1 to 4 C atoms, in particular methanol, ethanol, isopropanol and tert-butanol, diols having 2 to 4 C atoms, in particular ethylene glycol and propylene glycol, and mixtures thereof and the derivable from said classes of compounds ethers. Water-miscible solvents are preferably present in the compositions in amounts of from 1% to 60% by weight, especially from 2% to 40% by weight. If desired, water may be present in liquid agents according to the invention in amounts of up to 94% by weight. In preferred embodiments of low-water agents, the water content is not more than 15 wt .-%, in particular 1 wt .-% to 8 wt .-%.

Naturally derived polymers which can be used as thickening agents in aqueous liquid agents include agar-agar, carrageenan, tragacanth, gum arabic, alginates, pectins, polyoses, guar flour, locust bean gum, starch, dextrins, gelatin and casein. Cellulose derivatives such as carboxymethyl cellulose, hydroxyethyl and propyl cellulose, and polymeric polysaccharide thickeners such as xanthan; In addition, fully synthetic polymers such as polyacrylic and polymethacrylic compounds, vinyl polymers, polycarboxylic acids, polyethers, polyimines, polyamides and polyurethanes are also suitable as thickeners.

To establish a desired, by the mixture of the other components not automatically resulting pH, the agents can system and environmentally acceptable 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 metal hydroxides. Such pH regulators are preferably contained in the compositions not more than 20% by weight, in particular from 1.2% by weight to 17% by weight.

Soil release polymers, often referred to as "soil release" agents or because of their ability to impart soil repellency to the treated surface, for example fiber, are, for example, nonionic or cationic cellulose derivatives. The particularly polyester-active soil release polymers include copolyesters of dicarboxylic acids, for example adipic acid, phthalic acid or terephthalic acid, diols, for example ethylene glycol or propylene glycol, and polydiols, for example polyethylene glycol or polypropylene glycol. Preferred soil release polymers include those compounds which are formally accessible by esterification of two monomeric moieties, wherein the first monomer is a dicarboxylic acid HOOC-Ph-COOH and the second monomer is a diol HO- (CHR ¹¹ -) _a OH, also known as polymeric Diol H- (O- (CHR ¹¹ -) _a ) _b OH may be present. Therein, Ph is an o-, m- or p-phenylene radical which can carry 1 to 4 substituents selected from alkyl radicals having 1 to 22 C atoms, sulfonic acid groups, carboxyl groups and mixtures thereof, R ¹¹ denotes hydrogen, an alkyl radical having 1 to 22 C atoms and mixtures thereof, a is a number from 2 to 6 and b is a number from 1 to 300. Preferably, in the polyesters obtainable from these, both monomer diol units -O- (CHR ¹¹ -) _a O- and also polymeric diol units - ( O- (CHR ¹¹ -) _a ) _b O-. The molar ratio of monomer diol units to polymer diol units is preferably 100: 1 to 1: 100, in particular 10: 1 to 1:10. In the polymer diol units, the degree of polymerization b is preferably in the range of 4 to 200, especially 12 to 140. The molecular weight or the average molecular weight or the maximum molecular weight distribution of preferred soil release polyester is in the range of 250 to 100,000, especially 500 to 50,000 The acid underlying the radical Ph is preferably selected from terephthalic acid, isophthalic acid, phthalic acid, trimellitic acid, mellitic acid, the isomers of sulfophthalic acid, sulfoisophthalic acid and sulfoterephthalic acid and mixtures thereof. If their acid groups are not part of the ester bonds in the polymer, they are preferably in salt form, in particular as alkali or ammonium salt. Among these, the sodium and potassium salts are particularly preferable. If desired, in place of the monomer HOOC-Ph-COOH small proportions, in particular not more than 10 mol% based on the proportion of Ph having the meaning given above, of other acids having at least two carboxyl groups may be included in the soil release-capable polyester. These include, for example, alkylene and alkenylene dicarboxylic acids such as malonic acid, succinic acid, fumaric acid, maleic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid. The preferred diols HO- (CHR ¹¹ -) _a OH include those in which R ^{11 is} hydrogen and a is a number from 2 to 6, and those in which a is 2 and R ¹¹ is hydrogen and the alkyl radicals 1 to 10, in particular 1 to 3 C-atoms is selected. Among the latter diols, those of the formula HO-CH ₂ -CHR ¹¹ -OH in which R ^{11 has} the abovementioned meaning are particularly preferred. Examples of diol components are ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,2-decanediol, 1, 2-dodecanediol and neopentyl glycol. Particularly preferred among the polymeric diols is polyethylene glycol having an average molecular weight in the range of 1000 to 6000. If desired, these polyesters may also be endgruppenverschlossen, with alkyl groups having 1 to 22 carbon atoms and esters of monocarboxylic acids in question as end groups. The ester groups bonded via end groups can be based on alkyl, alkenyl and aryl monocarboxylic acids having 5 to 32 carbon atoms, in particular 5 to 18 carbon atoms. These include valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, undecenoic acid, lauric acid, lauroleinic acid, tridecanoic acid, myristic acid, myristoleic acid, pentadecanoic acid, palmitic acid, stearic acid, petroselinic acid, petroselaidic acid, oleic acid, linoleic acid, linolaidic acid, linolenic acid, levostearic acid, arachidic acid , Gadoleic acid, arachidonic acid, behenic acid, erucic acid, brassidic acid, clupanodonic acid, lignoceric acid, cerotic acid, melissic acid, benzoic acid, which may carry 1 to 5 substituents having a total of up to 25 carbon atoms, in particular 1 to 12 carbon atoms, for example tert-butylbenzoic acid , The end groups may also be based on hydroxymonocarboxylic acids having from 5 to 22 carbon atoms, including, for example, hydroxyvaleric acid, hydroxycaproic acid, ricinoleic acid, the hydrogenation product of which include hydroxystearic acid and also o-, m- and p-hydroxybenzoic acid. The hydroxymonocarboxylic acids may in turn be linked to one another via their hydroxyl group and their carboxyl group and thus be present several times in an end group. Preferably, the number of hydroxymonocarboxylic acid units per end group, that is to say their degree of oligomerization, is in the range from 1 to 50, in particular from 1 to 10. In a preferred embodiment of the invention, polymers of ethylene terephthalate and polyethylene oxide terephthalate in which the polyethylene glycol units have molecular weights of 750 to 5,000 and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate is 50:50 to 90:10, used alone or in combination with cellulose derivatives.

The agents may contain anti-crease agents, since textile fabrics, in particular of rayon, wool, cotton and their mixtures, can tend to wrinkle, because the individual fibers are sensitive to bending, buckling, pressing and squeezing transverse to the fiber direction. These include, for example, synthetic products based on fatty acids, fatty acid esters, fatty acid amides, alkylol esters, -alkylolamides or fatty alcohols, which are usually reacted with ethylene oxide, or products based on lecithin or modified phosphoric acid ester.

Graying inhibitors have the task of keeping suspended from the hard surface and in particular from the textile fiber suspended dirt in the fleet. Water-soluble colloids of mostly organic nature are suitable for this purpose, for example starch, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or of cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Also, water-soluble polyamides containing acidic groups are suitable for this purpose. Furthermore, other than the above-mentioned starch derivatives can be used, for example aldehyde starches. Preference is given to using cellulose ethers, such as carboxymethylcellulose (Na salt), methylcellulose, hydroxyalkylcellulose and mixed ethers, such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof, for example in amounts of from 0.1 to 5% by weight, based on the compositions.

The agents may contain optical brighteners, among these in particular derivatives of diaminostilbenedisulfonic acid or their alkali metal salts. Suitable salts are, for example, salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulphonic acid or compounds of similar construction which, instead of the morpholino Group carry a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group. Further, brighteners of the substituted diphenylstyrene 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). Mixtures of the aforementioned optical brightener can be used.

In particular when used in automatic washing processes, it may be advantageous to add conventional foam inhibitors to the compositions. As foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of C ₁₈ -C ₂₄ fatty acids. Suitable non-surfactant foam inhibitors are, for example, organopolysiloxanes and mixtures thereof with microfine, optionally silanized silica and paraffins, waxes, microcrystalline waxes and mixtures thereof with silanated silicic acid or bis-fatty acid alkylenediamides. It is also advantageous to use mixtures of various foam inhibitors, for example those of 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 dispersible carrier substance. In particular, mixtures of paraffins and bistearylethylenediamide are preferred.

As in the means, in particular the agents in solid form, optionally contained peroxygen compounds come in particular organic peracids or pers acid salts of organic acids such as phthalimidopercaproic acid, perbenzoic acid or salts of diperdodecanedioic acid, hydrogen peroxide and under the washing conditions hydrogen peroxide-releasing inorganic salts such as perborate, percarbonate and / or persilicate, into consideration. hydrogen peroxide It can also be produced by means of an enzymatic system, that is to say 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 enveloped in a manner known in principle. Particular preference is given to using alkali metal percarbonate, alkali metal perborate monohydrate, alkali metal perborate tetrahydrate or, in particular in liquid media, hydrogen peroxide in the form of aqueous solutions which contain from 3% by weight to 10% by weight of hydrogen peroxide. Preferably, peroxygen compounds are present in detergents in amounts of up to 50% by weight, especially from 5% to 30% by weight.

In addition, conventional bleach activators which form peroxycarboxylic acids or peroxoimidic acids under perhydrolysis conditions and / or customary bleach-activating transition metal complexes can be used. The optional, especially in amounts of 0.5 wt .-% to 6 wt .-%, present component of the bleach activators include the commonly used N- or O-acyl compounds, for example, polyacylated alkylenediamines, especially tetraacetylethylenediamine, acylated glycolurils, especially tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, urazoles, diketopiperazines, sulfuryl amides and cyanurates, in addition to carboxylic anhydrides, in particular phthalic anhydride, carboxylic acid esters, especially sodium isononanoyl-phenolsulfonat, and acylated sugar derivatives, in particular pentaacetylglucose, and cationic nitrile derivatives such as trimethylammoniumacetonitrile salts. In order to avoid the interaction with the peroxygen compounds, the bleach activators may have been coated or granulated in known manner with encapsulating substances, granulated tetraacetylethylenediamine having mean particle sizes of from 0.01 mm to 0.8 mm, granulated 1.5% by means of carboxymethylcellulose. Diacetyl-2,4-dioxohexahydro-1,3,5-triazine, and / or formulated in particulate trialkylammonium acetonitrile is particularly preferred. Such bleach activators are preferably contained in detergents in amounts of up to 8% by weight, in particular from 2% by weight to 6% by weight, based in each case on the total agent.

The preparation of solid compositions presents no difficulties and can be carried out in a manner known in the art, for example by spray-drying or granulation. For producing the compositions having an increased bulk density, in particular in the range from 650 g / l to 950 g / l, a process comprising an extrusion step is preferred. Detergents in the form of aqueous or other conventional solvent-containing solutions are particularly advantageously prepared by simply mixing the ingredients, which can be added in bulk or as a solution in an automatic mixer.

In an also preferred embodiment, the agents, in particular in concentrated liquid form, are present as a portion in a completely or partially water-soluble coating. Portioning makes it easier for the consumer to dose.

The funds can be packed, for example, in foil bags. Pouches made of water-soluble film make it unnecessary for the consumer to tear open the packaging. In this way, a convenient dosing of a single, sized for a wash portion by inserting the bag directly into the washing machine or by throwing the bag into a certain amount of water, for example in a bucket, a bowl or hand basin, possible. The film bag surrounding the washing portion dissolves without residue when it reaches a certain temperature.

There are numerous processes in the prior art for producing water-soluble detergent portions, which are in principle also suitable for the production of agents useful in the context of the present invention. The best known methods are the tubular film processes with horizontal and vertical sealing seams. Also suitable for the production of film bags or dimensionally stable detergent portions is the thermoforming process (thermoforming process). However, the water-soluble envelopes need not necessarily consist of a film material, but can also represent dimensionally stable containers that can be obtained for example by means of an injection molding process.

Furthermore, methods for producing water-soluble capsules of polyvinyl alcohol or gelatin are known, which in principle offer the possibility to provide capsules with a high degree of filling. The methods are based on introducing the water-soluble polymer into a shaping cavity. The filling and sealing of the capsules takes place either synchronously or in successive steps, in which case the filling of the capsules takes place through a small opening in the latter case. The filling of the capsules takes place, for example, by a Befüllkeil, which is above two mutually rotating drums, which have ball half shells on its surface, is arranged. The drums carry polymer bands that cover the ball half-shell cavities. At the positions where the polymer band of one drum coincides with the polymer tape of the opposite drum, a seal takes place. In parallel, the filling material is injected into the forming capsule, wherein the injection pressure of the filling liquid presses the polymer bands in the Kugelhalbschalenkavitäten. A process for the preparation of water-soluble capsules, in which first the filling and then the sealing takes place, is based on the so-called Bottle-Pack® process. In this case, a tubular preform is guided into a two-part cavity. The cavity is closed, the lower tube portion is sealed, then the tube is inflated to form the capsule shape in the cavity, filled and finally sealed.

The shell material used for the preparation of the water-soluble portion is preferably a water-soluble polymeric thermoplastic, more preferably selected from the group (optionally partially acetalized) polyvinyl alcohol, polyvinyl alcohol copolymers, polyvinylpyrrolidone, polyethylene oxide, gelatin, cellulose and derivatives thereof, starch and derivatives thereof, blends and composites, inorganic salts and mixtures of said materials, preferably hydroxypropylmethylcellulose and / or polyvinyl alcohol blends. Polyvinyl alcohols are commercially available, for example under the trademark Mowiol® (Clariant). Polyvinyl alcohols which are particularly suitable for the purposes of the present invention are, for example, Mowiol® 3-83, Mowiol® 4-88, Mowiol® 5-88, Mowiol® 8-88 and Clariant L648. The water-soluble thermoplastic used to prepare the portion may additionally optionally comprise polymers selected from the group comprising acrylic acid-containing polymers, polyacrylamides, oxazoline polymers, polystyrene sulfonates, polyurethanes, polyesters, polyethers and / or mixtures of the above polymers. It is preferred if the water-soluble thermoplastic used comprises a polyvinyl alcohol whose degree of hydrolysis makes up 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol%. It is further preferred that the water-soluble thermoplastic used comprises a polyvinyl alcohol whose molecular weight is in the range from 10,000 to 100,000 gmol ^-1 , preferably from 11,000 to 90,000 gmol ^-1 , more preferably from 12,000 to 80,000 gmol ^-1 and especially from 13,000 to 70,000 gmol ^-1 lies. It is further preferred if the thermoplastics are used in amounts of at least 50% by weight, preferably of at least 70% by weight, more preferably of at least 80% by weight and in particular of at least 90% by weight, based in each case on the weight the water-soluble polymeric thermoplastic.

Examples

By mixing the ingredients indicated in Table 1 below in the stated amounts (% by weight) liquid detergents were prepared: Table 1 Ingredient / agent V1 V2 V3 E1 V4 E2 V5 E3 V6 E4 E5 Rhamnolipid ^a) - - 6 6 6.5 6.5 - 6 - 6 6.5 C _9-13 Na alkyl benzene sulfonate 5.5 5.5 5.5 5.5 5.5 5.5 5.5 5.5 5.5 5.5 5.5 C _12-18 fatty alcohol, 7 EO 6 6 - - 6 6 6 - 6 - 6 C _12-14 Na Alcohol 2EO Sulfate 6.5 6.5 6.5 6.5 - - 6.5 6.5 6.5 6.5 - C _12-18 fatty acid, Na salt 3 3 3 3 3 3 3 3 3 3 3 citric acid 2 2 2 2 2 2 2 2 2 2 2 sodium hydroxide 2 2 2 2 2 2 2 2 2 2 2 boric acid 1 1 1 1 1 1 1 1 1 1 1 enzymes + + + + + + + + + + + Perfume + + + + + + + + + + + glycerin 2 2 2 2 2 2 2 2 2 2 2 ethanol 2 2 2 2 2 2 2 2 2 2 2 Phosphonic acid, Na salt 1 1 1 1 1 1 1 1 1 1 1 N-containing polymer 1 ^b) - 2 - 2 - 2 - - - - - N-containing polymer 2 ^c) - - - - - - 2 2 - - - N-containing polymer 3 ^d) - - - - - - - - 2 2 2 water on 100 a) R90L, manufacturer AGAE Technologies
b) Ethoxylated polyethyleneimine, Sokalan® HP 20, manufacturer BASF SE
c) Vinylpyrrolidone / vinylimidazole copolymer, Sokalan® HP 56k, manufacturer BASF SE
d) Vinylpyrrolidone / vinylcaprolactam copolymer

Standardized soilings (cotton, unless otherwise stated) or cotton blend fabrics were washed, then rinsed, dried and then their reflectance measured spectrophotometrically (Minolta® CR400-1) (washing temperature 25 ° C for greasy soils, 40 ° C for other soiling, washing time 1h, detergent dosage 4.12 g / l, 5-fold determination)

• Ruß/Olivenöl (A)
• Butterfett (B)
• Gebrauchtes Frittierfett, gefärbt (C)
• Gefärbter Rindertalg (D)
• Gefärbtes Schmalz (E)
• Pigment/Hautfett (F)

The following greasy soiling was used:

• Soot / olive oil (A)
• Butterfat (B)
• Used frying fat, colored (C)
• Colored beef tallow (D)
• Dyed lard (E)
• Pigment / skin fat (F)

• Schokoladenmilch/Ruß (G)
• Blut/Milch/Tusche (H)
• Ei/Pigment (I)
• Kakao (J)
• Blut/Milch/Tusche, auf Baumwolle/Polyester-Mischgewebe (K)
• Blaubeere (L)

The following other soiling were used:

• Chocolate Milk / Soot (G)
• Blood / milk / ink (H)
• Egg / pigment (I)
• Cocoa (J)
• Blood / milk / Indian ink, on cotton / polyester blend (K)
• Blueberry (L)

The values given in the following Tables 2 to 4 show the ΔY values of the remission measurement in comparison to the detergent V1, wherein higher values mean a better leachability. Table 2: Soiling / medium V2 V3 E1 V4 E2 B -1.7 2.0 2.7 nb nb C 0.1 1.2 1.9 4.4 5.0 e -1.7 3.0 4.7 5.6 6.1 nb: not determined Soiling / medium V5 V3 E3 B -0.3 2.0 2.5 e -1.8 3.0 3.3 F -0.7 -0.9 0.5 H 0 -0.9 0.5 Soiling / medium V6 V3 E4 V4 E5 A -2.6 nb nb -0.4 0.4 C -0.5 1.2 2.2 4.8 5 D 0.5 nb nb 7.7 9.2 e 0.6 3 4.4 nb nb G 2.8 -2.8 3.1 nb nb I -1.3 0 0.6 nb nb J 0 -1 0.5 nb nb K -0.8 0.8 1.1 nb nb L 0 -1.3 0.3 nb nb nb: not determined

The results in Tables 2 to 4 show that the combinations of rhamnolipid and N-containing polymers have synergistic performance improvements.

Claims (9)

1. A washing or cleaning agent, containing a rhamnolipid and an N-containing polymer, which is selected from the group consisting of alkoxylated polyamine and the polymers that are obtainable by polymerizing N-vinylcaprolactam, N-vinylpyrrolidone, N-vinylimidazole, N-vinylpiperidone, N-vinylsuccinimide, N-vinyl glutarimide, N-vinylacetamide, N-alkyl-N-vinylacetamide, N-vinylformamide, N-alkyl-N-vinylformamide and/or mixtures of at least two of these monomers, and mixtures of said polymers.
2. The agent according to claim 1, characterized in that it contains 0.01 wt.% to 75 wt.%, in particular 0.05 wt.% to 35 wt.%, of a rhamnolipid and 0.01 wt.% to 50 wt.%, in particular 0.05 wt.% to 30 wt.%, of an N-containing polymer.
3. The use of an N-containing polymer, which is selected from the group consisting of alkoxylated polyamine and the polymers that are obtainable by polymerizing N-vinylcaprolactam, N-vinylpyrrolidone, N-vinylimidazole, N-vinylpiperidone, N-vinylsuccinimide, N-vinyl glutarimide, N-vinylacetamide, N-alkyl-N-vinylacetamide, N-vinylformamide, N-alkyl-N-vinylformamide and/or mixtures of at least two of these monomers, and mixtures of said polymers, for increasing the washing or cleaning performance of rhamnolipid-containing washing or cleaning agents.
4. The use of combinations of a rhamnolipid and an N-containing polymer, which is selected from the group consisting of alkoxylated polyamine and the polymers that are obtainable by polymerizing N-vinylcaprolactam, N-vinylpyrrolidone, N-vinylimidazole, N-vinylpiperidone, N-vinylsuccinimide, N-vinyl glutarimide, N-vinylacetamide, N-alkyl-N-vinylacetamide, N-vinylformamide, N-alkyl-N-vinylformamide and/or mixtures of at least two of these monomers, and mixtures of said polymers, for increasing the washing or cleaning performance of washing or cleaning agents.
5. The use according to claim 3 or 4, characterized in that the N-containing polymer or the combination thereof with a rhamnolipid is added to a washing or cleaning agent-containing liquor or is introduced into the liquor as a component of a washing or cleaning agent, the use of the N-containing polymer alone requiring the use of a rhamnolipid-containing washing agent, and objects to be washed or cleaned being introduced into the liquor.
6. The agent according to claim 1 or 2 or the use according to one of claims 3 to 5, characterized in that the rhamnolipid has the general formula (I),

   

   in which

   m represents 0, 1 or 2,

   n represents 0 or 1,

   R¹ and R², independently of one another, represent identical or different hydrocarbon functional groups having 2 to 24, in particular 5 to 13, C atoms.
7. The agent according to claim 1, 2 or 6, or the use according to one of claims 3 to 6, characterized in that the N atoms in the polyamine are separated by alkylene groups having 2 to 12 C atoms, in particular 2 to 6 C atoms, it not being necessary for all the alkylene groups to have the same C atom number, and/or the primary amino functions in the polyamine carrying one or two polyalkoxy groups and the secondary amino functions carrying one polyalkoxy group, it not being necessary for each amino function to be alkoxy group-substituted, and/or the average proportion of alkoxy groups for each primary and secondary amino function in the polyalkoxylated polyamine being 5 to 100, in particular 10 to 50.
8. The agent according to claim 1, 2 or 6, or the use according to one of claims 3 to 6, characterized in that the N-containing polymer is made up of N-vinylcaprolactam and another of the above-mentioned ethylenically unsaturated monomers, in particular N-vinylpyrrolidone, or of N-vinylpyrrolidone and N-vinylimidazole.
9. The agent or the use according to one of the preceding claims, characterized in that the N-containing polymer has an average molecular weight (number average) in the range of 1,000 g/mol to 500,000 g/mol, in particular of 1,100 g/mol to 150,000 g/mol.