Detergents and cleaning agents comprising lignin derivatives

Abstract

Sulphated and / or carboxylated lignin derivatives are suitable as dispersing agents for detergents and cleaning applications.

Description

[0001] Detergents and cleaning agents containing lignin derivatives

[0002] The present invention relates to the use of functionalized lignin for washing textiles or cleaning hard surfaces as well as to washing or cleaning agents containing such lignin derivatives.

[0003] In addition to surfactants, which are primarily responsible for removing soiling from the objects to be washed or cleaned, washing and cleaning agents usually contain a not inconsiderable number of auxiliary substances that contribute to the washing or cleaning result, such as bleaching agents, enzymes or anti-redeposition agents, and probably the most important of these are so-called builder materials.

[0004] Builder materials are responsible for removing or neutralizing metal ions, such as calcium and magnesium, from the aqueous washing or cleaning solution and from soils on the items being washed or cleaned. This can be achieved by detrimental precipitation or, more preferably, by exchanging or complexing the metal ions and keeping them in solution. Complexing builders include tripolyphosphate, ethylenediaminetetraacetic acid, aminotrismethylenephosphonic acid, as well as polymeric organic polycarboxylic acids, such as polyacrylic acid and acrylic acid-maleic acid copolymers.

[0005] Some of the builder materials used long ago turned out to be ecologically questionable, and it is human nature to always search for more effective materials.

[0006] The present invention makes a contribution to the field of polymeric organic builder substances.

[0007] Esterified or etherified lignins that can be converted into carbon fibers are known from the German patent application DE 10 2017 128 339 A1.

[0008] The present invention relates to washing or cleaning agents containing sulfated and / or carboxylated lignin derivatives of the general formulas (I) or (II), in which M + represents a hydrogen or alkali metal cation or an ammonium ion and L represents a lignin to which the S atom of the general formula (I) and / or the carbonyl C atom of the formula (II) is bonded via an O atom located on the lignin.

[0009] Lignins have a structure according to the following formula and are generated as a waste product in paper production and biorefineries. They are a component of lignocelluloses, which essentially consist of the three main components cellulose, hemicellulose, and lignin. Lignins that are particularly useful for the production of derivatives according to the general formulas (I) and (II) are obtained through an organosolv process. In this process, lignocelluloses or lignocellulose-containing biomass are treated with organic solvents and, if necessary, catalysts at elevated temperatures of normally 100°C to 250°C. Suitable organic solvents include methanol, ethanol, butanol, ethylene glycol, propylene glycol, formic acid, acetic acid, tetrahydrofuran, glycerol, and acetone. Catalysts used include sulfuric or hydrochloric acid or aluminum trichloride.

[0010] Lignins thus obtainable can be reacted with sulfur trioxide to form derivatives of the general formula (I) or with dicarboxylic acids or their reactive derivatives, such as dicarboxylic anhydrides or dicarboxylic acid halides, to form lignin derivatives of the general formula (I). In a preferred embodiment of the invention, the lignin derivatives contain both sulfate groups and carboxylate groups, which can be achieved by reacting the lignins with dicarboxylic anhydrides and subsequently with sulfur trioxide. The lignin underlying the lignin derivative essential to the invention preferably has a number-average molecular weight in the range from 500 g / mol to 30,000 g / mol, in particular in the range from 1,000 g / mol to 15,000 g / mol.

[0011] The degree of functionalization in the lignin derivative essential to the invention is preferably in the range of 10% to 100% of sulfate groups and / or carboxylate groups, in particular from 40% to 95%. A degree of functionalization of 100% means that all OH groups of the lignin molecule are converted to dicarboxylic acid monoester functions or sulfuric acid half-ester functions, and a degree of functionalization of, for example, 10%, 40%, or 95% means that 10%, 40%, or 95% of the OH groups of the lignin molecule are correspondingly esterified, and the remainder to 100% is still present as free OH groups.

[0012] The lignin derivatives essential to the invention are suitable for keeping water hardness-induced precipitates dispersed in aqueous systems so that they do not deposit on textiles or hard surfaces and corresponding incrustations on laundry, dishes and / or machine parts are reduced or even completely avoided.

[0013] The invention further relates to the use of such lignin derivatives as dispersants and for reducing incrustation formation when washing textiles or cleaning hard surfaces. They are normally used together with water and, as a rule, other common ingredients of detergents or cleaning agents. This use can be carried out manually or, if necessary, with the aid of a conventional household washing machine or dishwasher. It is possible and expedient to apply the detergent or cleaning agent and the lignin derivative simultaneously. Simultaneous application can be carried out particularly advantageously by using a detergent or cleaning agent that contains the lignin derivative.

[0014] A textile washing process preferably takes place at a temperature of 15°C to 60°C, particularly preferably at a temperature of 20°C to 40°C. The textile washing process further preferably takes place at a pH of 6 to 11, particularly preferably at a pH of 7.5 to 9.5. The use concentration of the lignin derivative defined above in the washing or cleaning liquor is preferably in the range of 0.001 g / l to 5 g / l, in particular of 0.01 g / l to 0.5 g / l.

[0015] Agents that contain a lignin derivative essential to the invention or are used together with it can contain all other customary ingredients of such agents that do not interact undesirably with the active ingredient essential to the invention, in particular surfactant. The agent preferably contains the above-defined lignin derivative in amounts of 0.01 wt.% to 15 wt.%, in particular 0.5 wt.% to 10 wt.%, whereby this and the following wt.% data refer to the entire agent, unless otherwise stated.

[0016] Detergents usable in connection with the present invention, which may be in the form of powdered solids, in compacted particle form, as solutions, dispersions, or suspensions, may contain all known ingredients commonly found in such detergents. The detergents may, in particular, contain additional builders, surface-active surfactants, water-miscible organic solvents, enzymes, sequestering agents, electrolytes, pH regulators, polymers with special effects, such as soil-release polymers, dye transfer inhibitors, graying inhibitors, crease-reducing and shape-retaining polymeric active ingredients, and other auxiliaries, such as optical brighteners, foam regulators, dyes, and fragrances.

[0017] The agents may contain one or more surfactants, particularly anionic surfactants, non-ionic surfactants and mixtures thereof, but may also contain cationic and / or amphoteric surfactants.

[0018] All nonionic surfactants known to the person skilled in the art can be used as nonionic surfactants. Nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, especially primary alcohols with preferably 8 to 18 carbon atoms and an average of 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 can contain linear and methyl-branched radicals in a mixture, as is usually the case in oxo alcohol radicals. However, alcohol ethoxylates with linear radicals from alcohols of native origin with 12 to 18 carbon atoms, e.g., from coconut, palm, tallow, or oleyl alcohol, and an average of 2 to 8 moles of EO per mole of alcohol are particularly preferred.Preferred ethoxylated alcohols include, for example, C12-C14 alcohols with 3 EO or 4 EO, C8-C14 alcohols with 7 EO, C18-C19 alcohols with 3 EO, 5 EO, 7 EO, or 8 EO, C12-C18 alcohols with 3 EO, 5 EO, or 7 EO, and mixtures thereof, such as mixtures of C12-C14 alcohols with 3 EO and C8-C19 alcohols with 5 EO. The stated degrees of ethoxylation represent statistical averages, which for a specific product can correspond to a whole or fractional number. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).

[0019] Alternatively or in addition to these non-ionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO, or 40 EO. Alkyl glycosides of the general formula R can also be used as additional non-ionic surfactants. 5 O(G)x can be used in the R 5a 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.

[0020] Another class of preferably used nonionic surfactants, which are 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 with 1 to 4 carbon atoms in the alkyl chain.

[0021] Nonionic 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. The amount of these nonionic surfactants is preferably no more than that of the ethoxylated fatty alcohols, in particular no more than half that amount.

[0022] 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. Examples of anionic surfactants used are those of the sulfonate and sulfate type.Preferred sulfonate-type surfactants are C 8 -n-alkylbenzenesulfonates, olefinsulfonates, i.e., mixtures of alkene and hydroxyalkanesulfonates, and disulfonates, such as those obtained, for example, from C 12-18 monoolefins with terminal or internal double bonds by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products. Also suitable are alkanesulfonates obtained from C 18 -s-alkanes, for example, by sulfochlorination or sulfoxidation followed by hydrolysis or neutralization. Esters of α-sulfofatty acids (estersulfonates), for example, the α-sulfonated methyl esters of hydrogenated coconut, palm kernel, or tallow fatty acids, are also suitable.

[0023] Other suitable anionic surfactants are sulfated fatty acid glycerol esters. Fatty acid glycerol esters are understood to be the mono-, di-, and triesters, as well as mixtures thereof, as obtained by esterifying glycerol with 1 to 3 mol of fatty acid or by transesterifying triglycerides with 0.3 to 2 mol of glycerol. Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids with 6 to 22 carbon atoms, for example, caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid, or behenic acid.

[0024] Also suitable are alkyl sulfates of the general formula

[0025] RO-SOsM, in which R is a linear, branched-chain or cyclic saturated hydrocarbon radical having 12 to 18, in particular 12 to 14, carbon atoms and M is a countercation leading to the charge neutralization of the sulfuric acid half ester, in particular a sodium or potassium ion or an ammonium ion of the general formula R 1 R 2 R 3 R 4 N + , in the R 1 , R 2 , R 3 , and R 4independently of one another represents hydrogen, an alkyl group having 1 to 4 C atoms, or a hydroxyalkyl group having 2 to 3 C atoms. Preferred R radicals are derived from native C12-C18 fatty alcohols, such as, for example, coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl, or stearyl alcohol, or the C10-C20 oxo alcohols or secondary alcohols of these chain lengths. Also preferred are alkyl sulfates of the stated chain length which contain a synthetic, petrochemically produced straight-chain alkyl radical and which have degradation behavior analogous to that of the corresponding compounds based on oleochemical raw materials. C12-C16 alkyl sulfates and C12-C14 alkyl sulfates are particularly preferred.

[0026] 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 C8-n alcohols with an average of 3.5 mol of ethylene oxide (EO) or C8-s fatty alcohols with 1 to 4 EO. Other suitable anionic surfactants are the salts of alkyl sulfosuccinic acid, which are also referred to as sulfosuccinates or sulfosuccinic acid esters and are the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contain Ca-is fatty alcohol residues or mixtures thereof. Particularly preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants.Sulfosuccinates, whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are particularly preferred. It is also possible to use alk(en)ylsuccinic acid, preferably with 8 to 18 carbon atoms in the alk(en)yl chain, or its salts.

[0027] Other anionic surfactants that may be considered include soaps. Saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid, and behenic acid, as well as soap mixtures derived from natural fatty acids, such as coconut, palm kernel, or tallow fatty acids, are particularly suitable.

[0028] The anionic surfactants, including soaps, can be present in the form of their sodium, potassium, or ammonium salts, as well as soluble salts of organic bases, such as mono-, di-, or triethanolamine. The anionic surfactants are preferably present in the form of their sodium or potassium salts, especially in the form of the sodium salts.

[0029] Instead of the surfactants mentioned or in combination with them, cationic and / or amphoteric surfactants can also be used.

[0030] Cationic compounds of the following formulas can be used as cationic active substances:

[0031] Ri l +

[0032] Ri-N-(CH2) n -T-R2

[0033] (CH2) n -T-R2 where each group R 1 is independently selected from Ci-6 alkyl, alkenyl or hydroxyalkyl groups; each group R 2is independently selected from Ca-28 alkyl or alkenyl groups; R 3 = R 1 or (CH2)nTR 2 ; R 4 = R 1 or R 2 or (CH2)nTR 2 ; T = -CH2-, -O- CO- or -CO-O- and n is an integer from 0 to 5.

[0034] Surfactants are contained in detergents in amounts of preferably 5 wt% to 50 wt%, in particular 8 wt% to 30 wt%.

[0035] For the care of textiles and to improve textile properties such as a softer “handle 1Textile softening compounds can be used for softening (softening) and reduced electrostatic charge (increased wearing comfort). The active ingredients in these formulations are quaternary ammonium compounds with two hydrophobic residues, such as disteraryldimethylammonium chloride. However, due to its insufficient biodegradability, this is increasingly being replaced by quaternary ammonium compounds that contain ester groups in their hydrophobic residues as predetermined breaking points for biodegradation.

[0036] Such "esterquats" with improved biodegradability can be obtained, for example, by esterifying mixtures of methyldiethanolamine and / or triethanolamine with fatty acids and subsequently quaternizing the reaction products with alkylating agents in a conventional manner. Dimethylolethyleneurea is a suitable finishing agent.

[0037] In addition to the lignin derivative essential to the invention, a washing or cleaning agent may contain one or more further water-soluble and / or water-insoluble, organic and / or inorganic builders.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 as well as 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, in particular polycarboxylates accessible by oxidation of polysaccharides or dextrins, and / or polymeric acrylic acids, methacrylic acids, maleic acids and copolymers thereof, which may also contain small proportions of polymerizable substances without carboxylic acid functionality.The relative molecular mass of the homopolymers of unsaturated carboxylic acids is generally between 5,000 g / mol and 200,000 g / mol, and that of the copolymers between 2,000 g / mol and 200,000 g / mol, preferably 50,000 g / mol to 120,000 g / mol, in each case based on the free acid. A particularly preferred acrylic acid-maleic acid copolymer has a relative molecular mass of 50,000 g / mol to 100,000 g / mol. Suitable, albeit less preferred, compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinyl methyl ethers, vinyl esters, ethylene, propylene, and styrene, in which the proportion of acid is at least 50% by weight. Terpolymers containing two unsaturated acids and / or their salts as monomers and vinyl alcohol and / or an esterified vinyl alcohol or a carbohydrate as the third monomer can also be used as water-soluble organic builder substances.The first acidic monomer or its salt is derived from a monoethylenically unsaturated Cs-Cs carboxylic acid, 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-Cs dicarboxylic acid, with maleic acid being particularly preferred, and / or a derivative of an allylsulfonic acid substituted in the 2-position with an alkyl or aryl radical. Such polymers generally have a relative molecular weight between 1,000 g / mol and 200,000 g / mol. Further preferred copolymers are those containing acrolein and acrylic acid / acrylic acid salts or vinyl acetate as monomers. The organic builder substances can be used, in particular for the production of liquid compositions, 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, especially their alkali salts.

[0038] Such additional organic builders can, if desired, be present in amounts of up to 40 wt.%, in particular up to 25 wt.%, and preferably from 1 wt.% to 8 wt.%. Amounts in the upper half of the above-mentioned ranges are preferably used in paste-like or liquid, especially water-based, compositions.

[0039] As water-insoluble, water-dispersible inorganic builder materials, crystalline or amorphous alkali aluminosilicates are used in particular, in amounts of up to 50 wt. %, preferably not more than 40 wt. %, and in liquid compositions in particular from 1 wt. % to 5 wt. %. Among these, crystalline sodium aluminosilicates of detergent quality, in particular zeolite A, P and optionally 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 larger than 30 μm and preferably consist of at least 80 wt. % particles with a size smaller than 10 μm. Their calcium binding capacity is generally in the range of 100 mg to 200 mg CaO per gram.

[0040] Suitable substitutes or partial substitutes for the aluminosilicate mentioned are crystalline alkali silicates, which can be present alone or in a mixture with amorphous silicates. The alkali silicates which can be used as builders preferably have a molar ratio of alkali oxide to SiO2 of less than 0.95, in particular from 1:1.1 to 1:12, and can be amorphous or crystalline. Preferred alkali silicates are sodium silicates, in particular amorphous sodium silicates, with a molar ratio Na2O:SiO2 of 1:2 to 1:2.8. The crystalline silicates which can be present alone or in a mixture with amorphous silicates are preferably crystalline phyllosilicates of the general formula Na2Si xC>2x+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 assumes the values ​​2 or 3. In particular, both β- and β-sodium disilicates (Na2Si2O5 y H2O) are preferred. Practically anhydrous crystalline alkali silicates prepared 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 a further preferred embodiment, a crystalline sodium layered silicate with a modulus of 2 to 3 is used, such as can be prepared from sand and soda. Crystalline sodium silicates with a modulus in the range of 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, such as is commercially available 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 in particular 1:1 to 2:1.

[0041] Inorganic 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.

[0042] In a preferred embodiment, the agent has a water-soluble builder block. The use of the term “builder block” is intended to express that the agent contains no builder substances other than those that are water-soluble, i.e. all builder substances contained in the agent are combined in the thus characterized “block”, with the exception of those amounts of substances that may be commercially present in small quantities as impurities or stabilizing additives in the other ingredients of the agent. The term “water-soluble” is to be understood to mean that the builder block dissolves without leaving any residue at the concentration resulting from the amount of the agent containing it used under normal 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 in the detergents. This is preferably composed of the components a) 5 wt.% to 35 wt.% citric acid, alkali metal citrate and / or alkali metal carbonate, which can also be at least partially replaced by alkali metal bicarbonate, b) up to 10 wt.% alkali metal silicate with a modulus in the range of 1.8 to 2.5, c) up to 2 wt.% phosphonic acid and / or alkali metal phosphonate, d) up to 50 wt.% alkali metal phosphate, and e) 0.5 wt.% to 10 wt.% of the lignin derivative essential to the invention, wherein the amounts relate to the entire detergent.

[0043] In a preferred embodiment, the water-soluble builder block contains, in addition to component e), at least 1 of components a) and b) in amounts greater than 0 wt.%.

[0044] With regard to component a), in a preferred embodiment, 15% to 25% by weight of alkali metal carbonate, which may be at least partially replaced by alkali metal bicarbonate, and up to 5% by weight, in particular 0.5% to 2.5% by weight, of citric acid and / or alkali metal citrate are present. In an alternative embodiment, component a) contains 5% to 25% by weight, in particular 5% to 15% by weight, of citric acid and / or alkali metal citrate and up to 5% by weight, in particular 1% to 5% by weight, of alkali metal carbonate, which may be at least partially replaced by alkali metal bicarbonate. If both alkali metal carbonate and alkali metal bicarbonate are present, component a) preferably comprises alkali metal carbonate and alkali metal bicarbonate in a weight ratio of 10:1 to 1:1.

[0045] With regard to component b), a preferred embodiment contains 1 wt.% to 5 wt.% alkali silicate with a modulus in the range of 1.8 to 2.5.

[0046] With regard to component c), in a preferred embodiment, up to 1 wt.% phosphonic acid and / or alkali metal phosphonate are present. Phosphonic acids also include optionally substituted alkylphosphonic acids, which may also have multiple phosphonic acid moieties (so-called polyphosphonic acids). They are preferably selected from the hydroxy- and / or aminoalkylphosphonic acids and / or their alkali metal salts, such as, for example, dimethylaminomethanediphosphonic acid, 3-aminopropane-1-hydroxy-1,1-diphosphonic acid, 1-amino-1-phenylmethanediphosphonic 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 desired mixtures. In further preferred embodiments of agents according to the invention, neither phosphonic acid nor alkali phosphonate is contained.

[0047] With regard to component d), in a preferred embodiment, 15% to 35% by weight of alkali phosphate, in particular trisodium polyphosphate, may be present, if permitted. In further preferred embodiments of agents according to the invention, no alkali phosphate is present.

[0048] With regard to component e), in a preferred embodiment of the compositions, 1.5% 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, are optionally present in addition to the lignin derivative essential to the invention. Among these polymeric polycarboxylates, the homopolymers of acrylic acid are particularly preferred, and among these, those with an average molecular weight in the range of 5,000 g / mol to 15,000 g / mol (PA standard).

[0049] Enzymes that can be used in the products include those from the class of lipases, cutinases, amylases, pullulanases, mannanases, cellulases, hemicellulases, xylanases, and peroxidases, as well as 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®; and cellulases such as Celluzyme® and / or Carezyme®. Enzymatic active ingredients derived from fungi or bacteria, such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus, Humicola lanuginosa, Humicola insolens, Pseudomonas pseudoalcaligenes, or Pseudomonas cepacia, are particularly suitable. The enzymes used, if any, can be adsorbed on carriers and / or embedded in coating substances to protect them against premature inactivation. They are preferably present in detergents in amounts of up to 10 wt.%, in particular from 0.2 wt.% to 2 wt.%.

[0050] In a preferred embodiment, the agent contains 5 wt.% to 50 wt.%, in particular 8 to 30 wt.% anionic and / or non-ionic surfactant, up to 60 wt.%, in particular 5 to 40 wt.% builder substance and 0.2 wt.% to 2 wt.% enzyme selected from lipases, cutinases, amylases, pullulanases, mannanases, cellulases, oxidases and peroxidases and mixtures thereof.

[0051] The organic solvents usable in the detergents, especially when in liquid or pasty form, include alcohols with 1 to 4 carbon atoms, especially methanol, ethanol, isopropanol, and tert-butanol; diols with 2 to 4 carbon atoms, especially ethylene glycol and propylene glycol; and mixtures thereof and the ethers derived from the aforementioned classes of compounds. Such water-miscible solvents are preferably present in the detergents in amounts not exceeding 30% by weight, especially from 6% to 20% by weight.

[0052] Naturally derived polymers that can be used as thickeners in aqueous liquid agents include agar-agar, carrageenan, tragacanth, gum arabic, alginates, pectins, polyoses, guar gum, locust bean gum, starch, dextrins, gelatin and casein, cellulose derivatives such as carboxymethylcellulose, hydroxyethyl and propylcellulose, and polymeric polysaccharide thickeners such as xanthan gum; in addition, fully synthetic polymers such as polyacrylic and polymethacrylic compounds, vinyl polymers, polycarboxylic acids, polyethers, polyimines, polyamides and polyurethanes can also be used as thickeners.

[0053] To adjust a desired pH value that does not arise automatically from the mixing of the other components, the products may contain system- and environmentally-compatible acids, in particular citric acid, acetic acid, tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid, and / or adipic acid, but also mineral acids, in particular sulfuric acid, or bases, in particular ammonium or alkali hydroxides. Such pH regulators are preferably present in the products in amounts of no more than 20% by weight, in particular between 1.2% and 17% by weight.

[0054] Soil release polymers, often referred to as "soil release" agents or "soil repellents" due to their ability to render the treated surface, for example the fiber, soil-repellent, include nonionic or cationic cellulose derivatives. 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. The preferably used soil release polyesters include compounds that are formally obtainable by esterification of two monomer moieties, where the first monomer is a dicarboxylic acid HOOC-Ph-COOH and the second monomer is a diol HO-(CHR 11 -) a OH, which is also known as the polymeric diol H-(O-(CHR 11 -) a ) bOH may be present. Wherein Ph denotes an o-, m- or p-phenylene radical which may bear 1 to 4 substituents selected from alkyl radicals having 1 to 22 C atoms, sulfonic acid groups, carboxyl groups and mixtures thereof, R 11 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. The polyesters obtainable from these preferably contain both monomer diol units -O-(CHR 11 -) a O- and polymer diol units -(O-(CHR 11 - ) a)bO-. 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 from 4 to 200, in particular from 12 to 140. The molecular weight or the average molecular weight or the maximum of the molecular weight distribution of preferred soil-release polyesters is in the range from 250 to 100,000, in particular from 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. Unless their acid groups are part of the ester bonds in the polymer, they are preferably present in salt form, especially as alkali or ammonium salts. Among these, sodium and potassium salts are particularly preferred.If desired, instead of the monomer HOOC-Ph-COOH, small amounts, in particular not more than 10 mol% based on the proportion of Ph with the meaning given above, of other acids containing at least two carboxyl groups can be present in the soil-release 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. Preferred diols include HO-(CHR). 11 -) a OH includes those in which R 11 hydrogen and a is a number from 2 to 6, and those in which a has the value 2 and R 11 is selected from hydrogen and the alkyl radicals having 1 to 10, in particular 1 to 3, carbon atoms. Among the latter, diols are those of the formula HO-CH2-CHR 11 -OH, in the R 11has the abovementioned meaning, is 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 with an average molecular weight in the range from 1000 to 6000. If desired, these polyesters can also be end-capped, with suitable end groups being alkyl groups having 1 to 22 carbon atoms and esters of monocarboxylic acids. The end groups bound via ester bonds can be based on alkyl, alkenyl and aryl monocarboxylic acids with 5 to 32 C atoms, in particular 5 to 18 C atoms.These include valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, undecenoic acid, lauric acid, lauroleic 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, eleostearic acid, arachidic acid, gadoleic acid, arachidonic acid, behenic acid, erucic acid, brassidic acid, clupanodonic acid, lignoceric acid, cerotic acid, melissic acid, benzoic acid, which can carry 1 to 5 substituents with a total of up to 25 C atoms, in particular 1 to 12 C atoms, for example tert-butylbenzoic acid. The end groups can also be based on hydroxymonocarboxylic acids with 5 to 22 C atoms, which include, for example, hydroxyvaleric acid, hydroxycaproic acid, ricinoleic acid, its hydrogenation product hydroxystearic acid, and o-, m- and p-hydroxybenzoic acid.The hydroxymonocarboxylic acids can, in turn, be linked to one another via their hydroxyl group and their carboxyl group and thus be present multiple times in an end group. The number of hydroxymonocarboxylic acid units per end group, i.e., their degree of oligomerization, is preferably in the range from 1 to 50, especially 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 5000 and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate is 50:50 to 90:10, are used alone or in combination with cellulose derivatives.

[0055] The dye transfer inhibitors suitable for use in textile washing agents include, in particular, polyvinylpyrrolidones, polyvinylimidazoles, polymeric N-oxides such as poly(vinylpyridine N-oxide) and copolymers of vinylpyrrolidone with vinylimidazole and, if appropriate, other monomers.

[0056] The products may contain anti-crease agents, as textile fabrics, especially those made of rayon, wool, cotton, and their blends, can be prone to crease because the individual fibers are sensitive to bending, kinking, pressing, and crushing across the fiber direction. These include, for example, synthetic products based on fatty acids, fatty acid esters, fatty acid amides, fatty alkylol esters, fatty alkylolamides, or fatty alcohols, which are usually reacted with ethylene oxide, or products based on lecithin or modified phosphoric acid esters.

[0057] The purpose of graying inhibitors is to keep the dirt detached from the hard surface, and in particular from the textile fiber, suspended in the liquor. Suitable for this purpose are water-soluble colloids, usually of an organic nature, such as starch, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose, or salts of acidic sulfuric acid esters of cellulose or starch. Water-soluble polyamides containing acidic groups are also suitable for this purpose. Starch derivatives other than those mentioned above can also be used, for example aldehyde starches. Preference is given to cellulose ethers, such as carboxymethylcellulose (Na salt), methylcellulose, hydroxyalkylcellulose, and mixed ethers, such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose, and mixtures thereof, for example in amounts of 0.1 to 5% by weight, based on the agent.

[0058] The agents may contain optical brighteners, among these in particular derivatives of diaminostilbene disulfonic acid or its alkali metal salts. Suitable examples are salts of 4,4'-bis(2-anilino-4-morpholino-1,3,5-triazinyl-6-amino)stilbene-2,2'-disulfonic acid or similarly structured compounds that carry a diethanolamino group, a methylamino group, an anilino group, or a 2-methoxyethylamino group instead of the morpholino group. Furthermore, brighteners of the substituted diphenylstyryl type may be present, for example the alkali metal salts of 4,4'-bis(2-sulfostyryl)-diphenyl, 4,4'-bis(4-chloro-3-sulfostyryl)-diphenyl, or 4-(4-chlorostyryl)-4'-(2-sulfostyryl)-diphenyl. Mixtures of the above-mentioned optical brighteners can also be used.

[0059] Particularly when used in automatic washing processes, it can be advantageous to add conventional foam inhibitors to the detergents. Suitable foam inhibitors include, for example, soaps of natural or synthetic origin that contain a high proportion of C18-C24 fatty acids. Suitable non-surfactant foam inhibitors include, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica, as well as paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica or bisfatty acid alkylenediamides. Mixtures of different foam inhibitors, for example, those made of silicones, paraffins, or waxes, are also advantageously used. The foam inhibitors, in particular silicone- and / or paraffin-containing foam inhibitors, are preferably bound to a granular, water-soluble or water-dispersible carrier substance.In particular, mixtures of paraffins and bistearylethylenediamide are preferred.

[0060] Suitable peroxygen compounds optionally contained in the agents, particularly agents in solid form, are in particular organic peracids or peracidic salts of organic acids, such as phthalimidopercaproic acid, perbenzoic acid or salts of diperdodecanedioic acid, hydrogen peroxide and inorganic salts which release hydrogen peroxide under the washing conditions, such as perborate, percarbonate and / or persilicate. Hydrogen peroxide can also be generated with the aid of an enzymatic system, i.e. an oxidase and its substrate. If solid peroxygen compounds are to be used, these can be used in the form of powders or granules, which can also be coated in a manner known in principle. Particular preference is given to alkali percarbonate, alkali perborate monohydrate, alkali perborate tetrahydrate or, especially in liquid agents, hydrogen peroxide in the form of aqueous solutions containing 3% to 10% by weight.-% hydrogen peroxide. Peroxygen compounds are preferably present in detergents in amounts of up to 50 wt.%, in particular from 5 wt.% to 30 wt.%.

[0061] In addition, conventional bleach activators which form peroxocarboxylic acids or peroxoimidic acids under perhydrolysis conditions and / or conventional bleach-activating transition metal complexes can be used. The optional component of the bleach activators, which is present in particular in amounts of 0.5% by weight to 6% by weight, comprises the commonly used N- or O-acyl compounds, for example multiply acylated alkylenediamines, in particular tetraacetylethylenediamine, acylated glycolurils, in particular tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, urazoles, diketopiperazines, sulfurylamides and cyanurates, as well as carboxylic acid anhydrides, in particular phthalic anhydride, carboxylic acid esters, in particular sodium isononanoylphenolsulfonate, and acylated sugar derivatives, in particular pentaacetylglucose, and cationic nitrile derivatives such as trimethylammonium acetonitrile salts.To prevent interaction with the peroxygen compounds during storage, the bleach activators can be coated with coating substances or granulated in a known manner. Tetraacetylethylenediamine granulated with carboxymethylcellulose with average particle sizes of 0.01 mm to 0.8 mm, granulated 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine, and / or trialkylammonium acetonitrile formulated in particle form are particularly preferred. In detergents, such bleach activators are preferably present in amounts of up to 8 wt.%, in particular from 2 wt.% to 6 wt.%, based in each case on the total detergent.

[0062] The production of solid detergents is straightforward and can be carried out in a known manner, for example, by spray drying or granulation. For the production of detergents with increased bulk density, particularly in the range of 650 g / l to 950 g / l, a process including an extrusion step is preferred. Detergents in the form of aqueous solutions or solutions containing other conventional solvents are particularly advantageously produced by simply mixing the ingredients, which can be added in bulk or as a solution to an automatic mixer.

[0063] In a preferred embodiment, the agents, especially in concentrated liquid form, are presented as a portion in a fully or partially water-soluble coating. This portioning facilitates dosing for the consumer.

[0064] The products can be packaged in foil pouches, for example. Pouches made of water-soluble foil eliminate the need for consumers to tear open the packaging. This allows for convenient dosing of a single portion, sufficient for one wash cycle, by placing the pouch directly into the washing machine or dishwasher, or by dropping the pouch into a specific amount of water, for example, in a bucket, bowl, or hand basin. The foil pouch surrounding the portion of the product dissolves without leaving any residue when a certain temperature is reached.

[0065] Numerous processes exist in the prior art for producing water-soluble detergent or cleaning agent portions, which are also fundamentally suitable for producing agents usable within the scope of the present invention. The most well-known processes are the tubular film process with horizontal and vertical seals. The thermoforming process (deep-drawing process) is also suitable for producing film bags or dimensionally stable detergent or cleaning agent portions. However, the water-soluble enclosures do not necessarily have to be made of a film material; they can also be dimensionally stable containers, which can be obtained, for example, by means of an injection molding process.

[0066] Furthermore, processes for producing water-soluble capsules from polyvinyl alcohol or gelatin are known, which in principle offer the possibility of providing capsules with a high fill level. The processes are based on the introduction of the water-soluble polymer into a forming cavity. The filling and sealing of the capsules takes place either synchronously or in sequential steps, with the latter being done through a small opening. The capsules are filled, for example, by a filling wedge arranged above two counter-rotating drums that have spherical half-shells on their surface. The drums guide polymer bands that cover the spherical half-shell cavities. Sealing takes place at the positions where the polymer band of one drum meets the polymer band of the opposite drum.At the same time, the filling material is injected into the developing capsule, with the injection pressure of the filling liquid pressing the polymer bands into the spherical half-shell cavities. A process for producing water-soluble capsules, in which filling occurs first and then sealing, is based on the so-called Bottle-Pack® process. In this process, a tube-like preform is inserted into a two-part cavity. The cavity is closed, sealing the lower tube section. The tube is then inflated to form the capsule shape within the cavity, filled, and finally sealed.

[0067] The shell material used to produce the water-soluble portion is preferably a water-soluble polymeric thermoplastic, particularly preferably selected from the group consisting of (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 the materials mentioned, preferably hydroxypropylmethylcellulose and / or polyvinyl alcohol blends. Polyvinyl alcohols are commercially available, for example under the trademark Mowiol® (Clariant). Polyvinyl alcohols particularly suitable for the present invention include, for example, Mowiol® 3-83, Mowiol® 4-88, Mowiol® 5-88, Mowiol® 8-88, and Clariant L648.The water-soluble thermoplastic used to produce the portion may optionally additionally comprise polymers selected from the group comprising acrylic acid-containing polymers, polyacrylamides, oxazoline polymers, polystyrenesulfonates, 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 is 70 mol% to 100 mol%, preferably 80 mol% to 90 mol%, particularly preferably 81 mol% to 89 mol%, and in particular 82 mol% 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 g / mol to 100,000 g / mol, preferably from 11,000 g / mol to 90,000 g / mol, particularly preferably from 12,000 g / mol to 80,000 g / mol and in particular from 13,000 g / mol to 70,000 g / mol.It is further preferred if the thermoplastics are present in amounts of at least 50% by weight, preferably at least 70% by weight, particularly preferably at least 80% by weight and in particular at least 90% by weight, in each case based on the weight of the water-soluble polymeric thermoplastic.

[0068] Example 1 : Preparation of lignin derivatives a) Preparation of the sulfated derivative P1

[0069] Pyridine (8.83 ml) was added to a solution of Organosolv lignin (10.0 g) and pyridine-sulfur trioxide complex (8.69 g) in anhydrous dimethylformamide (200 ml) under an argon atmosphere, and the solution was heated at 60 °C for 16 hours. After cooling to room temperature, 5 M sodium hydroxide solution (21.8 ml) was added. Pyridine, water, and dimethylformamide were then removed under reduced pressure. The residue was dissolved in water (80 ml) and purified by dialysis using 100 times the amount of water (molecular weight cut-off: 1000 Da) to remove low-molecular-weight impurities. The water from the dialysis solution was removed under reduced pressure, and the residue was dried at 70 °C. The final product P1 (3.00 g) was obtained. b) Preparation of the carboxylated and sulfated derivative P2

[0070] Organosolv lignin (10.0 g) was added portionwise to a solution of succinic anhydride (5.58 g) in 2-methyltetrahydrofuran (133 ml) heated to 80 °C, and the solution was stirred at 80 °C for 18 hours. After cooling to room temperature, the functionalized lignin was precipitated in 15 times the amount of water and filtered off. The solid was dried at 50 °C under reduced pressure to yield a carboxylated derivative (10.3 g). Under an argon atmosphere, the carboxylated derivative (4.50 g) and pyridine-sulfur trioxide complex (2.17 g) were dissolved in anhydrous dimethylformamide (90 ml). Pyridine (3.13 ml) was added, and the solution was heated to 60 °C for 16 hours. After cooling to room temperature, 5 M sodium hydroxide solution (5.45 ml) was added. Pyridine, water and dimethylformamide were then removed under reduced pressure.The residue was dissolved in water (40 ml) and purified by dialysis with 100 times the volume of water (molecular weight cut-off: 1000 Da) to remove low molecular weight impurities. The water from the dialysis solution was removed under reduced pressure, and the residue was dried at 70 °C; the final product P2 (5.1 g) was obtained.

[0071] Table 1 : Elemental analysis data P1 to P2 For the gel permeation chromatography (GPC) measurements a PSS SECcurity 2 An SEC system with Agilent Infinity 1260 II hardware was used. The system was equipped with a refractive index detector. DMAc with 0.03 wt% lithium bromide (flow rate 1 ml / min) at 35 °C was used as the mobile phase. Characterization was performed using the following columns: Agilent Mixed-C column and Agilent Mixed-E column. Polystyrene standards ranging from 370 Da to 2,520,000 Da were used for calibration.

[0072] Table 2: Mean numbers (M n ) and weight average (Mw) molecular weights

[0073] Example 2: Dispersing effect

[0074] 4.97 ml each of an aqueous CaCl 2 H2O solution (20.641 g / l) and an aqueous MgSO 4 7 H2O solution (11.537 g / l) were added dropwise at a rate of 0.5 ml / min to 100 ml of a wash liquor WO heated to 40 °C and containing 3.59 g / l of a builder-free powder detergent in water, and the turbidities were determined photometrically. For comparison, wash liquors W1 and W2, which had the same composition as WO but additionally contained 10.5 mg each of one of the polymers P1 or P2 prepared in Example 1, were tested under the same conditions. The titration was carried out using a Metrohm® 905 Titrando, two Metrohm® 800 Dosinos for addition, and a Metrohm® 801 Stirrer. A Metrohm® 662 Photometer and a Metrohm® 856 Conductivity Module were used for the measurement. At the end of the titration, the water hardness was 50°dH.

[0075] Table 3: Light transmittance It can be seen that, compared to the detergent without additive, the lignin derivatives P1 to P2, which are essential to the invention, keep the resulting CaCCh and MgCCh in solution for a longer period.

Claims

Patent claims 1 . Washing or cleaning agents containing sulfated and / or carboxylated lignin derivatives of the general formulas (I) or (II), L-SOä M + (I) in which M + represents a hydrogen or alkali metal cation or an ammonium ion and L represents a lignin to which the S atom of the general formula (I) and / or the carbonyl C atom of the formula (II) is bonded via an O atom located on the lignin.

2. Agent according to claim 1, characterized in that it contains 0.01 wt.% to 15 wt.%, in particular from 0.5 wt.% to 10 wt.% of the lignin derivative.

3. Agent according to claim 1 or 2, characterized in that it is present as a powdered solid, in compacted particle form, as a solution, dispersion or suspension.

4. Agent according to one of claims 1 to 3, characterized in that it contains 5 wt.% to 50 wt.%, in particular from 8 wt.% to 30 wt.% surfactant.

5. Agent according to one of claims 1 to 4, characterized in that it contains up to 40% by weight, in particular 1% by weight to 8% by weight, of additional organic builder substances.

6. Agent according to one of claims 1 to 5, characterized in that it contains up to 60% by weight, in particular from 5% by weight to 40% by weight, of inorganic builder substances.

7. Agent according to one of claims 1 to 6, characterized in that it contains a) 5 wt.% to 35 wt.% citric acid, alkali citrate and / or alkali carbonate, which can also be at least partially replaced by alkali hydrogen carbonate, b) up to 10 wt.% alkali silicate with a modulus in the range from 1.8 to 2.5, c) up to 2 wt.% phosphonic acid and / or alkali phosphonate, d) up to 50 wt.% alkali phosphate, and e) 0.5 wt.% to 10 wt.% of the lignin derivative.

8. Use of sulfated and / or carboxylated lignin derivatives of the general Formulas (I) or (II), L-SOs M + (I) in which M +represents a hydrogen or alkali metal cation or an ammonium ion and L represents a lignin to which the S atom of the general formula (I) and the carbonyl C atom of the formula (II) are bonded via an O atom located on the lignin, as dispersants and for reducing incrustation formation when washing textiles or cleaning hard surfaces.

9. Use according to claim 8, characterized in that the use concentration of the lignin derivative in the washing or cleaning liquor is in the range from 0.001 g / l to 5 g / l, in particular from 0.01 g / l to 0.5 g / l.

10. Agent according to one of claims 1 to 7 or use according to claim 8 or 9, characterized in that the lignin underlying the lignin derivative has a number-average molecular weight in the range from 500 g / mol to 30,000 g / mol, in particular in the range from 1,000 g / mol to 15,000 g / mol, and / or that the degree of functionalization in the lignin derivative is in the range from 10% to 100%, in particular from 40% to 95% of sulfate groups and / or carboxylate groups.

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