Detergent with improved washing ability against oily and greasy dirt

Abstract

The invention relates to improving the washing ability of detergents against oily and greasy dirt. This is achieved by using compounds of general formula (I) in which each R is selected from-H and-O-C (= O)-R ', and R' is selected from alkyl groups having 6 to 10 C atoms, and mixtures thereof, in which at least 5% of the number of functional groups R is not H. # imgabs0 #

Description

[0001] The present invention relates to fabric washing agents comprising specific star polymers, methods for washing fabrics using such star polymers, and the use of the star polymers for improving the washing performance of fabric washing agents against grease- or oil-based soils.

[0002] As a contribution to combating climate change, one of the most important goals in textile washing is to reduce CO2 emissions per wash cycle. This can be achieved by lowering the washing temperature. To ensure that textile detergents have the desired cleaning performance even under low-temperature washing conditions, so-called cleaning performance enhancers are often used.

[0003] Another important goal is to use biodegradable detergent ingredients to minimize the accumulation of non-degradable or poorly degradable substances in the ecosystem.

[0004] The object of the present invention is to achieve both of these objectives simultaneously.An element which also hinders the achievement of said objectives is that when the washing temperature drops below the melting temperature range of oily soils, the soils harden into greasy soils and thereby become even more difficult to remove.

[0005] International Patent Application WO 2022 / 136389 A1 proposes the use of specific alkoxylated polyamines for improving washing properties under low-temperature washing conditions, and International Patent Application WO 2017 / 011733 A1 discloses specific cyclic amines as active ingredients that can be used to enhance washing performance under low-temperature washing conditions. International Patent Application WO 2014 / 095540 A1 teaches that alkoxylated polyamines have a particularly good washing performance-enhancing effect when combined with specific nonionic surfactants.

[0006] It has been unexpectedly found that polymers with a completely different structure improve the washing ability under low temperature washing conditions.

[0007] The present invention relates to the use of compounds of the general formula (I) for improving the cleaning power of detergents against grease- or oil-based textile stains.

[0008]

[0009] In the compounds of general formula (I), each R is selected from -H and -OC(=O)-R', and R' is selected from alkyl groups having 6 to 10 C atoms, and mixtures thereof, wherein at least 5% of the number of functional groups R are those other than H.

[0010] In the compounds of the general formula (I), 20% to 35%, in particular 25% to 30%, of the number of functional groups R are preferably not H. The functional groups R' are preferably linear, but can also be branched; they are preferably part of a hexanoic, heptanoic, octanoic, nonanoic or decanoic acid function -OC(=O)-R', not all functional groups R' having to be identical.

[0011] Further preferably, in the compounds of the general formula (I), 35% to 65%, in particular 40% to 60%, of the number of functional groups R' among the functional groups R that are not H are those with C7 alkyl groups, and 65% to 35%, in particular 60% to 40%, of the number of functional groups R' among the functional groups R that are not H are those with C9 alkyl groups.

[0012] The compounds of general formula (I) are biodegradable. They can be obtained by esterifying 1 molar equivalent of 2-ethyl-2-(hydroxymethyl)-propane-1,3-diol (also known as trimethylolpropane) with 29 molar equivalents of 2,2-bis(hydroxymethyl)-propionic acid (also known as dimethylolpropionic acid) and subsequently esterifying with a carboxylic acid R'-COOH, wherein so many molar equivalents of the carboxylic acid R'-COOH are used that the above-mentioned degree of esterification of at least 5%, in particular 20% to 35%, particularly preferably 25% to 30% is achieved.

[0013] The present invention also relates to a method for removing grease- or oil-based stains from fabrics, characterized in that a fabric requiring such cleaning is contacted with water and a compound of the general formula (I) or a detergent and a compound of the general formula (I). The method can be carried out manually or mechanically (for example, using a household washing machine). The detergent and the compound of the general formula (I) can be used simultaneously or sequentially. By using an agent (particularly a liquid agent) containing the compound of the general formula (I), both can be used simultaneously in a particularly advantageous manner. The concentration of the compound of the general formula (I) in the aqueous washing liquid is preferably 0.03 mg / l to 1 mg / l, particularly 0.05 mg / l to 0.09 mg / l. Particularly advantageously, the method can be carried out at a temperature ranging from room temperature to 60°C, particularly from 20°C to 40°C; preferred embodiments of the method according to the present invention operate within this range. Preferably, the compound of the general formula (I) is kept in contact with the fabric for a period of 80 to 160 minutes, particularly from 90 to 110 minutes; the fabric is then rinsed and dried in the usual manner.

[0014] The use according to the invention in detergents is preferably carried out by using the compound of the general formula (I) in an amount of 1% to 6% by weight, in particular 2% to 4% by weight, wherein, unless otherwise indicated, the expression "% by weight" here and below relates to the weight of the total detergent. Therefore, the present invention also relates to detergents comprising the compound of the general formula (I), in particular comprising the compound of the general formula (I) in the amount indicated in the preceding sentence.

[0015] The detergent containing the compound to be used according to the invention, or used together with the compound, or used in the method according to the invention may contain all other customary ingredients of such detergents which do not interact undesirably with the active ingredients essential to the invention. Preferably, the detergent is a liquid.

[0016] It has been unexpectedly found that compounds of general formula (I) have a positive influence on the action of certain other detergent and cleaning agent ingredients, and that the action of compounds of general formula (I) is in turn further enhanced by certain other ingredients. Therefore, preferably, the detergent comprises: 10% to 40% by weight, in particular 20% to 30% by weight of a synthetic anionic surfactant, in particular a synthetic anionic surfactant of the sulfate or sulfonate type; and / or 20% to 40% by weight, in particular 25% to 35% by weight of a 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 sulfates and / or alkenyl sulfates having 8 to 22 C atoms with ammonium ions substituted by alkali metals, ammonium or alkyl or hydroxyalkyl groups as counter cations. Derivatives of fatty alcohols and their branched analogs (so-called oxo alcohols) having in particular 12 to 18 C atoms are preferred. Alkyl sulfates and alkenyl sulfates can be prepared in a known manner by reacting the corresponding alcohol component with conventional sulfating agents (in particular, sulfur trioxide or chlorosulfonic acid) and subsequently neutralizing with an ammonium base substituted by alkali metals, ammonium or alkyl or hydroxyalkyl groups. Sulfate-type surfactants that can be used with particular preference include C 12-18Sulfated alkoxylation products of 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 α-sulfoesters obtainable by reacting fatty acid esters with sulfur trioxide and subsequent neutralization, in particular those derived from the sulfonation products of fatty acids having 8 to 22 C atoms, preferably 12 to 18 C atoms, and straight-chain alcohols having 1 to 6 C atoms, preferably 1 to 4 C atoms, and the sulfofatty acids obtained therefrom by standard saponification. Anionic surfactants that can be used also include salts of alkylsulfosuccinates, which are also known as alkylsulfosuccinates or dialkylsulfosuccinates and represent monoesters or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols, in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contain C8-C 18 Fatty alcohol groups or mixtures thereof. Particularly preferred sulfosuccinates contain ethoxylated fatty alcohol functional groups, which, when considered individually, represent nonionic surfactants. Of these, sulfosuccinates comprising fatty alcohol groups derived from ethoxylated fatty alcohols exhibiting a restricted distribution of homologs are particularly preferred.

[0018] Another embodiment of the reagent comprises an alkoxylated C 10 -C 22 In the presence of alcohol, the alkoxylated C 10 -C 22 The degree of alkoxylation of the alcohol in the alcohol is less than 20, preferably less than 10, and the alkoxylated C 10 -C 22 Alcohols can be obtained by reacting the corresponding alcohols with alkylene oxides, with straight-chain or branched primary alcohols being preferred. Thus, alkoxylates of primary alcohols having straight chains, in particular decyl, dodecyl, tridecyl, tetradecyl, hexadecyl, or octadecyl functional groups, and mixtures thereof, are useful. The degree of alkoxylation (i.e., the average number of alkoxy groups per alcohol functional group) can be integer or fractional, and is preferably in the range of 2 to 10, in particular 4 to 8. Preferred alkoxy groups are ethoxy, propoxy and butoxy, in particular ethoxy and mixtures of ethoxy and propoxy groups. Other nonionic surfactants are selected from fatty alkyl polyglycosides; fatty acid polyhydroxyamides; and / or ethoxylated products and / or propoxylated products of fatty alkylamines, vicinal glycols, fatty acid alkyl esters, and / or fatty acid amides; and mixtures thereof.

[0019] Suitable nonionic surfactants include alkoxylates, in particular ethoxylates and / or propoxylates, of saturated or monounsaturated to polyunsaturated linear or branched alcohols having 10 to 22 carbon atoms, preferably 12 to 18 carbon atoms, wherein the degree of alkoxylation of the alcohol is less than 20, preferably less than 10. These can be prepared in a known manner by reacting the corresponding alcohol with the corresponding alkylene oxide. Particularly suitable are derivatives of fatty alcohols, but their branched isomers, in particular so-called oxo alcohols, can also be used to prepare useful alkoxylates. In addition, the corresponding alkoxylation products of alkylamines, vicinal diols, and carboxylic acid amides corresponding to the alcohols in terms of the alkyl moiety are also useful.

[0020] Other surface active ingredients include soaps, of which saturated fatty acid soaps (such as salts of lauric acid, myristic acid, palmitic acid, or stearic acid) and soaps derived from natural fatty acid mixtures (e.g., coconut oil fatty acid, palm kernel fatty acid, or tallow fatty acid) are suitable. In particular, 50% to 100% by weight of saturated C 12 -C 18 Soap mixtures of fatty acid soaps and up to 50% by weight of oleic acid soap are preferred. The soap is preferably in the form of an alkali metal, ammonium, or alkyl- or hydroxyalkyl-substituted ammonium salt of a fatty acid.

[0021] If desired, the agent may also contain betaine and / or a cationic surfactant, which, if present, is preferably used in an amount of 0.5 to 7% by weight. Of these, esterquats are particularly preferred.

[0022] If desired, the agent may contain a peroxygen-based bleaching agent (in an amount particularly in the range of 5% to 70% by weight), and optionally a bleach activator (in an amount particularly in the range of 2% to 10% by weight). Suitable bleaching agents are preferably peroxy compounds commonly used in detergents, such as percarboxylic acids (e.g., dodecane diperoxyacid or phthalamidoperoxycaproic acid), hydrogen peroxide, alkali metal perborates (which may be in the form of tetrahydrates or monohydrates), percarbonates, perpyrophosphates, and persilicates (which are generally in the form of alkali metal salts, in particular sodium salts). Such bleaching agents are preferably present in the detergent in an amount of up to 25% by weight, in particular up to 15% by weight, particularly preferably from 5% to 15% by weight, based on the total agent, in particular using percarbonate. Optional bleach activator components include customary N-acyl compounds or O-acyl compounds, for example, polyacylated alkylenediamines (especially tetraacetylethylenediamine), acylated glycolurils (especially tetraacetylglycoluril), N-acylated hydantoins, hydrazides, triazoles, uracils, diketopiperazines, sulfonamides and cyanurates, as well as carboxylic anhydrides (especially phthalic anhydride), carboxylic esters (especially sodium isononanoylphenolsulfonate), acylated sugar derivatives (especially pentaacetyl glucose), and cationic nitrile derivatives (such as trimethylacetonitrile ammonium salt). The bleach activators may have been coated with a coating substance and / or granulated in a known manner to prevent interaction with peroxides during storage, with tetraacetylethylenediamine granulated with carboxymethylcellulose and having an average particle size of 0.01 mm to 0.8 mm, granulated 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine, and / or trialkylammonium acetonitrile produced in granular form being particularly preferred. Such bleach activators are preferably contained in the detergent in an amount of up to 8% by weight, in particular 2% to 6% by weight, based on the total reagent.

[0023] In another embodiment, the agent comprises water-soluble and / or water-insoluble builders, in particular chosen from alkali metal aluminosilicates, crystalline alkali metal silicates with a modulus greater than 1, monomeric polycarboxylates, polymeric polycarboxylates, and mixtures thereof, the amount of said water-soluble and / or water-insoluble builders in particular being in the range from 2.5% to 60% by weight.

[0024] The agent preferably comprises 20% to 55% by weight of water-soluble and / or water-insoluble, organic and / or inorganic builders. Water-soluble organic builders include in particular those from the following categories: polycarboxylic acids, in particular citric acid and sugar acids; and polymer (poly) carboxylic acids, in particular polycarboxylates, polymer acrylic acid, methacrylic acid, maleic acid and mixed polymers thereof, which may also contain a small amount of polymerizable substances without carboxylic acid functional groups in the polymer, based on free acid. The relative molecular mass of the homopolymer of the unsaturated carboxylic acid is generally 5000 g / mol to 200000 g / mol, and the relative molecular mass of the copolymer is 2000 g / mol to 200000 g / mol, preferably 50000 g / mol to 120000 g / mol. The relative molecular mass of particularly preferred acrylic acid-maleic acid copolymers is 50000 g / mol to 100000 g / mol. Suitable but less preferred such compounds are copolymers of acrylic acid or methacrylic acid and vinyl ether (such as vinyl methyl ether), vinyl ester, ethylene, propylene and styrene, wherein the ratio of acid is at least 50 weight %.Also terpolymers can be used as water-soluble organic wash builders, wherein the terpolymer comprises two kinds of carboxylic acids and / or their salts as monomers and vinyl alcohol and / or vinyl alcohol derivatives or carbohydrates as the third monomer.The first acidic monomer or its salt is derived from monoethylenically unsaturated C3-C8 carboxylic acid, preferably C3-C4 monocarboxylic acid, particularly (methyl) acrylic acid.The second acidic monomer or its salt can be a derivative of C4-C8 dicarboxylic acid, wherein maleic acid is particularly preferred.In this case, the third monomer unit is formed by vinyl alcohol and / or preferably esterified vinyl alcohol.Particularly, preferably vinyl alcohol derivatives, the vinyl alcohol derivatives are esters of short-chain carboxylic acids (for example, C1-C4 carboxylic acid) and vinyl alcohol. Preferred terpolymers contain 60% to 95% by weight, in particular 70% to 90% by weight, of (meth)acrylic acid and / or (meth)acrylic esters, particularly preferably acrylic acid and / or acrylic esters and maleic acid and / or maleic esters, and 5% to 40% by weight, preferably 10% to 30% by weight, of vinyl alcohol and / or vinyl acetate. Terpolymers in which the weight ratio of (meth)acrylic acid and / or (meth)acrylic ester to maleic acid and / or maleic ester is 1:1 to 4:1, preferably 2:1 to 3:1, in particular 2:1 to 2.5:1 are particularly preferred. Both the amount and the weight ratio are based on the acid. The second acidic monomer or its salt can also be an allylsulfonic acid derivative substituted in the second position with an alkyl function (preferably a C1-C4 alkyl function) or an aromatic function (preferably derived from benzene or a benzene derivative).Preferred terpolymers contain: 40% to 60% by weight, in particular 45% to 55% by weight, of (meth)acrylic acid and / or (meth)acrylic acid esters, particularly preferably acrylic acid and / or acrylic acid esters; 10% to 30% by weight, preferably 15% to 25% by weight, of methallylsulfonic acid and / or methallylsulfonic acid esters; and 15% to 40% by weight, preferably 20% to 40% by weight, of a carbohydrate as a third monomer. The carbohydrate can be, for example, a monosaccharide, disaccharide, oligosaccharide, or polysaccharide, with monosaccharides, disaccharides, or oligosaccharides being preferred, and sucrose being particularly preferred. The use of a third monomer is presumably to introduce a predetermined breakpoint into the polymer, which is responsible for its good biodegradability. The relative molecular weight of these terpolymers is typically 1,000 to 200,000 g / mol, preferably 2,000 to 50,000 g / mol, and in particular 3,000 to 10,000 g / mol. They can be used in particular for the preparation of liquid reagents in the form of aqueous solutions, preferably in the form of 30% to 50% by weight aqueous solutions.All the polycarboxylic acids mentioned are generally used in the form of their water-soluble salts, in particular their alkali metal salts.

[0025] The content of such organic builders is preferably up to 40% by weight, in particular up to 25% by weight, particularly preferably from 1% to 5% by weight. Amounts close to the stated upper limit are preferably used in pasty or liquid (in particular, aqueous) agents.

[0026] In particular, crystalline or amorphous alkali metal aluminosilicates are used as water-insoluble, water-dispersible inorganic builder materials in amounts of up to 50% by weight, preferably not more than 40% by weight, and in liquid formulations, in particular in amounts of 1% to 5% by weight. Of these, detergent-grade crystalline aluminosilicates, in particular zeolite NaA and optionally NaX, are preferred. In solid granular formulations, amounts close to the stated upper limit are preferably used. Suitable aluminosilicates in particular do not have particles with a particle size above 30 μm and preferably consist of at least 80% by weight of particles with a size below 10 μm. The calcium binding capacity of the aluminosilicates is generally in the range of 100 to 200 mg CaO per gram, which can be determined according to the specification in German patent DE 24 12 837. Suitable alternatives or partial alternatives to the aluminosilicates mentioned are crystalline alkali metal silicates, which can be present alone or in a mixture with amorphous silicates. The alkali metal silicates which can be used as builders in the agents preferably have a molar ratio of alkali metal oxide to SiO2 of less than 0.95, in particular from 1:1.1 to 1:12, and can be present in amorphous or crystalline form. Preferred alkali metal silicates are sodium silicates, in particular amorphous sodium silicates having a molar ratio of Na2O:SiO2 of from 1:2 to 1:2.8. Such amorphous alkali metal silicates are commercially available, for example under the name ). Those with a Na2O:SiO2 molar ratio of 1:1.9 to 1:2.8 are preferably added in solid form rather than in solution during preparation. x O 2x+1Crystalline silicates of ·yH2O (where x, referred to as the modulus, is a number from 1.9 to 4, y is a number from 0 to 20, and x is preferably 2, 3, or 4) are used as crystalline silicates, which can be present alone or in a mixture with amorphous silicates. Crystalline silicates encompassed by this general formula are described, for example, in European patent application EP 0 164 514. Preferred crystalline silicates are those in which x in the general formula mentioned is 2 or 3. In particular, both β-sodium disilicate and δ-sodium disilicate (Na2Si2O5·yH2O) are preferred. Almost anhydrous crystalline alkali metal silicates having the above general formula (where x is a number from 1.9 to 2.1) and prepared from amorphous alkali metal silicates can also be used in the agents according to the invention containing the active ingredient combination to be used. In another preferred embodiment of the agent according to the invention, crystalline sodium silicates with a modulus of 2 to 3 are used, which can be prepared, for example, from sand and soda ash. In another preferred embodiment of the detergent according to the invention containing the active ingredient combination used, crystalline sodium silicate is used with a modulus in the range of 1.9 to 3.5. Its alkali metal silicate content, based on the anhydrous active substance, is preferably 1% to 50% by weight, in particular 5% to 35% by weight. If an alkali metal aluminosilicate, in particular zeolite, is present as an additional builder, the alkali metal silicate content is preferably 1% to 15% by weight, in particular 2% 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 substance) is then preferably 4:1 to 10:1. In agents containing amorphous alkali metal silicate and crystalline alkali metal silicate, the weight ratio of amorphous alkali metal silicate to crystalline alkali metal silicate is preferably 1:2 to 2:1, in particular 1:1 to 2:1.

[0027] In addition to the aforementioned inorganic builders, other water-soluble or water-insoluble inorganic substances may also be included in the agents comprising the active ingredient combination to be used according to the invention, used together with the aforementioned inorganic builders, or used in the method according to the invention. In this case, suitable are alkali metal carbonates, alkali metal hydrogencarbonates and alkali metal sulfates and mixtures thereof. Such additional inorganic materials may be present in an amount of up to 70% by weight.

[0028] In a preferred embodiment of the invention, the agents according to the invention comprise a water-soluble builder component ( Builderblock). The use of the term "builder ingredient" is intended to express the fact that the reagent does not contain any builder other than water-soluble builders, that is, all builders contained in the reagent are combined in the "ingredients" so characterized, with the exception of any amount of substances that may normally be present in small amounts as impurities or stabilizing additives in other ingredients of the reagent. The term "water-soluble" should be understood to mean that, under normal conditions, at the concentration resulting from the amount of the reagent containing the builder ingredient used, the builder ingredient dissolves without residue. Preferably, at least 15% by weight and at most 55% by weight, in particular 25% to 50% by weight, of the water-soluble builder ingredient is contained in the reagent according to the present invention. This preferably consists of the following components:

[0029] a) 5 to 35% by weight of citric acid, alkali metal citrates, and / or alkali metal carbonates, the alkali metal carbonates also being at least partially replaced by alkali metal hydrogencarbonates,

[0030] b) up to 10% by weight of an alkali metal silicate having a modulus in the range from 1.8 to 2.5,

[0031] c) up to 2% by weight of phosphonic acid and / or alkali metal phosphonates,

[0032] d) up to 50% by weight of alkali metal phosphate, and

[0033] e) up to 10% by weight of polymeric polycarboxylates,

[0034] The amounts stated therein are expressed relative to the total detergent or cleaning agent.

[0035] In a preferred embodiment of the agents according to the invention, the water-soluble builder ingredient comprises at least two of the components b), c), d) and e) in an amount of greater than 0% by weight.

[0036] Regarding component a), a preferred embodiment of the agent according to the invention comprises: 15% to 25% by weight of alkali metal carbonate, which may be at least partially replaced by alkali metal hydrogencarbonate; and up to 5% by weight, in particular 0.5% to 2.5% by weight, of citric acid and / or alkali metal citrate. An alternative embodiment of the agent according to the invention comprises as component a): 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 hydrogencarbonate. If both alkali metal carbonate and alkali metal hydrogencarbonate are present, component a) preferably comprises alkali metal carbonate and alkali metal hydrogencarbonate in a weight ratio of 10:1 to 1:1.

[0037] As regards component b), a preferred embodiment of the agent according to the invention comprises from 1% to 5% by weight of an alkali metal silicate having a modulus in the range from 1.8 to 2.5.

[0038] Regarding component c), a preferred embodiment of the reagent according to the invention comprises 0.05% to 1% by weight of phosphonic acid and / or alkali metal phosphonates. Phosphonic acid should also be understood to mean optionally substituted alkylphosphonic acids, which may also have multiple phosphonic acid groups (so-called polyphosphonic acids). They are preferably selected from hydroxy and / or aminoalkylphosphonic acids and / or alkali metal salts thereof, such as dimethylaminomethanediphosphonic acid, 3-aminopropane-1-hydroxy-1,1-diphosphonic acid, 1-amino-1-phenylmethanediphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid, aminotris(methylenephosphonic acid), N,N,N',N'-ethylenediaminetetrakis(methylenephosphonic acid), and acylated derivatives of phosphorous acid, which may also be used in any mixture.

[0039] As regards component d), a preferred embodiment of the agent according to the invention comprises 15% to 35% by weight of alkali metal phosphate, in particular trisodium polyphosphate.

[0040] As regards component e), a preferred embodiment of the agent according to the invention comprises from 1.5 to 5% by weight of a polymeric polycarboxylate, in particular selected from the group consisting of polymerization products or copolymerization products of acrylic acid, methacrylic acid, and / or maleic acid. Of these, homopolymers of acrylic acid, and in turn those having an average molar mass in the range of 5000 to 15000 g / mol (PA standard), are particularly preferred.

[0041] In addition, the agent may contain other components conventional in detergents or cleaning agents. These optional ingredients include, in particular, enzymes, enzyme stabilizers, heavy metal complexing agents (e.g., aminopolycarboxylic acids, aminohydroxypolycarboxylic acids, polyphosphonic acids, and / or aminopolyphosphonic acids), foam suppressors (e.g., organopolysiloxanes or paraffins), solvents, and fluorescent whitening agents (e.g., stilbene disulfonic acid derivatives). Preferably, the agent containing the active ingredient combination used according to the invention contains up to 1% by weight, in particular 0.01% to 0.5% by weight of fluorescent whitening agents, 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% by weight, in particular 0.1% to 2% by weight of heavy metal complexing agents, in particular aminoalkylenephosphonic acids and their salts; and up to 2% by weight, in particular 0.1% to 1% by weight of foam suppressors, the given weight percentages each being relative to the total agent.

[0042] In addition to water, solvents that can be used in liquid agents are preferably water-miscible non-aqueous solvents. These include lower alcohols (e.g., ethanol, propanol, isopropanol and isomeric butanols), glycerol, lower glycols (e.g., ethylene glycol and propylene glycol), and ethers that can be derived from compounds of the class described. In such liquid agents, the active ingredient used according to the present invention is usually dissolved or suspended.

[0043] The optional enzymes are preferably selected from the group consisting of proteases, amylases, lipases, cellulases, hemicellulases, oxidases, peroxidases, pectinases, and mixtures thereof. Firstly, proteases of microbial origin (e.g., bacteria or fungi) are considered. Proteases can be obtained in a known manner from suitable microorganisms by fermentation processes. Proteases are commercially available (e.g., under the name or Lipases that can be used can be obtained, for example, from Humicola lanuginosa, Bacillus-Arten, Pseudomonas-Arten, Fusarium-Arten, Rhizopus-Arten, or Aspergillus-Arten. Suitable lipases are commercially available (e.g. under the name -Lipase、Toyo- -Lipase, -Lipase and - Lipase). Suitable amylases are commercially available (e.g. under the name and OxAm). The cellulase that can be used may be an enzyme that can be obtained from bacteria or fungi and has an optimum pH preferably in the weakly acidic to weakly alkaline range of 6 to 9.5. Such cellulase is commercially available (e.g., under the name and Suitable pectinases are, for example, those which may be named Pektinex X- or From Novozymes; under the name Rohapect Rohapect Rohapect Rohapect Rohapect MA plus HC, Rohapect Rohapect Rohapect from AB Enzymes; and under the name Obtained from Diversa Corp., San Diego, CA, USA.

[0044] Conventional enzyme stabilizers that are optionally present, particularly in liquid reagents, include amino alcohols (e.g., mono-, di-, triethanol- and -propanolamine, and mixtures thereof), lower carboxylic acids, boric acid, alkali metal borates, boric acid-carboxylic acid combinations, boric acid esters, boric acid derivatives, calcium salts (e.g., Ca-formic acid combinations), magnesium salts, and / or sulfur-containing reducing agents.

[0045] Suitable suds suppressors include long-chain soaps (especially behen soap), fatty acid amides, paraffins, waxes, microcrystalline waxes, organopolysiloxanes, and mixtures thereof, which may also contain finely divided, optionally silanized or otherwise hydrophobized, silicic acid. For use in granular agents, such suds suppressors are preferably incorporated into a particulate, water-soluble carrier material.

[0046] Known polyester active polymers that allow soil removal and can be used in addition to the active ingredient combination required by the present invention include copolyesters of dicarboxylic acids (e.g., adipic acid, phthalic acid, or terephthalic acid), diols (e.g., ethylene glycol or propylene glycol) and polyglycols (e.g., polyethylene glycol or polypropylene glycol). Preferred polyesters that allow soil removal include those compounds that can be obtained formally by partially esterifying two monomers, the first being a dicarboxylic acid HOOC-Ph-COOH and the second being a diol HO-(CHR 11 -) a OH, which can also be used as a polymer diol H-(O-(CHR 11 -) a ) b OH is present. Here, Ph represents an o-phenylene, m-phenylene, or p-phenylene functional group which may carry 1 to 4 substituents selected from alkyl functional groups having 1 to 22 carbon atoms, sulfonic acid groups, carboxyl groups, and mixtures thereof; R 11 represents hydrogen, an alkyl function having 1 to 22 C atoms, and mixtures thereof; a represents a number from 2 to 6; and b represents a number from 1 to 300. Preferably, in the polyesters obtainable from these, the monomeric diol units -O-(CHR 11 -) a O- and polymer diol units -(O-(CHR 11 -) a ) bO—both are present. The molar ratio of monomeric diol units to polymeric diol units is preferably from 100:1 to 1:100, in particular from 10:1 to 1:10. The degree of polymerization b in the polymeric diol units is preferably in the range of 4 to 200, in particular from 12 to 140. Preferred polyesters that allow soil removal have a molecular weight, average molecular weight, or maximum molecular weight distribution in the range of 250 g / mol to 100,000 g / mol, in particular from 500 g / mol to 50,000 g / mol. The acid forming the basis of the functional group Ph is preferably selected from terephthalic acid; isophthalic acid; phthalic acid; trimellitic acid; mellitic acid; isomers of sulfophthalic acid, sulfoisophthalic acid, and sulfoterephthalic acid; and mixtures thereof. If the acid groups are not part of an ester bond in the polymer, they are preferably in the form of salts, in particular alkali metal salts or ammonium salts. Of these, sodium and potassium salts are particularly preferred. If desired, instead of the monomeric HOOC-Ph-COOH, small proportions, in particular not more than 10 mol %, based on the proportion of Ph having the meaning given above, of other acids having at least two carboxyl groups, which allow soil removal, may be present in the 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 HO-(CHR 11 -) a OH including R 11 is hydrogen and a is a number from 2 to 6, and wherein the value of a is 2 and R 11 are selected from hydrogen and those having alkyl functions of 1 to 10, in particular 1 to 3, C atoms. In the last-mentioned diols, the formula HO-CH2-CHR 11 -OH (where R 11 Those with the above-mentioned meanings) are particularly preferred. Examples of diol components are ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,2-decanediol, 1,2-dodecanediol and neopentyl glycol. Particularly preferred polymer diols are polyethylene glycols with an average molar mass in the range of 1000 g / mol to 6000 g / mol. If desired, the polyesters may also be end-capped, wherein alkyl groups with 1 to 22 C atoms and esters of monocarboxylic acids are suitable as end groups. The end groups bonded 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, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, undecylenic acid, lauric acid, laureic acid Tridecanoic acid, myristic acid, myristoleic acid, pentadecanoic acid, palmitic acid, stearic acid, petroselinic acid, trans-petroselinic acid Oleic acid, linoleic acid, and trans-linoleic acid Linolenic acid, eleostearic acid, arachidic acid, cis-9-eicosenoic acid, arachidonic acid, behenic acid, erucic acid, cis-ramic acid The end groups may be hydroxy monocarboxylic acids with 5 to 22 C atoms, including hydroxyvaleric acid, hydroxycaproic acid, ricinoleic acid (its hydrogenation products include hydroxystearic acid) and o-hydroxybenzoic acid, m-hydroxybenzoic acid and p-hydroxybenzoic acid. The hydroxy monocarboxylic acids may then be connected to each other via their hydroxyl groups and their carboxyl groups, and thus may be present several times in the end groups. Preferably, the number of hydroxy monocarboxylic acid units (i.e., their degree of oligomerization) of each end group is between 1 and 50, particularly within the range of 1 to 10. In a preferred embodiment of the present invention, polymers of ethylene terephthalate and polyethylene oxide terephthalate are used together with the active ingredient combination essential for the present invention, wherein the molecular weight of the polyethylene glycol units in the polymer is 750 g / mol to 5000 g / mol and the molar ratio of ethylene terephthalate to polyethylene oxide terephthalate is 50:50 to 90:10. The polymers which allow the removal of dirt are preferably water-soluble, the term "water-soluble" being understood to mean having a solubility of at least 0.01 g, preferably at least 0.1 g, of polymer per liter of water at room temperature and pH 8. However, polymers which preferably are used have a solubility of at least 1 g / liter, in particular at least 10 g / liter, under these conditions.

[0047] The preparation of the solid agent according to the invention presents no difficulties and can be carried out in a known manner, for example by spray drying or granulation, wherein the enzyme and possibly other heat-sensitive ingredients (such as bleach) are optionally added separately later. For the preparation of the agent according to the invention with an increased bulk weight (in particular, in the range of 650 g / l to 950 g / l), a process with an extrusion step is preferred.

[0048] In order to prepare the agent according to the present invention in tablet form (which can be single-phase or multi-phase, monochrome or multi-color, and can be composed of one or more layers, especially two layers), all components (optionally respective layers) are preferably mixed with each other in a mixer, and a conventional tablet press (such as an eccentric press or a rotary tablet press) is used to compress the mixture using a pressure in the range of about 50 to 100 kN, preferably 60 to 70 kN. In the case of multi-layer tablets, it can be advantageous if at least one layer is pre-compressed. This is preferably carried out under a pressure of 5 to 20 kN, particularly 10 to 15 kN. This easily produces a rupture-resistant tablet with a common rupture strength and bending strength of 100 to 200 N, but preferably higher than 150 N, yet the tablet dissolves quickly enough under the conditions of use. The tablet thus prepared preferably has a weight of 10 g to 50 g, particularly 15 g to 40 g. The tablet can have any physical shape, and they can be circular, oval, or angular, with intermediate shapes also possible. Advantageously, corners and edges are rounded. The round tablets preferably have a diameter of 30 mm to 40 mm. In particular, the size of angular or cubic tablets, which are primarily introduced via a dosing device (e.g., a dishwasher), depends on the geometry and volume of the dosing device. For example, preferred embodiments have a base area of ​​(20 to 30 mm) x (34 to 40 mm), in particular 26 x 36 mm or 24 x 38 mm.

[0049] The liquid or pasty agents according to the invention in the form of solutions containing customary solvents, in particular water, are generally prepared by simply mixing the ingredients, which can be added in batches or in solution in an automatic mixer.

[0050] In another preferred embodiment, the reagent according to the present invention is pre-packed in a chamber formed by a water-soluble material in a single dose form; Then the reagent preferably contains less than 15 % by weight, particularly water in the range of 1 % by weight to 12 % by weight. The sub-packaging part (Portion) is an independent dosing unit with at least one chamber, contains product to be dosed in the chamber. Chamber is a space defined by a wall (for example, by a film), and the space can also exist (optionally by changing its shape) in the absence of product to be dosed. Therefore, surface coating or surface coating layer are not walls according to the present invention.

[0051] The walls of the chamber are made of a water-soluble material. The water solubility of this material can be determined according to the following measurement protocol using a square film of the material (film: 22×22 mm, thickness 76 μm) fixed in a square frame (inner side length: 20 mm). The framed film is immersed in 800 ml of distilled water, temperature-controlled to 20°C, in a 1-liter round-bottomed glass beaker (Schott, Mainz, 1000 ml glass beaker, low version) so that the surface of the stretched film is arranged at right angles to the beaker bottom, the upper edge of the frame is 1 cm below the water surface, and the lower edge of the frame is oriented parallel to the glass beaker bottom so that the lower edge of the frame extends along the radius of the glass beaker bottom and the center of the lower edge of the frame is arranged above the center of the radius of the glass beaker bottom. When stirred (magnetic stirrer stirring speed 300 rpm, stirring rod: 5 cm long), the material dissolves within 600 seconds, so that no solid particles are visible to the naked eye.

[0052] The walls of the chamber of the detergent according to the invention and thus the water-soluble wrapping are preferably formed from a water-soluble film material.Such water-soluble packaging can be produced by means of a vertical fill and seal method or by means of a thermoforming method.

[0053] The thermoforming method generally includes: forming a first layer from a water-soluble film material to create a protrusion for receiving the composition; pouring the composition into the protrusion; covering the protrusion filled with the composition with a second layer made of a water-soluble film material; and sealing the first and second layers to each other at least around the protrusion.

[0054] The water-soluble film material is preferably selected from a polymer or a polymer mixture. The wrapper may be composed of one layer or two or more layers of water-soluble film material. The water-soluble film material of the first layer and the additional layer (if present) may be the same or different.

[0055] The water-soluble coating preferably contains polyvinyl alcohol or a polyvinyl alcohol copolymer; particularly preferably, it consists of polyvinyl alcohol or a polyvinyl alcohol copolymer.

[0056] The water-soluble film used to prepare the water-soluble wrapping is preferably based on polyvinyl alcohol or a polyvinyl alcohol copolymer having a molecular weight of 10,000 to 1,000,000 gmol. -1 , preferably 20,000 to 500,000 gmol -1 , particularly preferably 30,000 to 100,000 gmol -1 , especially 40,000 to 80,000 gmol -1 within the range.

[0057] Polyvinyl alcohol is usually prepared by hydrolysis of polyvinyl acetate, since a direct synthetic route is not possible. The same applies to polyvinyl alcohol copolymers, which are correspondingly prepared from polyvinyl acetate copolymers. Preferably, at least one layer of the water-soluble coating comprises polyvinyl alcohol with a degree of hydrolysis of 70 to 100 mol %, preferably 80 to 90 mol %, particularly preferably 81 to 89 mol %, and in particular 82 to 88 mol %.

[0058] Polymers selected from the group consisting of acrylic acid-containing polymers, polyacrylamides, oxazoline polymers, polystyrene sulfonates, polyurethanes, polyesters, polyethers, polylactic acid, and / or mixtures thereof may be additionally added to the film material suitable for preparing the water-soluble wrapper. Monomers of the type on which the polymers are based may also be copolymerized with vinyl acetate, either individually or as a mixture of two or more thereof.

[0059] In addition to vinyl alcohol, preferred polyvinyl alcohol copolymers also contain ethylenically unsaturated carboxylic acids, or salts or esters thereof. In addition to vinyl alcohol, such polyvinyl alcohol copolymers particularly preferably contain acrylic acid, methacrylic acid, acrylic acid esters, methacrylic acid esters, or mixtures thereof; in the esters, C 1-4 Alkyl ester or C 1-4 Hydroxyalkyl esters are preferred. Polyvinyl alcohol copolymers which contain ethylenically unsaturated dicarboxylic acids as further monomers in addition to vinyl alcohol are also preferred. Suitable dicarboxylic acids are, for example, itaconic acid, maleic acid, fumaric acid, and mixtures thereof, with itaconic acid being particularly preferred.

[0060] Water soluble films suitable for use in the wrapping of the water soluble packages according to the present invention are those sold by MonoSol LLC, for example under the names M8630, C8400 or M8900. Other suitable films include those sold under the names PT, GA, KC, or Membranes of KL (Aicello Chemical Europe GmbH) or VF-HP membranes (Kuraray).

[0061] The detergent portion comprising detergent and water-soluble wrapper can comprise one or more chambers. The water-soluble wrapper with chamber can have a substantially dimensionally stable spherical, spheroidal, cubic, cubical, or pillow-shaped design, the design having a circular, oval, square, or rectangular basic shape. Reagent can be contained in one or more chambers (if present) of the water-soluble wrapper.

[0062] In a preferred embodiment, the water-soluble wrapper has two compartments. In this embodiment, the two compartments can each contain a single solid composition or a single liquid composition, or the first compartment contains a single liquid composition and the second compartment contains a single solid composition.

[0063] The ratios of the reagents contained in the different compartments of a water-soluble package having two or more compartments may have the same composition. However, preferably, the reagents in a water-soluble package having at least two compartments have separate compositions that differ in at least one component and / or the content of at least one component. Preferably, the separate composition of such reagents according to the invention comprises an enzyme and / or a bleach activator, and the separate, further separate composition comprises a peroxide bleach, whereby the first separate composition in particular does not comprise a peroxide bleach, and the second separate composition in particular does not comprise an enzyme or a bleach activator.

[0064] Encapsulating the portioned items in a water-soluble wrapper allows the user to place one or (if necessary) multiple (preferably one) portioned items in a washing machine, in particular in the detergent drawer of a washing machine, or in a container for performing a manual washing method, in one application. This sub-packaging meets the consumer's demand for simplified dosage. After adding water, the wrapping material dissolves so that the ingredients can be released and act in the liquid. Preferably, the weight of the portioned items of the water-soluble wrapper is 10 g to 35 g, in particular 12 g to 28 g, particularly preferably 12 g to 15 g, wherein the content of 0.3 g to 2.5 g, in particular 0.7 g to 1.2 g of the water-soluble wrapper contained in the weight is omitted. Example

[0065] A compound (M1) according to the general formula (I) was used, the functional group R of which consisted of 72% H and 28% of a 55:45 mixture of octanoate and decanoate. For comparison, a compound (V1) corresponding to another general formula (I) was used, the functional group R of which consisted of 100% H. From these, detergents W2 and W3, shown in the table below in terms of their composition (wt%), were prepared. For comparison, a compound W1 without either of these was also tested.

[0066] Table 1: Composition of detergent [wt %]

[0067]

[0068] These were used to wash cotton items soiled with the standard soils detailed in Table 2 below at 20°C for 150 minutes (with a main wash cycle duration of 90 minutes) and the increase in the washing power (lightness difference ΔY) of reagents W2 and W3 compared to the washing power of reagent W1 was determined:

[0069] Table 2: Increase in washing capacity [%]

[0070] Dirt / reagents W2 W3 milk fat 0.3 4.5 lipstick 1.5 6.4 Mineral oil / soot 0.3 9.0

[0071] It can be seen that the agent W3 according to the invention has a particularly high increase in washing power.

Claims

1. A detergent comprising a compound of formula (I), In the compounds of general formula (I), each R is selected from -H and -OC(=O)-R', and R' is selected from alkyl groups having 6 to 10 C atoms, and mixtures thereof, wherein at least 5% of the number of functional groups R are those other than H.

2. The reagent according to claim 1, characterized in that The agent contains 1% to 6% by weight, in particular 2% to 4% by weight, of the compound of the general formula (I).

3. The reagent according to claim 1 or claim 2, characterized in that The reagent is liquid.

4. The reagent according to claim 3, characterized in that The agent is pre-packaged in a single-dose form in a chamber formed of a water-soluble material and contains water in an amount of up to 15% by weight.

5. The reagent according to any one of claims 1 to 4, characterized in that The agent comprises 10 to 40% by weight, in particular 20 to 30% by weight, of synthetic anionic surfactants and / or the agent comprises 20 to 40% by weight, in particular 25 to 35% by weight, of nonionic surfactants and / or the agent comprises 5 to 20% by weight, in particular 7 to 15% by weight, of soap.

6. Use of compounds of the general formula (I) for improving the cleaning power of detergents against grease- or oil-based textile stains, In the compounds of general formula (I), each R is selected from -H and -OC(=O)-R', and R' is selected from alkyl groups having 6 to 10 C atoms, and mixtures thereof, wherein at least 5% of the number of functional groups R are those other than H.

7. A method for removing grease- or oil-based soiling from fabrics, characterized in that bringing the fabrics in need of such cleaning into contact with water and a compound of general formula (I) or an agent according to one of claims 1 to 5, In the compounds of general formula (I), each R is selected from -H and -OC(=O)-R', and R' is selected from alkyl groups having 6 to 10 C atoms, and mixtures thereof, wherein at least 5% of the number of functional groups R are those other than H.

8. The method according to claim 7, characterized in that The process is carried out at a temperature ranging from room temperature to 60°C, in particular from 20°C to 40°C.

9. The agent according to one of claims 1 to 5, the use according to claim 6, or the method according to claim 7 or claim 8, characterized in that 20% to 35%, in particular 25% to 30%, of the number of functional groups R in the compounds of general formula (I) are not H.

10. The agent according to one of claims 1 to 5 or 9, the use according to claim 6 or claim 9, or the method according to one of claims 7 to 9, characterized in that In the compounds of the general formula (I), 35% to 65%, in particular 40% to 60%, of the number of functional groups R' among the functional groups R that are not H are those having C7 alkyl groups, and 65% to 35%, in particular 60% to 40% of the number of functional groups R' among the functional groups R that are not H are those having C9 alkyl groups.

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