Lipase-biosurfactant systems for grease removal

Abstract

The invention relates to a system for removing grease- or oil-containing soiling from textiles or hard surfaces, the system containing at least one sophorolipid and at least one lipase, and to a detergent or cleaning agent containing a system of this type, and to a method for removing grease- or oil-containing soiling from textiles or hard surfaces using said agents.

Description

[0001] Lipase-biosurfactant systems for fat removal

[0002] The invention relates to a system for removing greasy or oily soils from textiles or hard surfaces, which contains at least one sophorolipid and at least one lipase, as well as to a washing or cleaning agent containing such a system, and to a method for removing greasy or oily soils from textiles or hard surfaces, in which the washing or cleaning agent is used.

[0003] Grease or oily soils on hard surfaces or textiles are among the more stubborn types of soiling that are not easy to remove. In conventional washing and / or cleaning processes, such soiling is removed by the washing and / or cleaning temperature, usually between approximately 40°C and approximately 60°C, first liquefying the fats and then detaching them from the surface by surfactants contained in the washing and / or cleaning agents ("roll-up mechanism"). The detached, liquefied fat molecules are then carried away, i.e., rinsed away, by mechanical forces during the washing and / or rinsing process. Additionally or alternatively, grease and / or oily soils can be removed by esterases, lipolytic enzymes, or lipases, in which the enzyme breaks down the fats and / or oils, and the degradation products are then rinsed away. However, there are currently no effective methods for removing fats and / or oils at low temperatures, i.e.At temperatures below 40°C, especially at temperatures of approximately 20°C or 30°C, this is not a satisfactory alternative for removing greasy and / or oily soils, as the greases do not liquefy or only insufficiently liquefy at temperatures below approximately 30°C or 40°C. Removal by lipase can be achieved at lower temperatures, but it is time-consuming. The combination of lipases with surfactants has been shown to achieve faster removal; however, these surfactants are often not biodegradable and / or are not derived from renewable resources.

[0004] There was therefore a desire to remove greasy or oily soiling from textiles or hard surfaces, even at low temperatures, using more sustainable, biodegradable and thus more environmentally friendly agents in an energy- and time-efficient manner.

[0005] It was surprisingly found that a system containing at least one sophorolipid and at least one lipase is particularly suitable for this purpose.

[0006] A first aspect of the invention is therefore a system for removing greasy or oily soils from textiles or hard surfaces, wherein the system contains at least one sophorolipid and at least one lipase. A further aspect is the use of a system containing at least one sophorolipid and at least one lipase for removing greasy or oily soils from textiles or hard surfaces.

[0007] The system can be used in detergents or cleaning agents to improve the removal of greasy or oily soils. This invention therefore further relates to detergents or cleaning agents containing such a system. These detergents and cleaning agents can be used in a process for removing greasy or oily soils from textiles or hard surfaces.

[0008] These and other aspects, features, and advantages of the invention will become apparent to those skilled in the art from a study of the following detailed description and claims. Any feature of one aspect of the invention may be employed in any other aspect of the invention. Furthermore, it is to be understood that the examples contained herein are intended to describe and illustrate the invention, but not to limit it, and in particular, the invention is not limited to these examples.

[0009] Unless otherwise stated, all percentages are by weight (wt%), based on the total weight of the corresponding composition or agent.

[0010] Numerical ranges specified in the format "from x to y" include the specified values. If multiple preferred numerical ranges are specified in this format, it goes without saying that all ranges resulting from the combination of the different endpoints will also be included.

[0011] "At least one," as used herein, means one or more, i.e., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or more. With respect to an ingredient, the information refers to the type of ingredient and not to the absolute number of molecules. Together with weight information, the information refers to all compounds of the specified type contained in a product, i.e., the product typically contains no further compounds of this type beyond the stated amount of the corresponding compounds.

[0012] "Approximately" or "approximately" as used herein with reference to numerical values ​​means the corresponding value ±10%, preferably ±5%.

[0013] The term "washing and cleaning agent" or "washing or cleaning agent" as used herein is synonymous with the term "agent" and refers to a composition for cleaning textiles, in particular containing or consisting of cotton, polyester and mixtures thereof, and / or hard surfaces, in particular tableware (preferably made of ceramic such as porcelain or earthenware as well as plastic), metal (e.g. cutlery or pots) or glass as well as surfaces in the kitchen.

[0014] For the purposes of the invention, the term "room temperature" refers to 20°C at 1,013 mbar, unless explicitly stated otherwise. "Liquid," as used herein, includes liquids and gels as well as pasty compositions. It is preferred that the liquid compositions be flowable and pourable at room temperature, but it is also possible that they have a yield point.

[0015] A substance, e.g. a composition or an agent, is solid according to the definition of the invention if it is in the solid state at 20°C and 1,013 mbar.

[0016] A substance, e.g., a composition or agent, is liquid according to the invention's definition if it exists in the liquid state at 20°C and 1,013 mbar. Liquid also includes gel.

[0017] In the context of the present invention, a "fatty or oily surface" is understood to mean a surface that contains or consists of fats and / or oils, and / or a surface that is coated with fats and / or oils, and / or a surface that is provided with at least one fatty and / or oily soil, preferably soiled. In the context of the present invention, "fat" or "fats" are understood to mean macromolecules formed from glycerol and fatty acids, in addition to mono- and diglycerides, in particular the so-called triacylglycerols or triglycerides, in which three fatty acids are bonded to the glycerol. Furthermore, according to the invention, all known fatty acids with 8 to 36, preferably 10 to 24, carbon atoms, both mono- and polyunsaturated and saturated fatty acids, are encompassed. In the context of the present invention, "oil" or "oils" are understood to mean fatty acids that are liquid or soluble at room temperature.Flowable, fatty substances that do not mix with water are understood. Both synthetic and bio-based fats and / or oils are encompassed within the scope of the invention. Within the scope of the present invention, "fatty or oily soiling" is understood to mean soiling on a surface, in particular a hard surface and / or textile surface, that contains or consists of a fat and / or oil. Examples of typical fat- or oil-containing soiling are fat- or oil-containing food and food residue soiling, such as vegetable fats (e.g., coconut fat), animal fats (e.g., butter, clarified butter), cooking oils (e.g., olive oil, sunflower oil, rapeseed oil), frying fat, mayonnaise, margarine, deep-fryer fat, meat fat (e.g., beef tallow, pork fat, lard), also burnt-in food residues, and / or synthetic fats and / or oils, such as, for example,Mineral oil(s) and / or greases, engine oil, bicycle chain oil, pigment greases, pigment oils, and / or fats and / or oils from personal care products such as lipstick, make-up, lotion, cream, and / or body fat deposits such as sebum and sebum.

[0018] The first subject of the invention is a system for removing greasy or oily soils from textiles or hard surfaces. A first component of the system is sophorolipids. These are biosurfactants consisting of a sophorose residue in which two glucose molecules are linked together in a ß-1,2'-glycosidic manner, to which a hydroxyl group of a hydroxycarboxylic acid is bonded in a ß-glycosidic manner. The hydroxycarboxylic acid can bear the hydroxyl group on the terminal C atom or on a C atom located within the carbon chain, and can be saturated or unsaturated.

[0019] Examples of sophorolipids are: They can be in the open form shown above as an example or in the form of monomeric or dimeric lactones, such as:

[0020] The open form and the lactone form can also exist side by side, and both can be converted into one another by intramolecular esterification or hydrolysis. In the compounds of formula (I), the sophorolipids are present in the open form. The hydroxyl groups on the sophorose residues of the sophorolipids can also be fully or partially esterified with carboxylic acids, with acetic acid, for example, being a possible carboxylic acid, and the primary hydroxyl groups being the primary esterification points. Sophorolipids are formed, for example, by yeasts such as Candida albicans, Candida apicola, Candida floricola, Candida kuoi, Candida riodocensis, Candida stellata, Candida tropicalis, Candida parapsilosis, Rhodotorula bajevae, Rhodotorula bogoriensis, Wickerhamiella domercqiae, Wickerhamomyces anomalus, and Starmerella bombicola, and can be obtained from the fermentation of such microorganisms.

[0021] Another component of the system is at least one lipase. Lipases are enzymes that catalyze the hydrolysis of ester bonds in lipid substrates, particularly in fats and oils. Lipases therefore represent a group of esterases. Lipases are generally versatile enzymes that accept a wide variety of substrates, e.g. aliphatic, alicyclic, bicyclic and aromatic esters, thioesters and activated amines. Lipases are effective, for example, against grease residues in laundry and catalyze their hydrolysis (lipolysis). Lipases with broad substrate spectra are used in particular where inhomogeneous raw materials or substrate mixtures have to be converted, such as in detergents and cleaning agents, since soiling can consist of fats and oils with different structures. The lipases used in detergents or cleaning agents known from the state of the art are usually of microbial origin and usually come from bacteria or fungi, e.g.E.g., of the genera Thermomyces, Bacillus, Pseudomonas, Acinetobacter, Micrococcus, Humicola, Trichoderma, or Trichosporon. Lipases are usually produced by suitable microorganisms using known biotechnological processes, e.g., by transgenic expression hosts of the genera Bacillus or by filamentous fungi.

[0022] In general, only selected lipases are suitable for use in liquid surfactant preparations. Many lipases do not demonstrate sufficient catalytic performance or stability in such preparations. However, the use of lipases results in an unpleasant odor on the washed items, especially textiles, after the washing process, because the lipase is absorbed by the textiles and continues to hydrolyze fatty acid esters into low-molecular-weight fatty acids. These low-molecular-weight fatty acids are then perceived by their unpleasant odor. The intensity of the odor can vary depending on the nature of the textile.

[0023] Examples of suitable lipases are, for example, lipase from Thermomyces, e.g. from T. lanuginosus (formerly Humicola lanuginosa), as described in EP 0258068 and EP 0305216, lipase from strains of Pseudomonas (some of them now renamed Burkholderia), e.g. P. alcaligenes or P. pseudoalcaligenes, P. cepacia, P. sp. strain SD705, P. wisconsinensis, Streptomyces lipases of the GDSL type, lipase from Thermobifida fusca, lipase from Geobacillus stearothermophilus, lipase from Bacillus subtilis and lipase from Streptomyces griseus and S. pristinaespiralis. The preferred lipases include, for example, the lipases originally obtainable from Humicola lanuginosa (Thermomyces lanuginosus) or further developed therefrom, in particular those with one or more of the following amino acid substitutions starting from the said lipase in the positions D96L, T213R and / or N233R, particularly preferably T213R and N233R.Preferred commercial lipase products include Lipolase™, Lipex™, Lipolex™ and Lipoclean™ (Novozymes A / S), Lumafast (Genencor / DuPont) and Lipomax (Gist-Brocades).

[0024] Methods for determining lipase activity are familiar to those skilled in the field of enzyme technology and are routinely used by them (see, for example, Bruno Stellmach, "Bebestimmungsmethoden Enzyme für Pharmazie, Lebensmittelchemie, Technik, Biochemie, Biologie, Medizin", Steinkopff Verlag Darmstadt, 1988, p. 172ff). Lipase-containing samples are added to an olive oil emulsion in emulsifier-containing water and incubated at 30°C and pH 9.0. This releases fatty acids. These are continuously titrated with 0.01 N sodium hydroxide solution using an autotitrator for 20 minutes so that the pH remains constant ("pH-stat titration"). Lipase activity is determined based on the sodium hydroxide consumption by reference to a reference lipase sample. An alternative test for determining the lipolytic activity of the lipases according to the invention is an optical measurement method, preferably a photometric method.The test suitable for this purpose involves the lipase-dependent cleavage of the substrate para-nitrophenol butyrate (pNP-butyrate). This is cleaved by lipase into para-nitrophenolate and butyrate. The presence of para-nitrophenolate can be determined at 405 nm using a photometer, e.g., the Tecan Sunrise device and the XFLUOR software, and thus allows conclusions to be drawn about the enzymatic activity of the lipase.

[0025] The system, containing at least one sophorolipid and at least one lipase, can be used to remove greasy or oily soils from textiles or hard surfaces. It can also be used in detergents and cleaning agents.

[0026] Washing or cleaning agents according to the invention preferably contain at least one further active ingredient, preferably selected from the group comprising further surfactants, builders, complexing agents, polymers, glass corrosion inhibitors, corrosion inhibitors, bleaching agents, bleach activators, bleach catalysts, water-miscible organic solvents, hydrotropes, further enzymes, enzyme stabilizers, sequestering agents, electrolytes, pH adjusters, opacifiers, pearlescent agents, viscosity regulators, fluorescent agents, optical brighteners, anti-redeposition agents, graying inhibitors, soil-removing polymers, dye transfer inhibitors, antistatic agents, crease inhibitors, shrinkage inhibitors, ironing aids, repellents and impregnating agents, swelling and slip-resistant agents, skin-care active ingredients, softening components, UV absorbers, foam inhibitors, antimicrobial active ingredients, germicides, fungicides, antioxidants, preservatives,Bitters as well as colorings and fragrances.,

[0027] Other suitable surfactants include, in particular, anionic surfactants, nonionic surfactants, and mixtures thereof, but cationic, zwitterionic, and / or amphoteric surfactants may also be present. The detergents preferably contain 0.5 to 70% by weight of surfactant. In textile detergents, preferably 35 to 60% by weight, and more preferably 40 to 55% by weight, of surfactant is used, based on the total weight of the detergent; in preferred embodiments, the detergents preferably contain 3 to 35% by weight, preferably 5 to 30% by weight, of surfactant, based on the total weight of the detergent.

[0028] Suitable anionic surfactants are, in particular, those containing sulfate or sulfonate groups with preferably alkali ions as cations. Suitable sulfate-type surfactants include the salts of the sulfuric acid half-esters of C 8 fatty alcohols and the sulfation products of the above-mentioned non-ionic surfactants with a low degree of ethoxylation. Suitable sulfonate-type surfactants include, for example, C 8-14 alkylbenzenesulfonates, alkanesulfonates obtained from C 12-18 alkanes, for example, by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization, C 12-18 olefinsulfonates obtained from the reaction of corresponding monoolefins with sulfur trioxide, mixtures of alkene and hydroxyalkanesulfonates, disulfonates, as can be obtained, for example,from Ci2-18 monoolefins with terminal or internal double bonds by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products, as well as a-sulfofatty acid esters (ester sulfonates) which are formed during the sulfonation of fatty acid methyl or ethyl esters, e.g. a-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.

[0029] The agent, in particular the textile detergents, preferably contains 2 to 55 wt.%, preferably 3 to 35 wt.%, of anionic surfactant, based on the total weight of the agent. Most preferably, the agent contains 3 to 25 wt.% alkylbenzenesulfonate. Furthermore, the agent may preferably contain other anionic surfactants, in particular alkyl ether sulfates, as well as nonionic surfactants, in particular fatty alcohol alkoxylates. These can then make up the remainder of the surfactants.

[0030] Suitable alkylbenzenesulfonates are preferably selected from linear or branched alkylbenzenesulfonates of the formula in which R' and R" are independently H or alkyl and together contain 6 to 19, preferably 7 to 15 and in particular 9 to 13 C atoms. A particularly preferred representative is sodium dodecylbenzenesulfonate.

[0031] Preferred alk(en)yl sulfates are the alkali metal salts, especially the sodium salts, of the sulfuric acid half-esters of C12-C18 fatty alcohols, e.g., coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl, or stearyl alcohol, or C10-C20 oxo alcohols, and those half-esters of secondary alcohols of these chain lengths. Also preferred are alk(en)yl sulfates of the stated chain length that contain a synthetic, petrochemically produced straight-chain alkyl radical, which exhibit degradation behavior similar to that of equivalent compounds based on oleochemical raw materials. For washing purposes, C12-C16 alkyl sulfates and C18-C16 alkyl sulfates, as well as C18-C16 alkyl sulfates, are preferred.

[0032] Also suitable are the sulfuric acid monoesters of straight-chain or branched C7-2i alcohols ethoxylated with 1 to 6 mol of ethylene oxide, such as 2-methyl-branched Cg-n alcohols with an average of 3.5 mol of ethylene oxide (EO) or C12-18 fatty alcohols with 1 to 4 EO.

[0033] Suitable alkyl ether sulfates are, for example, compounds of the formula R 1 -O-(AO) n -SO3- X + .

[0034] In this formula, R 1 represents a linear or branched, substituted or unsubstituted alkyl radical, preferably a linear, unsubstituted alkyl radical, particularly preferably a fatty alcohol radical. Preferred radicals R 1 are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl radicals and mixtures thereof, with the representatives having an even number of carbon atoms being preferred. Particularly preferred radicals R 1are derived from C s fatty alcohols, e.g., from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl, or stearyl alcohol, or from C 10-20 oxo alcohols. AO stands for an ethylene oxide (EO) or propylene oxide (PO) group, preferably an ethylene oxide group. The index n stands for an integer from 1 to 50, preferably from 1 to 20, and in particular from 2 to 10. Most preferably, n stands for the numbers 2, 3, 4, 5, 6, 7, or 8. X + stands for a monovalent cation or the n-th part of an n-valent cation, preferred are the alkali metal ions and among them Na + or K + , where Na + is highly preferred. Other cations X + can be selected from NHT, % Zn 2+ , % Mg 2+ , % Ca 2+ , % Mn 2+ and their mixtures.

[0035] In various embodiments, the alkyl ether sulfate may be selected from fatty alcohol ether sulfates of the formula with k = 1 from 1 to 19, n = 2, 3, 4, 5, 6, 7, or 8. Particularly preferred representatives are Na-Ci2-14 fatty alcohol ether sulfates with 2 EO (k = 11-13, n = 2). The stated degree of ethoxylation represents a statistical mean, which can be a whole or fractional number for a specific product. The stated degrees of alkoxylation represent statistical mean, which can be a whole or fractional number for a specific product. Preferred alkoxylates / ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).

[0036] It has proven advantageous for cold-wash performance if the detergents also contain soap(s). Suitable soaps are preferably the alkali salts of saturated or unsaturated C 12-18 fatty acids. Such fatty acids can also be used in a non-fully neutralized form. Preferred detergents are therefore characterized by containing soap(s). Particularly suitable are saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid, and behenic acid, as well as, in particular, soap mixtures derived from natural fatty acids, e.g., coconut, palm kernel, or tallow fatty acids. 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 polyglycosides, and mixtures thereof. Alkyl glycosides of the general formula R are also suitable as further nonionic surfactants.5 O(G) X be used in the R 5 a primary straight-chain or methyl-branched, in particular 2-methyl-branched, aliphatic radical having 8 to 22, preferably 12 to 18, carbon atoms, and G is the symbol representing a glycose unit having 5 or 6 carbon atoms, preferably glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably, x is between 1.2 and 1.4.

[0037] Another class of non-ionic surfactants, which are used either as the sole non-ionic surfactant or in combination with other additional non-ionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain.

[0038] 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.

[0039] Other suitable surfactants are polyhydroxy fatty acid amides of the formula, in which R is an aliphatic acyl radical having 6 to 22 carbon atoms, R 1represents hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z] represents a linear or branched polyhydroxyalkyl radical having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups. Polyhydroxy fatty acid amides are known substances that can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride. The group of polyhydroxy fatty acid amides also includes compounds of the formula in which R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R 1 represents a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R 2represents a linear, branched, or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, with C 1-4 alkyl or phenyl radicals being preferred, and [Z] represents a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this radical. [Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose, or xylose. The N-alkoxy- or N-aryloxy-substituted compounds can be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.

[0040] A washing or cleaning agent according to the invention preferably contains at least one water-soluble and / or water-insoluble, organic and / or inorganic builder.The water-soluble organic builder substances include polycarboxylic acids, in particular citric acid and sugar acids, monomeric and polymeric aminopolycarboxylic acids, in particular glycinediacetic acid, methylglycinediacetic acid, nitrilotriacetic acid, iminodisuccinates such as ethylenediamine-N,N'-disuccinic acid and hydroxyiminodisuccinates, ethylenediaminetetraacetic acid and polyaspartic acid, polyphosphonic acids, in particular aminotris(methylenephosphonic acid), ethylenediaminetetrakis(methylenephosphonic acid), lysinetetra(methylenephosphonic acid) and 1-hydroxyethane-1,1-diphosphonic acid, polymeric hydroxy compounds such as dextrin and polymeric (poly)carboxylic acids, in particular polycarboxylates accessible by oxidation of polysaccharides, polymeric acrylic acids, methacrylic acids, maleic acids and copolymers thereof, which also contain small amounts of polymerizable substances without carboxylic acid functionality. may contain.The relative average molecular weight of homopolymers of unsaturated carboxylic acids is generally between 5,000 g / mol and 200,000 g / mol, and that of 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 weight of 50,000 to 100,000. Suitable, albeit less preferred, compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinyl methyl ethers, vinyl esters, ethylene, propylene, and styrene, in which the acid content is at least 50% by weight. Terpolymers containing two unsaturated acids and / or their salts as monomers and vinyl alcohol and / or a vinyl alcohol derivative or a carbohydrate as the third monomer can also be used as water-soluble organic builder substances.The first acidic monomer or its salt is derived from a monoethylenically unsaturated C8-C12 carboxylic acid, preferably from a C3-C4 monocarboxylic acid, in particular from (meth)acrylic acid. The second acidic monomer or its salt can be a derivative of a C4-C12 dicarboxylic acid, with maleic acid being particularly preferred. The third monomer unit is formed in this case from vinyl alcohol and / or preferably from an esterified vinyl alcohol. Vinyl alcohol derivatives that represent an ester of short-chain carboxylic acids, for example, C1-C4 carboxylic acids, with vinyl alcohol are particularly preferred. Preferred polymers contain 60 wt.% to 95 wt.%, in particular 70 wt.% to 90 wt.% of (meth)acrylic acid or (meth)acrylate, particularly preferably acrylic acid or acrylate, and maleic acid or maleate and 5 wt.% to 40 wt.%, preferably 10 wt.% to 30 wt.% of vinyl alcohol and / or vinyl acetate.Very particular preference is given to polymers in which the weight ratio of (meth)acrylic acid or (meth)acrylate to maleic acid or maleate is between 1:1 and 4:1, preferably between 2:1 and 3:1, and in particular between 2:1 and 2.5:1. Both the amounts and the weight ratios are based on the acids. The second acidic monomer or its salt can also be a derivative of an allylsulfonic acid substituted in the 2-position by an alkyl radical, preferably a C1-C4-alkyl radical, or an aromatic radical, preferably derived from benzene or benzene derivatives. Preferred terpolymers contain 40 wt.% to 60 wt.%, in particular 45 to 55 wt.% of (meth)acrylic acid or (meth)acrylate, particularly preferably acrylic acid or acrylate, 10 wt.% to 30 wt.%, preferably 15 wt.% to 25 wt.% of methallylsulfonic acid or methallylsulfonate and as a third monomer 15 wt.% to 40 wt.-%, preferably 20 wt.% to 40 wt.% of a carbohydrate. This carbohydrate can, for example, be a mono-, di-, oligo-, or polysaccharide, with mono-, di-, or oligosaccharides being preferred. Sucrose is particularly preferred. The use of the third monomer presumably creates predetermined breaking points in the polymer, which are responsible for the polymer's good biodegradability. These terpolymers generally have a relative average molecular weight between 1,000 g / mol and 200,000 g / mol, preferably between 200 g / mol and 50,000 g / mol. Other preferred copolymers are those which have acrolein and acrylic acid / acrylic acid salts or vinyl acetate as monomers. The organic builder substances can be used in the form of aqueous solutions, preferably in the form of 30 to 50 wt.% aqueous solutions, in particular for the production of liquid agents.All of the acids mentioned are generally used in the form of their water-soluble salts, especially their alkali salts.

[0041] Such organic builder substances can, if desired, be present in amounts of up to 40 wt.%, in particular up to 25 wt.%, and preferably from 1 wt.% to 8 wt.%. Amounts in the upper half of the above-mentioned ranges are preferably used in paste-like or liquid, especially water-based, detergents or cleaning agents.

[0042] Polyphosphates, preferably sodium triphosphate, are particularly suitable as water-soluble inorganic builder materials. Crystalline or amorphous, water-dispersible alkali aluminosilicates are particularly suitable as water-insoluble inorganic builder materials, in amounts not exceeding 25% by weight, preferably from 3% to 20% by weight, and in particular in amounts from 5% to 15% by weight. Among these, crystalline sodium aluminosilicates of detergent quality, in particular zeolite A, zeolite P, zeolite MAP, and optionally zeolite X, are preferred. Amounts close to the stated upper limit are preferably used in solid, particulate compositions. Suitable aluminosilicates, in particular, have no particles with a grain size exceeding 30 μm and preferably consist of at least 80% by weight of particles with a size below 10 μm. Their calcium-binding capacity is generally in the range of 100 to 200 mg CaO per gram.

[0043] In addition to or as an alternative to the aforementioned water-insoluble aluminosilicate and alkali metal carbonate, other water-soluble inorganic builder materials may be present. These include, in particular, polyphosphates such as sodium triphosphate, water-soluble crystalline and / or amorphous alkali metal silicate builders. Such water-soluble inorganic builder materials are preferably present in the agents in amounts of 1 wt.% to 20 wt.%, in particular 5 wt.% to 15 wt.%. The alkali metal silicates usable as builder materials preferably have a molar ratio of alkali metal oxide to SiO2 of less than 0.95, in particular of 1:1.1 to 1:12, and can be amorphous or crystalline. Preferred alkali metal silicates are sodium silicates, in particular amorphous sodium silicates, with a molar Na2O:SiO2 ratio of 1:2 to 1:2.8.Crystalline silicates, which can be present alone or in a mixture with amorphous silicates, are preferably crystalline layered silicates of the general formula Na2Si. xO2x+iy H2O is 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 takes on the values ​​2 or 3. In particular, both β- and β-sodium disilicates (Na2Si2O5 y H2O) are preferred. Practically anhydrous crystalline alkali silicates produced 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 layered silicate with a modulus of 2 to 3 is used, such as can be produced from sand and soda. Sodium silicates with a modulus in the range from 1.9 to 3.5 are used in a further embodiment.In a preferred embodiment of such agents, a granular compound of alkali silicate and alkali carbonate is used, such as that commercially available under the name Nabion® 15.

[0044] Another preferred component of agents according to the invention are complexing agents.

[0045] Particularly preferred complexing agents are phosphonates, provided their use is permitted by regulations. In addition to 1-hydroxyethane-1,1-diphosphonic acid, complexing phosphonates include a number of different compounds, such as:

[0046] Diethylenetriaminepenta(methylenephosphonic acid) (DTPMP). In this application, hydroxyalkane and aminoalkanephosphonates are particularly preferred. Among the hydroxyalkanephosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a cobuilder. It is preferably used as the sodium salt, with the disodium salt being neutral and the tetrasodium salt being alkaline (pH 9). Preferred aminoalkanephosphonates are ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP), and their higher homologues. They are preferably used in the form of the neutral sodium salts, e.g., as the hexasodium salt of EDTMP or as the hepta- and octasodium salts of DTPMP. HEDP is the preferred builder from the phosphonate class. Aminoalkanephosphonates also possess pronounced heavy metal binding capacity.Accordingly, especially if the agents also contain bleach, it may be preferable to use aminoalkanephosphonates, in particular DTPMP, or mixtures of the aforementioned phosphonates. A preferred agent in the context of this application contains one or more phosphonate(s) from the group consisting of aminotrimethylenephosphonic acid (ATMP) and / or salts thereof.

[0047] Ethylenediaminetetra(methylenephosphonic acid) (EDTMP) and / or its salts; diethylenetriaminepenta(methylenephosphonic acid) (DTPMP) and / or its salts; 1-hydroxyethane-1,1-diphosphonic acid (HEDP) and / or its salts; 2-phosphonobutane-1,2,4-tricarboxylic acid (PBTC) and / or its salts; hexamethylenediaminetetra(methylenephosphonic acid) (HDTMP) and / or its salts; nitrilotri(methylenephosphonic acid) (NTMP) and / or its salts.

[0048] Particularly preferred are agents which contain 1-hydroxyethane-1,1-diphosphonic acid (HEDP) or diethylenetriaminepenta(methylenephosphonic acid) (DTPMP) as phosphonates.

[0049] Of course, agents according to the invention can contain two or more different phosphonates.

[0050] In further preferred embodiments, agents according to the invention are substantially free of phosphonate-containing compounds. "Substantially free of phosphonate-containing compounds" in this context means that the corresponding agents or compositions contain, based on the total weight of the agent, less than 2 wt.%, preferably less than 1 wt.%, more preferably less than 0.5 wt.%, and particularly preferably less than 0.1 wt.%, of phosphonate-containing compounds. In particularly preferred embodiments, these agents / compositions are free of phosphonate-containing compounds.

[0051] Graying inhibitors or soil-release active ingredients (soil release polymers) particularly suitable for textile detergents are cellulose ethers such as carboxymethylcellulose, methylcellulose, hydroxyalkylcelluloses and cellulose mixed ethers such as methylhydroxyethylcellulose, methylhydroxypropylcellulose and methylcarboxymethylcellulose. Preference is given to using sodium carboxymethylcellulose, hydroxypropylmethylcellulose and mixtures thereof and optionally mixtures thereof with methylcellulose. The commonly used soil-release active ingredients include copolyesters containing dicarboxylic acid units, alkylene glycol units and polyalkylene glycol units. The proportion of graying inhibitors and / or soil-release active ingredients in agents according to the invention generally does not exceed 2% by weight and is preferably 0.5 to 1.5% by weight, particularly preferably 0.5 to 2% by weight, based on the total weight of the agent.

[0052] Derivatives of diaminostilbenedisulfonic acid or its alkali metal salts can be used as optical brighteners in textile detergents, particularly for textiles made from cellulose fibers (e.g., cotton). Suitable brighteners include salts of 4,4'-bis(2-anilino-4-morpholino-1,3,5-triazin-6-ylamino)stilbene-2,2'-disulfonic acid or similarly structured compounds that carry a diethanolamino group, a methylamino group, or a 2-methoxyethylamino group instead of the morpholino group. Furthermore, brighteners of the substituted 4,4'-distyryldiphenyl type, e.g., 4,4'-bis(4-chloro-3-sulfostyryl)diphenyl, can be present. Mixtures of brighteners can also be used. Brighteners of the 1,3-diaryl-2-pyrazoline type, e.g., 1-(p-sulfoamoylphenyl)-3-(p-chlorophenyl)-2-pyrazoline, and similarly structured compounds, are particularly suitable for polyamide fibers. The optical brightener or brightener mixture content of the agent generally does not exceed 1 wt.-%, preferably 0.05 to 0.5 wt.%, based on the total weight of the agent. In a preferred embodiment of the invention, the agent is free of such active ingredients.

[0053] The conventional foam regulators that can be used in the compositions according to the invention include, for example, polysiloxane-silica mixtures, the finely divided silica contained therein preferably being silanized or otherwise hydrophobized. The polysiloxanes can consist of linear compounds as well as crosslinked polysiloxane resins, as well as mixtures thereof. Other defoamers are paraffin hydrocarbons, in particular microparaffins and paraffin waxes, whose melting point is above 40°C, saturated fatty acids or soaps with, in particular, 20 to 22 carbon atoms, e.g., sodium behenate, and alkali metal salts of phosphoric acid mono- and / or dialkyl esters in which the alkyl chains each have 12 to 22 carbon atoms. Among these, sodium monoalkyl phosphate and / or dialkyl phosphate with C16-18 alkyl groups is preferably used. The proportion of foam regulators may preferably be 0.2 to 2 wt.%, particularly preferably not more than 1 wt.-%, based on the total weight of the product.

[0054] To adjust the desired pH, 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 alkali metal hydrogen sulfates, or bases, in particular ammonium or alkali metal hydroxides, preferably sodium hydroxide. Such pH regulators are preferably present in the agents according to the invention in amounts of no more than 10% by weight, in particular from 0.5 to 6% by weight, particularly preferably from 0.3 to 2% by weight, based on the total weight of the agent.

[0055] As a further component, agents according to the invention may contain an organic solvent. The addition of organic solvents has a beneficial effect on the enzyme stability and cleaning performance of these agents. Preferred organic solvents come from the group of mono- or polyhydric alcohols, alkanolamines, or glycol ethers.The solvents are preferably selected from ethanol, n- or i-propanol, butanol, glycol, propanediol, butanediol, glycerin, diglycol, propyl diglycol, butyl diglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, methoxytriglycol, ethoxytriglycol, butoxytriglycol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, propylene glycol t-butyl ether and mixtures of these solvents. The weight proportion of these organic solvents in the total weight of the compositions according to the invention is preferably 0.1 to 10 wt.%, preferably 0.2 to 8.0 wt.% and more preferably 0.5 to 5.0 wt.%.A particularly preferred organic solvent that is particularly effective with regard to stabilizing the compositions is glycerol and 1,2-propylene glycol. Liquid compositions preferably comprise at least one polyol, preferably from the group consisting of glycerol and 1,2-propylene glycol, based on the total weight of the composition, preferably in an amount of 0.1 to 10 wt. %, preferably 0.2 to 8.0 wt. %, and more preferably 0.5 to 5.0 wt. %. Further preferred organic solvents are organic amines and alkanolamines. Compositions according to the invention preferably contain these amines in amounts of 0.1 to 10 wt. %, preferably 0.2 to 8.0 wt. % and more preferably 0.5 to 5.0 wt. % based on the total weight of the composition. A particularly preferred alkanolamine is ethanolamine.

[0056] Furthermore, the agents according to the invention (in particular for automatic dishwashing) can contain bleach catalysts. The usable bleach catalysts include, but are not limited to, the group of bleach-enhancing transition metal salts and transition metal complexes, preferably Mn, Fe, Co, Ru, or Mo complexes, particularly preferably from the group of manganese and / or cobalt salts and / or complexes, in particular cobalt (ammine) complexes, cobalt (acetate) complexes, cobalt (carbonyl) complexes, cobalt or manganese chlorides, manganese sulfate, and complexes of manganese with 1,4,7-trimethyl-1,4,7-triazacyclononane (Mn5-TACN) or 1,2,4,7-tetramethyl-1,4,7-triazacyclononane (Mn4-TACN).

[0057] Preference is given to automatic dishwashing detergents which contain 0.001 to 1% by weight, preferably 0.01 to 0.1% by weight, of bleach catalyst, preferably a Mn complex, in particular a complex of manganese with 1,4,7-trimethyl-1,4,7-triazacyclononane (Mns-TACN) or 1,2,4,7-tetramethyl-1,4,7-triazacyclononane (M-TACN).

[0058] Agents according to the invention can contain further hydrolytic enzymes or other enzymes in a concentration appropriate for the effectiveness of the agent. A further embodiment of the invention thus represents agents which further comprise one or more enzymes. Preferred enzymes are all enzymes which can exhibit catalytic activity in the agent according to the invention, in particular selected from proteases, amylases, cellulases, hemicellulases, mannanases, tannases, xylanases, xanthanases, xyloglucanases, ß-glucosidases, pectinases, carrageenases, perhydrolases, oxidases, oxidoreductases, and mixtures thereof. Enzymes are advantageously present in the agent in an amount of 1 x 10 -8 to 5 wt.%, based on active protein and total weight of the agent. Increasingly preferably, each enzyme is present in an amount of 1 x 10 -7to 3 wt. %, from 0.00001 to 1 wt. %, from 0.00005 to 0.5 wt. %, from 0.0001 to 0.1 wt. %, and particularly preferably from 0.0001 to 0.05 wt. %, based on the active protein and the total weight of the agent. Enzymes particularly preferably exhibit synergistic cleaning performance against certain soils or stains, i.e., the enzymes contained in the agent composition support each other in their cleaning performance.

[0059] Further active ingredients may also be contained in washing or cleaning agents according to the invention.

[0060] Another subject of the invention is a method for removing greasy or oily soiling from textiles or hard surfaces, comprising the steps

[0061] (i) Providing a washing or cleaning agent according to one of claims 3 or 4

[0062] (ii) Where appropriate, preparing a washing or cleaning solution by diluting the washing or cleaning agent with water;

[0063] (iii) bringing the washing or cleaning agent or the washing or cleaning solution into contact with the surface to be cleaned;

[0064] (iv) allowing the washing or cleaning agent or the washing or cleaning solution to take effect;

[0065] (v) Rinse with water.

[0066] In such a process, it is preferred that the pH of the washing or cleaning agent or the washing or cleaning solution during use is between 2 and 12, preferably between 3 and 10, particularly preferably between 4 and 9 (measured at room temperature). Furthermore, it is preferred that at least one of steps (ii) to (iv), preferably all steps (ii) to (iv), is carried out at a temperature of 20 to 80°C, preferably at a temperature of less than 50°C, particularly preferably at a temperature of 20 to 30°C.

[0067] In a preferred embodiment, this is a method for dishwashing. This includes both manual and automatic methods. It is particularly preferred to use a method for automatic dishwashing.

[0068] In a further preferred embodiment, this is a process for textile washing, preferably a mechanical process for textile washing. EXAMPLES

[0069] Example 1: Biosurfactants as additives in lipase-catalyzed hydrolysis of solid fats

[0070] The removal of fats from a surface by lipases alone or in combination with biosurfactants was investigated using a quartz crystal microbalance with dissipation monitoring (QCM-D for short; QCM = quartz crystal microbalance; D = dissipation). Using this surface-sensitive method, the adsorption and desorption processes of materials or substances (as well as the associated processes, e.g., swelling) on ​​a sensor surface can be monitored in situ with ng resolution. The sensors used for this purpose consist of a thin quartz crystal disc surrounded by two metal electrodes (thin gold layer on both sides). Due to the piezoelectric properties of the quartz, it can be mechanically deformed when an external electrical voltage is applied (depending on the crystal cut and the sign of the voltage). When an alternating voltage is applied, the quartz sensor begins to oscillate.At a specific frequency, the resonance frequency f, the quartz sensor oscillates in resonance. Since the resonance frequency depends on the thickness of the disc, by measuring changes in the resonance frequency over time, conclusions can be drawn about changes in mass or layer thickness for the processes mentioned above. In addition to the change in the resonance frequency Af, the change in dissipation AD (energy loss) is also measured. This parameter describes the energy loss of the oscillating system due to viscoelastic properties of the adsorbed or desorbed material film. By simultaneously measuring Af and AD, viscoelastic models can be created. In simple cases, i.e. with rigid, thin and homogeneously distributed films that are firmly bonded to the quartz crystal surface, mass changes Am due to adsorption and desorption processes can be calculated solely from the frequency change Af (Sauerbrey equation) (see, for example, Snabe et al.(2003), Lag phase and hydrolysis mechanisms of triacylglycerol film lipolysis, Chemistry and Physics of Lipids, 125: 69-82; QSense analysis documentation & manufacturer's instructions, available at: https: / / www.biolinscientific.eom / asense / instruments / gsense-pro#knowledae).

[0071] Implementation:

[0072] The quartz sensors of the quartz crystal microbalance (QSense Analyzer in the QSense Flow module QFM 401, ex. QSense®), coated with a thin layer of gold, were prepared for testing by cleaning them with a hydrogen peroxide-ammonia-Millipore water solution (ratio 1:1:5) at 75°C. Subsequently, the frequencies and dissipations of the fundamental tone and the overtones of the cleaned quartz sensors were measured in air at 20°C (termination criterion: temporally constant values ​​for frequency and dissipation, i.e., the frequency and dissipation were determined over a time course at which the system adjusted to a stable frequency and dissipation). The quartz sensors were then spin-coated with a model grease solution (1% tricaprin in toluene). Spin coating is a method known to those skilled in the art and allows the application of very thin substrate layers with a thickness of a few nm or mm (see, for example, Olesen et al., Revealing Detergent Efficiency and Mechanism by Real-Time Measurement Using a Novel and Tailored QCM-D methodology, Tenside Surf. Det. 53 (2016) 5: 488-494). Subsequently, the frequencies and dissipations of the fundamental tone and the overtones of the grease-coated quartz sensors were measured in air.

[0073] The measuring cell was then filled with Millipore water and the frequencies and dissipations of the fundamental tone and the overtones of the grease-coated quartz sensors were measured in water at 20°C (baseline). The respective biosurfactant or lipase solution (in Millipore water) was then passed through at 20°C and a flow rate of 50 pl / min. The frequencies and dissipations of the fundamental tone and the overtones of the grease-coated quartz sensors were measured over time (termination criterion: temporally constant values ​​for frequency and dissipation).

[0074] After completion of the measurement, the measuring cell was rinsed with a 2% aqueous surfactant solution.

[0075] The described process thus comprises one main process step: cleavage of tricaprin by lipase and removal of the fatty layer by biosurfactants. Lipex Evity 200 L (Novozymes) was used as the lipase. The following biosurfactants were tested:

[0076] Sophance LA-A (lactonic sophorolipid)

[0077] Mirasoft SL A60.

[0078] In further experiments, the following surfactants were used instead of these sophorolipids:

[0079] Rewoferm RL 100 (dirhamnolipid)

[0080] Glucopon 600 CSUP (alkyl polyglycoside)

[0081] Mannosylerythritol lipid.

[0082] The reaction times for the removal of tricaprin from the sensor surface were determined from the temporal progression of the frequency values. The reaction time is calculated from the difference between the time of the maximum frequency change and the time of the frequency change after the addition of lipase and sophorolipid. The reaction times thus determined were compared with experiments in which no sophorolipid was added, but the removal of tricaprin was achieved exclusively by lipase, as well as with experiments in which a different surfactant was used instead of sophorolipid.

[0083] The results are shown in the table below:

[0084] It is clear that the exclusive use of sophorolipids does not result in measurable fat removal, but rather requires the addition of lipids. Other biosurfactants such as rhamnolipid or mannosylerythritol lipid do not lead to any improvement over the use of lipids alone. Only the conventional surfactant, an alkyl polyglycoside, led to even faster fat removal.

Claims

Patent claims: 1 . System for removing greasy or oily soils from textiles or hard surfaces, the system containing at least one sophorolipid and at least one lipase.

2. Use of a system containing at least one sophorolipid and at least one lipase for removing greasy or oily soils from textiles or hard surfaces.

3. Washing or cleaning agent containing a system for removing greasy or oily soils from textiles or hard surfaces according to claim 1.

4. Washing or cleaning agent according to claim 3, characterized in that it contains at least one further active ingredient, preferably selected from the group comprising further surfactants, builders, complexing agents, polymers, glass corrosion inhibitors, corrosion inhibitors, bleaching agents, bleach activators, bleach catalysts, water-miscible organic solvents, hydrotropes, further enzymes, enzyme stabilizers, sequestering agents, electrolytes, pH adjusters, opacifiers, pearlescent agents, viscosity regulators, fluorescent agents, optical brighteners, anti-redeposition agents, graying inhibitors, soil-removing polymers, dye transfer inhibitors, antistatic agents, crease inhibitors, shrinkage inhibitors, ironing aids, repellents and impregnating agents, swelling and slip-resistant agents, skin-care active ingredients, softening components, UV absorbers, foam inhibitors, antimicrobial active ingredients, germicides, fungicides, antioxidants,Preservatives, bittering agents, colors and fragrances.

5. A method for removing greasy or oily soiling from textiles or hard surfaces, comprising the steps (i) Providing a washing or cleaning agent according to one of claims 3 or 4 (ii) Where appropriate, preparing a washing or cleaning solution by diluting the washing or cleaning agent with water; (iii) bringing the washing or cleaning agent or the washing or cleaning solution into contact with the surface to be cleaned; (iv) allowing the washing or cleaning agent or the washing or cleaning solution to take effect; (v) Rinse with water.

6. The method according to claim 5, characterized in that the pH of the washing or cleaning agent or the washing or cleaning solution during use is between 2 and 12, preferably between 3 and 10, particularly preferably between 4 and 9 (measured at room temperature).

7. The process according to claim 5 or 6, characterized in that at least one of steps (ii) to (iv), preferably all steps (ii) to (iv), is carried out at a temperature of 20 to 80°C, preferably at a temperature of less than 50°C, particularly preferably at a temperature of 20 to 30°C.

8. A method according to any one of claims 5 to 7, characterized in that it is a method for dishwashing.

9. A method according to any one of claims 5 to 7, characterized in that it is a method for textile washing, preferably a mechanical method for textile washing.

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