Detergent having increased washing power against oily and greasy soiling

Abstract

The invention relates to increasing the washing power of detergents against oily and greasy soiling. This is achieved by the use of compounds of general formula (I) in which each R is selected from -H and -O-C(=O)-R', and R' is selected from the alkyl groups having 6 to 10 C atoms and mixtures thereof, wherein at least 5% of the number of functional groups R are those which are not H.

Description

[0001] Detergent with increased washing power against oily and greasy soils

[0002] The present invention relates to textile detergents containing a specific star polymer, a textile washing process using such a star polymer, and the use of the star polymer to increase the washing performance of textile detergents against fat- or oil-based soils.

[0003] As a contribution to combating climate change, one of the most important goals in textile washing is to reduce carbon dioxide emissions per wash cycle. This can be achieved by lowering the washing temperature. To ensure that detergents used in textile washing maintain the desired washing power even under cold wash conditions, so-called washing power enhancers are often used.

[0004] Another important goal is the use of biodegradable detergent ingredients in order to avoid, as far as possible, the accumulation of non- or poorly degradable substances in the ecosystem.

[0005] The present invention aims to simultaneously meet both objectives. An additional factor that interferes with achieving this objective is that when the washing temperature is lowered below the melting point of oily soils, they harden into greasy soils, making them even more difficult to remove.

[0006] International patent application WO 2022 / 136389 A1 proposes the use of certain alkoxylated polyamines to improve washing properties under cold-wash conditions, and international patent application WO 2017 / 011733 A1 discloses certain cyclic amines as active ingredients for increasing washing power under cold-wash conditions. International patent application WO 2014 / 095540 A1 teaches that alkoxylated polyamines have a particularly good washing power-enhancing effect when combined with certain nonionic surfactants.

[0007] Surprisingly, it was found that structurally completely different polymers increase the washing power under cold wash conditions.

[0008] One object of the invention is the use of a compound of general formula (I)

[0009] in which each R is selected from -H and -OC(=O)-R', and R' is selected from the alkyl groups having 6 to 10 C atoms and mixtures thereof, wherein at least 5% of the number of R radicals are those which are not H, for increasing the detergency of detergents against fat- or oil-based textile soiling.

[0010] In the compound of general formula (I), preferably 20% to 35%, in particular 25% to 30% of the number of R radicals are not H. The R' radicals are preferably linear, but may also be branched; they are preferably part of a caproic acid, enanthic acid, caprylic acid, pelargonic acid or capric acid radical -OC(=O)-R', where not all R' radicals need to be the same.

[0011] Furthermore, in the compound of the general formula (I), 35% to 65%, in particular 40% to 60% of the number of R' radicals in the R radicals which are not H are preferably those having a Cy-alkyl group and 65% to 35%, in particular 60% to 40% of the number of R' radicals in the R radicals which are not H are preferably those having a Cg-alkyl group.

[0012] The compounds of general formula (I) are biodegradable. They are obtainable by esterification of 1 molar equivalent of 2-ethyl-2-(hydroxymethyl)-propane-1,3-diol (also called trimethylolpropane) with 29 molar equivalents of 2,2-bis(hydroxymethyl)propionic acid (also called dimethylolpropionic acid) followed by esterification with carboxylic acids R'-COOH, using sufficient molar equivalents of the latter to achieve the above-mentioned degree of esterification of at least 5%, in particular 20% to 35%, and particularly preferably 25% to 30%.

[0013] The invention further provides a process for removing grease- or oil-based soiling from textiles, characterized in that textiles requiring cleaning in this way are brought into contact with water and a compound of the general formula (I) or with a detergent and a compound of the general formula (I). This process can be carried out manually or mechanically, for example using a household washing machine. It is possible to apply the detergent and the compound of the general formula (I) simultaneously or sequentially. Simultaneous application can be carried out particularly advantageously by using a particularly liquid agent which contains the compound of the general formula (I). The concentration of the compound of the general formula (I) in the aqueous wash liquor is preferably 0.03 mg / l to 1 mg / l, in particular 0.05 mg / l to 0.09 mg / l.It is particularly advantageous that the process can be carried out at temperatures from room temperature to 60°C, in particular in the range from 20°C to 40°C; preferred embodiments of the process according to the invention operate at this temperature. Preferably, the compound of general formula (I) remains in contact with the textile for a period in the range from 80 minutes to 160 minutes, in particular from 90 minutes to 110 minutes; the textile is then rinsed and dried in the usual manner.

[0014] The inventive use in detergents is preferably carried out by employing the compound of general formula (I) in an amount of 1 wt.% to 6 wt.%, in particular 2 wt.% to 4 wt.%, whereby here and below, the terms "wt.%" refer to the weight of the entire detergent, unless otherwise stated. The invention therefore further relates to a detergent containing a compound of general formula (I), in particular in the amounts stated in the preceding sentence.

[0015] Detergents containing the compound to be used according to the invention, or used together with it, or employed in the process according to the invention may contain all other customary constituents of such agents that do not interact undesirably with an active ingredient essential to the invention. The detergent is preferably liquid.

[0016] Surprisingly, it has been found that the compounds of general formula (I) positively influence the action of certain other detergent and cleaning agent ingredients, and that, conversely, the action of the compounds of general formula (I) is further enhanced by certain other ingredients. It is therefore preferred that the detergent contains 10% to 40% by weight, in particular 20% to 30% by weight, of synthetic anionic surfactant, in particular of the sulfate or sulfonate type, and / or 20% to 40% by weight, in particular 25% to 35% by weight, of nonionic surfactant and / or 5% to 20% by weight, in particular 7% to 15% by weight, of soap.

[0017] Synthetic anionic surfactants particularly suitable for use in such agents include alkyl and / or alkenyl sulfates with 8 to 22 carbon atoms, which carry an alkali, ammonium, or alkyl- or hydroxyalkyl-substituted ammonium ion as the countercation. Preferred are derivatives of fatty alcohols, particularly with 12 to 18 carbon atoms, and their branched-chain analogues, the so-called oxo alcohols. The alkyl and alkenyl sulfates can be prepared in a known manner by reacting the corresponding alcohol component with a conventional sulfating reagent, in particular sulfur trioxide or chlorosulfonic acid, followed by neutralization with alkali, ammonium, or alkyl- or hydroxyalkyl-substituted ammonium bases. Particularly preferred sulfate-type surfactants include the sulfated alkoxylation products of C12-C18 alcohols, so-called ether sulfates.Such ether sulfates preferably contain 2 to 30, in particular 4 to 10, ethylene glycol groups per molecule. Suitable anionic surfactants of the sulfonate type include the α-sulfoesters obtainable by reacting fatty acid esters with sulfur trioxide and subsequent neutralization, in particular the sulfonation products derived from fatty acids having 8 to 22 carbon atoms, preferably 12 to 18 carbon atoms, and linear alcohols having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, as well as the sulfofatty acids obtained from these by formal saponification. Also among the usable anionic surfactants are the salts of sulfosuccinic acid esters, which are also referred to as alkyl sulfosuccinates or dialkyl sulfosuccinates and are the monoesters or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contain Cs to Cis fatty alcohol residues or mixtures thereof.Particularly preferred sulfosuccinates contain an ethoxylated fatty alcohol residue, which in itself represents a nonionic surfactant. Sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution are particularly preferred.

[0018] A further embodiment of the agents comprises the presence of alkoxylated C1-C22 alcohols in which the degree of alkoxylation of the alcohols is below 20, preferably below 10, and which are obtainable by reacting corresponding alcohols with alkylene oxides, with primary linear or branched-chain alcohols being preferred. Accordingly, the alkoxylates of primary alcohols with linear, in particular decyl, dodecyl, tridecyl, tetradecyl, hexadecyl, or octadecyl radicals, and mixtures thereof, are suitable. The degree of alkoxylation, i.e., the average number of alkoxy groups per alcohol function, can assume integer or fractional numerical values ​​and is preferably in the range from 2 to 10, in particular from 4 to 8. Preferred alkoxy groups are ethoxy, propoxy, and butoxy groups, in particular ethoxy groups and mixtures of ethoxy and propoxy groups.Other non-ionic surfactants are selected from fatty alkyl polyglycosides, fatty acid polyhydroxyamides and / or ethoxylation and / or propoxylation products of fatty alkylamines, vicinal diols, fatty acid alkyl esters and / or fatty acid amides and mixtures thereof.

[0019] Suitable nonionic surfactants include alkoxylates, particularly ethoxylates and / or propoxylates of saturated or mono- to polyunsaturated linear or branched-chain alcohols having 10 to 22 carbon atoms, preferably 12 to 18 carbon atoms, in which the degree of alkoxylation of the alcohols is below 20, preferably below 10. They can be prepared in a known manner by reacting the corresponding alcohols with the corresponding alkylene oxides. Derivatives of fatty alcohols are particularly suitable, although their branched-chain isomers, particularly so-called oxo alcohols, can also be used to prepare useful alkoxylates. Corresponding alkoxylation products of alkylamines, vicinal diols, and carboxamides, which correspond to the aforementioned alcohols with regard to the alkyl moiety, can also be used.

[0020] Other surfactant ingredients that may be considered include soaps, with saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, or stearic acid, as well as soaps derived from natural fatty acid mixtures, for example, coconut, palm kernel, or tallow fatty acids, being suitable. Particularly preferred are soap mixtures that consist of 50% to 100% by weight of saturated C12-C18 fatty acid soaps and up to 50% by weight of oleic acid soap. The soaps are preferably in the form of alkali metal, ammonium, or alkyl- or hydroxyalkyl-substituted ammonium salts of the fatty acids.

[0021] If desired, the agents may also contain betaines and / or cationic surfactants, which—if present—are preferably used in amounts of 0.5% to 7% by weight. Among these, esterquats are particularly preferred.

[0022] If desired, the agents can contain peroxygen-based bleaching agents, in particular in amounts ranging from 5% to 70% by weight, and optionally bleach activator, in particular in amounts ranging from 2% to 10% by weight. The bleaching agents considered are preferably the peroxygen compounds generally used in detergents, such as percarboxylic acids, for example dodecanediperic acid or phthaloylaminoperoxicaproic acid, hydrogen peroxide, alkali perborate, which can be present as tetrahydrate or monohydrate, percarbonate, perpyrophosphate and persilicate, which are generally present as alkali salts, in particular as sodium salts. Such bleaching agents are preferably present in detergents in amounts of up to 25% by weight, in particular up to 15% by weight and particularly preferably from 5% to 15% by weight, in each case based on the total agent, with percarbonate being used in particular.The optionally present component of the bleach activators 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, as well as cationic nitrile derivatives such as trimethylammonium acetonitrile salts.To prevent interaction with the peroxide compounds during storage, the bleach activators can be coated with coating substances and / 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.

[0023] In a further embodiment, the agent contains water-soluble and / or water-insoluble builder, in particular selected from alkali aluminosilicate, crystalline alkali silicate with a modulus above 1, monomeric polycarboxylate, polymeric polycarboxylate and mixtures thereof, in particular in amounts in the range from 2.5% by weight to 60% by weight.

[0024] The agent preferably contains 20% to 55% by weight of water-soluble and / or water-insoluble, organic and / or inorganic builders. The water-soluble organic builder substances include, in particular, those from the class of polycarboxylic acids, in particular citric acid and sugar acids, as well as polymeric (poly)carboxylic acids, in particular the polycarboxylates accessible by oxidation of polysaccharides, 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, that of the copolymers between 2,000 g / mol and 200,000 g / mol, preferably 50,000 g / mol to 120,000 g / mol, based on the free acid.A particularly preferred acrylic acid-maleic acid copolymer has a relative molecular weight 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 acid content is at least 50% by weight. Terpolymers containing two carboxylic 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 builders. The first acidic monomer or its salt is derived from a monoethylenically unsaturated Cs-Cs carboxylic acid, and preferably from a C3-C4 monocarboxylic acid, in particular from (meth)acrylic acid. The second acidic monomer or its salt may be a derivative of a C4-C8 dicarboxylic acid, with maleic acid being particularly preferred.The third monomeric unit in this case is formed by vinyl alcohol and / or preferably an esterified vinyl alcohol. Vinyl alcohol derivatives which are an ester of short-chain carboxylic acids, for example of C1-C4 carboxylic acids, with vinyl alcohol are particularly preferred. Preferred terpolymers contain 60% to 95% by weight, in particular 70% to 90% by weight, of (meth)acrylic acid and / or (meth)acrylate, particularly preferably acrylic acid and / or acrylate, and maleic acid and / or maleate, as well as 5% to 40% by weight, preferably 10% to 30% by weight, of vinyl alcohol and / or vinyl acetate. Particularly preferred terpolymers are those in which the weight ratio of (meth)acrylic acid and / or (meth)acrylate to maleic acid and / 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% to 60% by weight, in particular 45% to 55% by weight, of (meth)acrylic acid and / or (meth)acrylate, particularly preferably acrylic acid and / or acrylate, 10% to 30% by weight, preferably 15% to 25% by weight, of methallylsulfonic acid and / or methallylsulfonate, and, as a third monomer, 15% to 40% by weight, preferably 20% to 40% by weight, of a carbohydrate. This carbohydrate can be, for example, a mono-, di-, oligo- or polysaccharide, with mono-, di- or oligosaccharides being preferred, and sucrose being particularly preferred.The use of the third monomer presumably creates predetermined breaking points in the polymer, which are responsible for its good biodegradability. These terpolymers generally have a relative molecular mass between 1000 g / mol and 200,000 g / mol, preferably between 2000 g / mol and 50,000 g / mol, and especially between 3000 g / mol and 10,000 g / mol. They can be used, particularly for the production of liquid agents, in the form of aqueous solutions, preferably in the form of 30 to 50 percent by weight aqueous solutions. All of the polycarboxylic acids mentioned are generally used in the form of their water-soluble salts, especially their alkali metal salts.

[0025] Such organic builder substances are preferably present in amounts of up to 40 wt.%, in particular up to 25 wt.%, and particularly preferably from 1 wt.% to 5 wt.%. Amounts close to the stated upper limit are preferably used in paste-like or liquid, especially water-based, compositions.

[0026] 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 aluminosilicates of detergent quality, in particular zeolite NaA and optionally NaX, 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, which can be determined according to the information in German patent DE 24 12 837, is in the range of 100 to 200 mg CaO per gram.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 usable as builders in the agents 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. Such amorphous alkali silicates are commercially available, for example, under the name Portil®. Those with a molar ratio Na2O:SiO2 of 1:1.9 to 1:2.8 are preferably added during production as a solid rather than in the form of a solution. 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+i yH2O, 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. Crystalline layered silicates which fall under this general formula are described, for example, in European patent application EP 0 164 514. 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 (Na2Si2Os yH2O) are preferred. Practically anhydrous crystalline alkali silicates of the above general formula, in which x is a number from 1.9 to 2.1 and which are prepared from amorphous alkali silicates, can also be used in agents which contain an active ingredient combination to be used according to the invention.In a further preferred embodiment of agents according to the invention, a crystalline sodium layer silicate with a modulus of 2 to 3 is used, such as can be produced from sand and soda. Crystalline sodium silicates with a modulus in the range from 1.9 to 3.5 are used in a further preferred embodiment of detergents which contain an active ingredient combination used according to the invention. Their alkali silicate content is preferably 1% by weight to 50% by weight and in particular 5% by weight to 35% by weight, based on the anhydrous active substance. If alkali aluminosilicate, in particular zeolite, is also present as an additional builder substance, the alkali silicate content is preferably 1% by weight to 15% by weight and in particular 2% by weight to 8% by weight, based on the anhydrous active substance. The weight ratio of aluminosilicate to silicate, in each case based on the anhydrous active substances, is then preferably 4:1 to 10:1.In agents containing both amorphous and crystalline alkali silicates, the weight ratio of amorphous alkali silicate to crystalline alkali silicate is preferably 1:2 to 2:1 and in particular 1:1 to 2:1.

[0027] In addition to the aforementioned inorganic builder, other water-soluble or water-insoluble inorganic substances may be present in the compositions containing an active ingredient combination to be used according to the invention, used together with it, or employed in processes according to the invention. Suitable in this context are alkali metal carbonates, alkali metal bicarbonates, and alkali metal sulfates, as well as mixtures thereof. Such additional inorganic material may be present in amounts of up to 70% by weight.

[0028] In a preferred embodiment of the invention, an agent according to the invention 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 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, are used.-% of water-soluble builder block in the agents according to the invention. 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 from 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) up to 10 wt.% polymeric polycarboxylate, wherein the amounts relate to the entire washing or cleaning agent.

[0029] In a preferred embodiment of agents according to the invention, the water-soluble builder block contains at least 2 of components b), c), d) and e) in amounts greater than 0% by weight.

[0030] With regard to component a), in a preferred embodiment of the agent according to the invention, 15% by weight to 25% by weight of alkali metal carbonate, which can be at least partially replaced by alkali metal bicarbonate, and up to 5% by weight, in particular 0.5% by weight to 2.5% by weight of citric acid and / or alkali metal citrate are contained. In an alternative embodiment of the agent according to the invention, component a) contains 5% by weight to 25% by weight, in particular 5% by weight to 15% by weight of citric acid and / or alkali metal citrate and up to 5% by weight, in particular 1% by weight to 5% by weight of alkali metal carbonate, which can be at least partially replaced by alkali metal bicarbonate. If both alkali carbonate and alkali metal bicarbonate are present, component a) preferably comprises alkali carbonate and alkali metal bicarbonate in a weight ratio of 10:1 to 1:1. With regard to component b), in a preferred embodiment of the agent according to the invention, 1% by weight to 5% by weight-% alkali silicate with a modulus in the range of 1.8 to 2.5.

[0031] With regard to component c), a preferred embodiment of the compositions according to the invention contains 0.05% to 1% by weight of phosphonic acid and / or alkali metal phosphonate. Phosphonic acids also include optionally substituted alkylphosphonic acids, which may also contain 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.

[0032] With regard to component d), a preferred embodiment of agents according to the invention contains 15% by weight to 35% by weight of alkali phosphate, in particular trisodium polyphosphate.

[0033] With regard to component e), a preferred embodiment of the compositions according to the invention contains 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. Among these, 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).

[0034] In addition, the agents may contain other ingredients commonly found in detergents or cleaning agents. These optional ingredients include, in particular, enzymes, enzyme stabilizers, complexing agents for heavy metals, for example, aminopolycarboxylic acids, aminohydroxypolycarboxylic acids, polyphosphonic acids and / or aminopolyphosphonic acids, foam inhibitors, for example, organopolysiloxanes or paraffins, solvents, and optical brighteners, for example, stilbene disulfonic acid derivatives. Preferably, in agents which contain an active ingredient combination used according to the invention, up to 1 wt.%, in particular 0.01 wt.% to 0.5 wt.% of optical brighteners, in particular compounds from the class of substituted 4,4'-bis-(2,4,6-triamino-s-triazinyl)-stilbene-2,2'-disulfonic acids, up to 5 wt.%, in particular 0.1 wt.% to 2 wt.% of complexing agents for heavy metals, in particular aminoalkylenephosphonic acids and their salts and up to 2 wt.%, in particular 0.1 wt.-% to 1 wt.% foam inhibitors, whereby the stated weight proportions refer to the entire agent.

[0035] Solvents that can be used, particularly in liquid formulations, are preferably non-aqueous solvents that are water-miscible, in addition to water. These include lower alcohols, for example, ethanol, propanol, isopropanol, and the isomeric butanols, glycerin, lower glycols, for example, ethylene and propylene glycol, and the ethers derived from the aforementioned classes of compounds. In such liquid formulations, the active ingredients used according to the invention are generally present in dissolved or suspended form.

[0036] Any enzymes present are preferably selected from the group comprising protease, amylase, lipase, cellulase, hemicellulase, oxidase, peroxidase, pectinase, and mixtures thereof. Protease obtained from microorganisms such as bacteria or fungi is primarily suitable. It can be obtained from suitable microorganisms in a known manner through fermentation processes. Proteases are commercially available, for example, under the names BLAP®, Savinase®, Esperase®, Maxatase®, Optimase®, Alcalase®, Durazym®, or Maxapem®. The lipase used can be obtained, for example, from Humicola lanuginosa, Bacillus species, Pseudomonas species, Fusarium species, Rhizopus species, or Aspergillus species. Suitable lipases are commercially available under the names Lipolase®, Lipozym®, Lipomax®, Lipex®, Amano® Lipase, Toyo-Jozo® Lipase, Meito® Lipase and Diosynth® Lipase.Suitable amylases are commercially available under the names Maxamyl®, Termamyl®, Duramyl®, and Purafect® OxAm. The cellulase used can be an enzyme obtained from bacteria or fungi, which has an optimum pH, preferably in the slightly acidic to slightly alkaline range of 6 to 9.5. Such cellulases are commercially available under the names Celluzyme®, Carezyme®, and Ecostone®. Suitable pectinases are available, for example, under the names Gamanase®, Pektinex AR®, X-Pect® or Pectaway® from Novozymes, under the names Rohapect UF®, Rohapect TPL®, Rohapect PTE100®, Rohapect MPE®, Rohapect MA plus HC, Rohapect DA12L®, Rohapect 10L®, Rohapect B1 L® from AB Enzymes and under the name Pyrolase® from Diversa Corp., San Diego, CA, USA.

[0037] The usual enzyme stabilizers that may be present, particularly in liquid agents, include amino alcohols, for example mono-, di-, triethanol- and -propanolamine and mixtures thereof, lower carboxylic acids, boric acid, alkali borates, boric acid-carboxylic acid combinations, boric acid esters, boronic acid derivatives, calcium salts, for example Ca-formic acid combination, magnesium salts, and / or sulfur-containing reducing agents.

[0038] Suitable foam inhibitors include long-chain soaps, especially behen soap, fatty acid amides, paraffins, waxes, microcrystalline waxes, organopolysiloxanes, and mixtures thereof, which may also contain microfine, optionally sealed or otherwise hydrophobicized silica. For use in particulate agents, such foam inhibitors are preferably bound to granular, water-soluble carrier substances.

[0039] The known polyester-active soil-release polymers that can be used in addition to the active ingredient combination essential to the invention 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 those 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-(CHRn-) 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 11Hydrogen, 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-(CHRn-) 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 g / mol to 100,000 g / mol, in particular from 500 g / mol to 50,000 g / mol. 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 g / mol to 6000 g / mol. If desired, the 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, in particular from 1 to 10. In a preferred embodiment of the invention, polymers of ethylene terephthalate and polyethylene oxide terephthalate, in which the polyethylene glycol units have molecular weights of 750 g / mol to 5000 g / mol and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate is 50:50 to 90:10, are used together with an active ingredient combination essential to the invention. The soil-removing polymers are preferably water-soluble, whereby the term “water-soluble” is understood to mean a solubility of at least 0.01 g, preferably at least 0.1 g of the polymer per liter of water at room temperature and pH 8.However, polymers preferably used have a solubility of at least 1 g per liter, in particular at least 10 g per liter, under these conditions.

[0040] The production of solid compositions according to the invention presents no difficulties and can be carried out in a known manner, for example by spray drying or granulation, with enzymes and any other thermally sensitive ingredients, such as bleaching agents, being added separately later if necessary. For the production of compositions according to the invention with increased bulk density, in particular in the range of 650 g / l to 950 g / l, a process comprising an extrusion step is preferred.

[0041] To produce compositions according to the invention in tablet form, which may be single-phase or multi-phase, single-colored or multi-colored, and in particular consist of one or more layers, in particular two layers, the preferred procedure is to mix all the components - optionally one layer each - in a mixer and compress the mixture using conventional tablet presses, for example eccentric presses or rotary presses, with pressing forces in the range of approximately 50 to 100 kN, preferably 60 to 70 kN. Particularly in the case of multi-layer tablets, it can be advantageous if at least one layer is pre-compressed. This is preferably carried out at pressing forces between 5 and 20 kN, in particular 10 to 15 kN. This gives tablets which are readily break-resistant and yet dissolve sufficiently quickly under application conditions, with breaking and flexural strengths of normally 100 to 200 N, but preferably over 150 N.A tablet produced in this way preferably has a weight of 10 g to 50 g, in particular of 15 g to 40 g. The three-dimensional shape of the tablets is arbitrary and can be round, oval, or square, although intermediate shapes are also possible. Corners and edges are advantageously rounded. Round tablets preferably have a diameter of 30 mm to 40 mm. In particular, the size of square or cuboid-shaped tablets, which are predominantly introduced via the dosing device of a dishwasher, for example, depends on the geometry and volume of this dosing device. Exemplary preferred embodiments have a base area of ​​(20 to 30 mm) x (34 to 40 mm), in particular of 26 x 36 mm or 24 x 38 mm.

[0042] Liquid or pasty agents according to the invention in the form of solutions containing conventional solvents, in particular water, are generally prepared by simply mixing the ingredients, which can be added in bulk or as a solution to an automatic mixer. In a further preferred embodiment, an agent according to the invention is present in single-dose portions in a chamber made of water-soluble material; in this case, the agent preferably contains less than 15% by weight, in particular in the range of 1% to 12% by weight, of water. A portion is an independent dosing unit with at least one chamber containing the product to be dosed. A chamber is a space delimited by walls (for example, by a film) which can also exist without the product to be dosed (optionally with a change in its shape).A surface coating or a layer of a surface coating is therefore not a wall according to the present invention.

[0043] The chamber walls are made of a water-soluble material. The water solubility of the material can be determined using a square film of the material in question (film: 22 x 22 mm with a thickness of 76 μm) fixed in a square frame (inner edge length: 20 mm) according to the following measurement protocol. The framed film is placed in 800 ml of distilled water at 20 °C in a 1-liter beaker with a circular bottom (made by Co.Schott, Mainz, 1000 ml beaker, low form) so that the surface of the clamped film is arranged at a right angle to the bottom of the beaker, the upper edge of the frame is 1 cm below the water surface, and the lower edge of the frame is aligned parallel to the bottom of the beaker such that the lower edge of the frame runs along the radius of the bottom of the beaker and the center of the lower edge of the frame is arranged above the center of the radius of the beaker bottom. The material dissolves with stirring (magnetic stirrer speed 300 rpm, stirring rod: 5 cm long) within 600 seconds such that no individual solid particles are visible to the naked eye. The walls of the chambers and thus the water-soluble coatings of the detergents according to the invention are preferably formed from a water-soluble film material.Such water-soluble packaging can be produced either by vertical form-fill-seal processes or by thermoforming processes.

[0044] The thermoforming process generally includes forming a first layer of a water-soluble film material to form recesses for receiving a composition therein, filling the composition into the recesses, covering the composition-filled recesses with a second layer of a water-soluble film material, and sealing the first and second layers together at least around the recesses.

[0045] The water-soluble film material is preferably selected from polymers or polymer blends. The wrapper can be formed from one or two or more layers of water-soluble film material. The water-soluble film materials of the first layer and the additional layers, if present, can be the same or different.

[0046] It is preferred that the water-soluble coating contains polyvinyl alcohol or a polyvinyl alcohol copolymer; more preferably, it consists of polyvinyl alcohol or polyvinyl alcohol copolymer.

[0047] Water-soluble films for producing the water-soluble coating are preferably based on a polyvinyl alcohol or a polyvinyl alcohol copolymer whose molecular weight is in the range of 10,000 to 1,000,000 gmol -1 , preferably from 20,000 to 500,000 gmol -1 , particularly preferably from 30,000 to 100,000 gmol -1 and especially from 40,000 to 80,000 gmol -1lies.

[0048] Polyvinyl alcohol is typically produced by hydrolysis of polyvinyl acetate, since the direct synthesis route is not possible. The same applies to polyvinyl alcohol copolymers, which are produced from polyvinyl acetate copolymers. It is preferred if at least one layer of the water-soluble coating comprises a polyvinyl alcohol whose degree of hydrolysis is 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol%, and especially 82 to 88 mol%.

[0049] A film material suitable for producing the water-soluble wrapping may additionally contain polymers selected from the group comprising acrylic acid-containing polymers, polyacrylamides, oxazoline polymers, polystyrenesulfonates, polyurethanes, polyesters, polyethers, polylactic acid, and / or mixtures of the above polymers. The copolymerization of monomers underlying such polymers, individually or in mixtures of two or more, with vinyl acetate is also possible. Preferred polyvinyl alcohol copolymers comprise, in addition to vinyl alcohol, an ethylenically unsaturated carboxylic acid, its salt, or its ester. Particularly preferably, such polyvinyl alcohol copolymers contain, in addition to vinyl alcohol, acrylic acid, methacrylic acid, acrylic acid esters, methacrylic acid esters, or mixtures thereof; among the esters, C 1-4 alkyl esters or hydroxyalkyl esters are preferred.Likewise preferred polyvinyl alcohol copolymers comprise, in addition to vinyl alcohol, ethylenically unsaturated dicarboxylic acids as further monomers. Suitable dicarboxylic acids include, for example, itaconic acid, maleic acid, fumaric acid, and mixtures thereof, with itaconic acid being particularly preferred.

[0050] Suitable water-soluble films for use in the wrappers of the water-soluble packages according to the invention are films sold by MonoSol LLC, for example, under the designation M8630, C8400, or M8900. Other suitable films include films designated Solublon® PT, Solublon® GA, Solublon® KC, or Solublon® KL by Aicello Chemical Europe GmbH, or VF-HP films by Kuraray.

[0051] The detergent portion, comprising the detergent and the water-soluble coating, can have one or more chambers. Water-soluble coatings with one chamber can have a substantially dimensionally stable spherical, spherical, ellipsoidal, cube-shaped, cuboid-shaped, or pillow-shaped configuration with a circular, elliptical, square, or rectangular basic shape. The detergent can be contained in one or more chambers, if present, of the water-soluble coating.

[0052] In a preferred embodiment, the water-soluble coating has two chambers. In this embodiment, each chamber can contain a solid partial composition or a liquid partial composition, or the first chamber can contain a liquid partial composition and the second chamber a solid partial composition.

[0053] The proportions of the agents contained in the different chambers of a water-soluble casing with two or more chambers can have the same composition. However, the agents in a water-soluble casing with at least two chambers preferably have partial compositions that differ in at least one ingredient and / or in the content of at least one ingredient. Preferably, one partial composition of such agents according to the invention comprises an enzyme and / or bleach activator, and a further partial composition present separately comprises a peroxidic bleaching agent, wherein the first-mentioned partial composition then comprises, in particular, no peroxidic bleaching agent, and the second-mentioned partial composition then comprises, in particular, no enzyme and no bleach activator.

[0054] By packaging the portions in a water-soluble casing, the user is able to put one or, if desired, several, preferably one, of the portions into a washing machine, in particular into the detergent drawer of a washing machine, or into a container for carrying out a manual washing process. Such portion packs meet the consumer's desire for simplified dosing. After water is added, the casing material dissolves, so that the ingredients are released and can develop their effect in the wash. A water-soluble casing preferably weighs 10 g to 35 g, in particular 12 g to 28 g and particularly preferably 12 g to 15 g, wherein the proportion of the water-soluble casing contained in the weight specification accounts for 0.3 g to 2.5 g, in particular 0.7 g to 1.2 g.

[0055] Examples

[0056] A compound according to general formula (I) was used, whose R residues consisted of 72% H and 28% of a 55:45 mixture of octanoic acid and decanoic acid esters (M1). For comparison, a compound (V1) otherwise corresponding to general formula (I) was used, whose R residues consisted of 100% H. From these compounds, the detergents W2 and W3 were prepared, the compositions (wt%) given in the table below. For comparison, a detergent W1 free of both was also tested.

[0057] Table 1 : Composition of detergents [wt.%1

[0058] These were used to wash cotton textiles with the standardised soiling specified in Table 2 below at 20 °C for 150 minutes with a main wash cycle duration of 90 minutes, and to determine the increase in washing power of agents W2 and W3 compared to the washing power of agent W1 (brightness differences AY):

[0059] Table 2: Percentage increase in washing power [%1

[0060] It can be seen that the agent W3 according to the invention has a particularly high increase in washing power.

Claims

Patent claims 1 . Detergent containing a compound of general formula (I), in which each R is selected from -H and -OC(=O)-R', and R' is selected from the alkyl groups having 6 to 10 C atoms and mixtures thereof, at least 5% of the number of R radicals being those which are not H.

2. Agent according to claim 1, characterized in that it contains 1 wt.% to 6 wt.%, in particular 2 wt.% to 4 wt.%, of the compound of general formula (I).

3. Agent according to claim 1 or 2, characterized in that it is liquid.

4. Agent according to claim 3, characterized in that it is present in single-dose portions in a chamber formed from water-soluble material and contains water in amounts of up to 15% by weight.

5. Agent according to one of claims 1 to 4, characterized in that it contains 10 wt.% to 40 wt.%, in particular 20 wt.% to 30 wt.% synthetic anionic surfactant and / or that it contains 20 wt.% to 40 wt.%, in particular 25 wt.% to 35 wt.% non-ionic surfactant and / or that it contains 5 wt.% to 20 wt.%, in particular 7 wt.% to 15 wt.% soap. . Use of a compound of general formula (I) in which each R is selected from -H and -OC(=O)-R', and R' is selected from the alkyl groups having 6 to 10 C atoms and mixtures thereof, wherein at least 5% of the number of R radicals are those which are not H, for increasing the detergency of detergents against fat- or oil-based textile soiling.

7. A process for removing grease or oil-based soiling from textiles, characterized in that textiles requiring cleaning in this way are treated with water and a compound of the general formula (I) in which each R is selected from -H and -OC(=O)-R', and R' is selected from the alkyl groups having 6 to 10 C atoms and mixtures thereof, at least 5% of the number of R radicals being those which are not H, or an agent according to any one of claims 1 to 5.

8. The method according to claim 7, characterized in that it is carried out at temperatures from room temperature to 60 °C, in particular in the range from 20 °C to 40 °C.

9. Agent according to one of claims 1 to 5, use according to claim 6, or process according to claim 7 or 8, characterized in that in the compound of general formula (I) 20% to 35%, in particular 25% to 30% of the number of radicals R are not H.

10. Agent according to one of claims 1 to 5 or 9, use according to claim 6 or 9, or process according to one of claims 7 to 9, characterized in that in the compound of the general formula (I) 35% to 65%, in particular 40% to 60% of the number of R' radicals in the R radicals which are not H are those having a C 1 -C 6 alkyl group and 65% to 35%, in particular 60% to 40% of the R' radicals in the R radicals which are not H are those having a C 9 -C 6 alkyl group.

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