DE102019218828A1 - Use of copolymers as active ingredients that increase tensile strength - Google Patents

Abstract

The invention relates to the use of copolymers of ethylenically unsaturated monomers in the form of methacrylic acid esters of ammonium alcohols and of oligoether alcohols to increase the tear strength of textiles.

Description

The invention relates to the use of certain copolymers of ethylenically unsaturated compounds for increasing the tear resistance of textiles.

Consumers want the laundry not only to be clean and fresh after washing, but also to retain its stability in the end.

Surprisingly, it has been found that the use of copolymers of ethylenically unsaturated monomers in the form of methacrylic acid esters of ammonium alcohols and oligoether alcohols during washing leads to an increase in the tear resistance of textiles and the use of detergents or laundry treatment agents leads to an increase in the tear resistance of the textile when the Agents contain such a copolymer.

in der n für eine Zahl gleich oder größer 3, insbesondere für eine Zahl im Bereich von 3 bis 120, bevorzugter für eine Zahl im Bereich von 5 bis 50 und besonders bevorzugt für eine Zahl im Bereich von 7 bis 46 steht, wobei in einer Ausführungsform n ausgewählt ist aus der Gruppe umfassend die Zahlen 7, 23 und 46, mit mindestens einer Verbindung der Formel (II),

in der A^- für ein Anion, insbesondere ausgewählt aus Halogeniden wie Fluorid, Chlorid, Bromid, lodid, Sulfat, Hydrogensulfat, Alkylsulfat wie Methylsulfat und Mischungen aus diesen, steht, zur Erhöhung der Reißfestigkeit von Textilien.The invention therefore relates to the use of copolymers obtainable by radical copolymerization of at least one compound of the formula (I),

in which n is a number equal to or greater than 3, in particular a number in the range from 3 to 120, more preferably a number in the range from 5 to 50 and particularly preferably a number in the range from 7 to 46, in one embodiment n is selected from the group comprising the numbers 7, 23 and 46, with at least one compound of the formula (II),

in which A ^{- stands} for an anion, in particular selected from halides such as fluoride, chloride, bromide, iodide, sulfate, hydrogen sulfate, alkyl sulfate such as methyl sulfate and mixtures of these, for increasing the tensile strength of textiles.

The tear resistance of textiles is determined by determining the tear strength. The determination of the tear strength of textiles with the ballistic pendulum (Elmendorf) is carried out in accordance with DIN EN ISO 13937-1: 2000 and is used to evaluate the tear strength of textiles. The test simulates the practical case in which the textile fabric is exposed to a sudden load and thus - starting from an existing interface, for example the pocket corner of a pair of pants or a skirt, a slit or a buttonhole - tears. The work of tearing through is measured directly with the ballistic pendulum and is generally given as the tearing force. The greater the value determined, the higher the tear resistance of the textiles.

The polymers essential to the invention can be obtained by free radical polymerization processes known in principle. A mixture of compound of general formula (I) and compound of general formula (II) is used in the presence of a radical initiator, such as a bi-azo compound, a persulfate, a peroxide or a hydroperoxide, if desired in the presence of a reducing agent such as Ascorbic acid or hydroxymethyl sulfinate, to random copolymers. Alternatively, the monomer of the general formula (I) or the monomer of the general formula (II) can first be polymerized by free radicals and then the monomer of the general formula (II) or the monomer of the general formula (I) can be polymerized radically, so that block Copolymers obtained. Random copolymers are preferred according to the invention. About 0.01% by weight to 5% by weight of free radical initiators, based on the total amount of monomers used, is generally present in the polymerization.

ersetzt sein. Bei der Herstellung der erfindungsgemäß eingesetzten Polymere kann man auch von der Monomerverbindung (III) ausgehen und das nach Umsetzung mit der Verbindung der allgemeinen Formel (I) erhaltene Copolymer mit einem Methylierungsmittel umsetzen. Derartige Polymere und Verfahren zu ihrer Herstellung sind beispielsweise aus der europäischen Patentanmeldung EP 3 196 283 A1 bekannt.Preferred polymers used according to the invention are obtainable by copolymerization of the compound according to general formula (I) and the compound according to general formula (II) in molar ratios in the range from 1:99 to 75:25, in particular in the range from 5:95 to 70: 30th The polymers used according to the invention preferably contain no parts originating from monomers other than the compounds of the general formulas (I) and (II), with the exception of parts originating from radical initiator or radical termination compounds. However, part of the amount of compounds of the general formula (II), preferably not more than 60 mol%, can be replaced by the corresponding non-quaternized compound of the formula (III),

be replaced. In the preparation of the polymers used according to the invention, one can also start from the monomer compound (III) and react the copolymer obtained after reaction with the compound of the general formula (I) with a methylating agent. Such polymers and processes for their production are, for example, from the European patent application EP 3 196 283 A1 known.

The mean molecular weight (weight average) of the copolymers used according to the invention is preferably in the range from 10,000 g / mol to 100,000 g / mol, in particular from 20,000 g / mol to 70,000 g / mol.

Another object of the invention is a method for increasing the tear resistance of textiles, wherein an above-mentioned copolymer in substance or as a component of a liquid preparation, such as a solution, suspension or dispersion, is brought into contact with the textile and, if desired, excess material from the textile surface removed.

The use according to the invention can be carried out in a simple manner in that the copolymer, in substance or as a component of a liquid preparation, such as a solution, suspension or dispersion (in acetone, for example), is applied to the textile surface, in particular of textiles made of polyester or with a polyester component , applies, for example by pouring or spraying, and, if desired, excess material, for example with the help of a cloth or sponge, removed from the textile surface. Preferably 0.01 ml to 1 ml, in particular 0.1 ml of a 1 percent by weight to 10 percent by weight, in particular 2 percent by weight liquid preparation, in particular solution, of the copolymer is applied per cm ^{2 of} the surface, and it is allowed to act for at least 30 minutes, wherein the solvent, dispersant or suspending agent of the liquid preparation can optionally, completely or partially, evaporate. It is also possible to immerse the textile in a liquid preparation mentioned. In a preferred embodiment of the invention, the polymer essential to the invention is applied to textiles by spraying an aqueous preparation containing the polymer, for example by means of a spray can (pressurized gas can, pressurized gas pack, aerosol pack) or a mechanically operated pump atomizer (pump spray), from which the polymer preparation is formed, for example spray, foam, paste or jet of liquid emerges.

The liquid preparation mentioned can be an in particular water-containing wash or laundry aftertreatment liquor which contains the copolymer mentioned. The use according to the invention can, however, also take place through the application, in particular in one of the liquors mentioned, of a laundry detergent or laundry aftertreatment agent which contains the copolymer, and embodiments of the process according to the invention can be carried out using such a laundry detergent or laundry aftertreatment agent.

The agent preferably contains 0.0006% by weight to 6% by weight, in particular 0.006% by weight to 0.6% by weight, of the copolymer, the percentages by weight here and below referring to the refer to total funds unless otherwise stated. A laundry treatment agent is to be understood here as an agent which, when used, does not focus on removing dirt, as is the case with a detergent, but primarily serves to care for the laundry, such as a fabric softener or a fabric softener used in the laundry post-treatment step Laundry ironing aid. Finally, in a preferred embodiment, the laundry treatment agent to be used is transparent and is also suitable for spraying.

By using the copolymer or the detergent or laundry treatment agent it contains, the copolymer is deposited on the textile surface, which leads to a sustained increase in the tear resistance of the textile. This effect can be observed in particular over a longer period of time after the application of the copolymer or the agent, for example three weeks.

The use according to the invention can be carried out in the context of a washing process in such a way that the active ingredient which increases tear resistance is added to a detergent-containing liquor or, preferably, the active ingredient is introduced into the liquor as a component of a detergent which contains the textile to be treated or which is brought into contact with it.

The use according to the invention in the context of a laundry aftertreatment process can accordingly be carried out in such a way that the active ingredient which increases tear resistance is added separately to the rinsing liquor, which is used after the wash cycle, in particular using a detergent containing bleach, or it is incorporated as a component of the laundry aftertreatment agent, in particular a fabric softener. In this aspect of the invention, the detergent used before the laundry aftertreatment agent can also contain an active ingredient to be used according to the invention, but is preferably free of this.

The washing process is preferably carried out at a temperature of 15 ° C to 60 ° C, particularly preferably at a temperature of 20 ° C to 40 ° C. The washing process is also preferably carried out at a pH of 6 to 11, particularly preferably at a pH of 7.5 to 9.5. The use concentration of the above-defined copolymer in the washing or laundry aftertreatment liquor is preferably in the range from 0.3 mg / l to 100 mg / l, in particular from 1 mg / l to 5 mg / l.

In the context of the use according to the invention and the method according to the invention, it is possible to use the tear strength-increasing active ingredient as such; The active ingredient can, however, also be present in a formulation form that makes use by the user easier for the user, for example in a mixture or granulated with carrier substances, binders, coating materials, extrusion aids, flow improvers, stabilizers, solvents, rheology modifiers and / or emulsifiers. This embodiment of the invention makes it possible for the consumer to benefit from the advantages of the invention by using the tear strength-increasing active ingredient in addition to conventional detergents and / or laundry aftertreatment agents only when they are desired.

Agents that contain an active ingredient to be used according to the invention in the form of the named copolymer or are used together with this or are used in the method according to the invention can contain all the usual other components of such agents that do not interact in an undesirable manner with the active ingredient according to the invention, in particular surfactant. It is preferred if such agents contain 1% by weight to 50% by weight, in particular 3% by weight to 20% by weight, of surfactant.

In a preferred embodiment, an agent used according to the invention or used in the process according to the invention contains nonionic surfactant selected from fatty alkyl polyglycosides, fatty alkyl polyalkoxylates, in particular ethoxylates and / or propoxylates, fatty acid polyhydroxyamides and / or ethoxylation and / or propoxylation products of fatty alkylamines, vicinal diols, fatty acids / or fatty acid amides and mixtures thereof, in particular in an amount in the range from 2% by weight to 25% by weight.

Another embodiment of such agents comprises the presence of synthetic anionic surfactant of the sulfate and / or sulfonate type, in particular fatty alkyl sulfate, fatty alkyl ether sulfate, sulfo fatty acid esters and / or sulfo fatty acid disalts, in particular in an amount in the range from 2% by weight to 25% by weight. The anionic surfactant is preferably selected from the alkyl or alkenyl sulfates and / or the alkyl or alkenyl ether sulfates in which the alkyl or alkenyl group has 8 to 22, in particular 12 to 18, carbon atoms. These are usually not individual substances, but cuts or mixtures. Of these, preference is given to those whose proportion of compounds with longer-chain radicals in the range from 16 to 18 carbon atoms is more than 20% by weight.

The nonionic surfactants in question include the alkoxylates, in particular the 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. The degree of alkoxylation of the alcohols is generally between 1 and 20, preferably between 3 and 10. They can be used in a known manner Way can be prepared by reacting the corresponding alcohols with the corresponding alkylene oxides. The derivatives of fatty alcohols are particularly suitable, although their branched-chain isomers, in particular so-called oxo alcohols, can also be used to prepare usable alkoxylates. Accordingly, the alkoxylates, in particular the ethoxylates, of primary alcohols with linear, in particular dodecyl, tetradecyl, hexadecyl or octadecyl radicals and mixtures thereof can be used. Corresponding alkoxylation products of alkylamines, vicinal diols and carboxamides which correspond to the alcohols mentioned with regard to the alkyl moiety can also be used. The ethylene oxide and / or propylene oxide insertion products of fatty acid alkyl esters and fatty acid polyhydroxyamides are also suitable. So-called alkyl polyglycosides suitable for incorporation into the agents are compounds of the general formula (G) _n -OR ¹² , in which R ^{12 is} an alkyl or alkenyl radical having 8 to 22 carbon atoms, G is a glycose unit and n is a number between 1 and 10 . The glycoside component (G) _n is oligo- or polymers from naturally occurring aldose or ketose monomers, to which in particular glucose, mannose, fructose, galactose, talose, gulose, altrose, allose, idose, ribose, arabinose, Include xylose and lyxosis. The oligomers consisting of such glycosidically linked monomers are characterized not only by the type of sugars they contain but also by their number, the so-called degree of oligomerization. The mean degree of oligomerization n generally assumes fractional numerical values as a variable to be determined analytically; it is between 1 and 10, in the case of the glycosides preferably used below a value of 1.5, in particular in the range from 1.2 to 1.4. The preferred monomer building block is glucose because of its ready availability. The alkyl or alkenyl part R ^{12 of} the glycosides also preferably comes from easily accessible derivatives of renewable raw materials, in particular from fatty alcohols, although their branched-chain isomers, in particular so-called oxo alcohols, can also be used to produce usable glycosides. Accordingly, the primary alcohols with linear octyl, decyl, dodecyl, tetradecyl, hexadecyl or octadecyl radicals and mixtures thereof are particularly useful. Particularly preferred alkyl glycosides contain a coconut fatty alkyl radical, that is to say mixtures with essentially R ¹² = dodecyl and R ¹² = tetradecyl.

Nonionic surfactant is used in agents which contain a soil release agent used according to the invention or are used in the process according to the invention, preferably in amounts of 1% by weight to 30% by weight, in particular from 1% by weight to 25% % By weight, amounts in the upper part of this range are more likely to be found in liquid detergents and particulate detergents preferably contain smaller amounts of up to 5% by weight.

Instead or in addition, the agents can contain further surfactants, preferably synthetic anionic surfactants of the sulfate or sulfonate type, such as, for example, alkylbenzenesulfonates, in amounts of preferably not more than 20% by weight, in particular from 0.1% by weight to 18% by weight. %, each based on the total mean. Particularly suitable synthetic anionic surfactants for use in such agents are the alkyl and / or alkenyl sulfates with 8 to 22 carbon atoms which have an alkali, ammonium or alkyl or hydroxyalkyl-substituted ammonium ion as a counter cation. The derivatives of fatty alcohols having in particular 12 to 18 carbon atoms and their branched-chain analogs, the so-called oxo alcohols, are preferred. The alkyl and alkenyl sulfates can be prepared in a known manner by reacting the corresponding alcohol component with a customary sulfating reagent, in particular sulfur trioxide or chlorosulfonic acid, and subsequent neutralization with alkali, ammonium or alkyl or hydroxyalkyl-substituted ammonium bases. The sulfate-type surfactants that can be used also include the sulfated alkoxylation products of the alcohols mentioned, 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 those derived from fatty acids with 8 to 22 carbon atoms, preferably 12 to 18 carbon atoms, and linear alcohols with 1 up to 6 carbon atoms, preferably 1 to 4 carbon atoms, derived sulfonation products, as well as the sulfo fatty acids resulting from these by formal saponification.

Other optional surfactant ingredients are soaps, saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid or stearic acid, and soaps derived from natural fatty acid mixtures, for example coconut, palm kernel or tallow fatty acids, being suitable. In particular, preference is given to soap mixtures which are composed of 50% by weight to 100% by weight of saturated C ₁₂ -C ₁₈ fatty acid soaps and up to 50% by weight of oleic acid soap. Soap is preferably contained in amounts of 0.1% by weight to 5% by weight. In particular, however, liquid agents which contain a polymer used according to the invention can also contain higher amounts of soap, generally up to 20% by weight.

If desired, the agents can also contain betaines and / or cationic surfactants, which - if present - are preferably used in amounts of 0.5% by weight to 7% by weight. Among these, the esterquats discussed below are particularly preferred.

An agent which contains an active ingredient to be used according to the invention or is used together with it or is used in the process according to the invention preferably contains peroxygen-based bleaching agents, in particular in amounts in the range from 5% by weight to 70% by weight, and optionally However, in another preferred embodiment, bleach activator, in particular in amounts in the range from 0.3% by weight to 10% by weight, can also be free from bleaching agent and bleach activator. The bleaching agents which can be used are preferably the peroxygen compounds usually used in detergents, such as percarboxylic acids, for example dodecanediperic acid or phthaloylaminoperoxicaproic acid, hydrogen peroxide, alkali perborate, which can be present as tetra- or monohydrate, percarbonate, perpyrophosphate and persilicate, which are usually as alkali salts, in particular as sodium salts. Such bleaches are in detergents which contain an active ingredient used according to the invention, preferably in amounts of up to 25% by weight, in particular up to 15% by weight and particularly preferably from 5% by weight to 15% by weight, in each case on the entire medium, with percarbonate in particular being used. The optionally present component of the bleach activators comprises the commonly used N- or O-acyl compounds, for example poly-acylated alkylenediamines, in particular tetraacetylethylenediamine, acylated glycolurils, in particular tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, urazoles, diketopiperazines and carboxylic acid anurylamides , in particular phthalic anhydride, carboxylic acid esters, in particular sodium nonanoyl and isononanoyl phenol sulfonate, and acylated sugar derivatives, in particular pentaacetyl glucose, and cationic nitrile derivatives such as trimethylammonium acetonitrile salts. To avoid interaction with the peroxygen compounds during storage, the bleach activators may have been coated or granulated with coating substances in a known manner, with the aid of carboxymethylcellulose granulated tetraacetylethylenediamine with weight-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 made up in particulate form is particularly preferred. Such bleach activators are preferably contained in detergents in amounts of up to 8% by weight, in particular from 2% by weight to 6% by weight, based in each case on the total detergent.

In a further preferred embodiment, the agent contains water-soluble and / or water-insoluble builders, in particular selected from alkali metal alumosilicate, crystalline alkali metal silicate with a modulus greater than 1, monomeric polycarboxylate, polymeric polycarboxylate and mixtures thereof, in particular in amounts in the range from 2.5 wt 60% by weight.

The agent preferably contains 20% by weight 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, and polymeric (poly) carboxylic acids, in particular the polycarboxylates, polymeric acrylic acids, methacrylic acids, maleic acids and copolymers of these, which can also be obtained by oxidation of polysaccharides may contain small amounts of polymerizable substances without carboxylic acid functionality polymerized. The relative molecular weight of the homopolymers of unsaturated carboxylic acids is generally between 5000 g / mol and 200,000 g / mol, that of the copolymers between 2000 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 makes up at least 50% by weight. Terpolymers which contain two carboxylic acids and / or their salts as monomers and vinyl alcohol and / or a vinyl alcohol derivative or a carbohydrate as a third monomer can also be used as water-soluble organic builder substances. The first acidic monomer or its salt is derived from a monoethylenically unsaturated C ₃ -C ₈ carboxylic acid and preferably from a C ₃ -C ₄ monocarboxylic acid, in particular from (meth) acrylic acid. The second acidic monomer or its salt can be a derivative of a C ₄ -C ₈ dicarboxylic acid, maleic acid being particularly preferred. The third monomeric unit is formed in this case by vinyl alcohol and / or preferably an esterified vinyl alcohol. In particular, vinyl alcohol derivatives are preferred which represent an ester of short-chain carboxylic acids, for example of C ₁ -C ₄ carboxylic acids, with vinyl alcohol. Preferred terpolymers contain 60% by weight to 95% by weight, in particular 70% by weight to 90% by weight (meth) acrylic acid and / or (meth) acrylate, particularly preferably acrylic acid and / or acrylate, and maleic acid and / or maleate and 5% by weight to 40% by weight, preferably 10% by weight to 30% by weight, vinyl alcohol and / or vinyl acetate. Terpolymers 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 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 which is in the 2-position with an alkyl radical, preferably with a C ₁ -C ₄ -alkyl radical, or an aromatic radical which is preferably derived from benzene or benzene derivatives , is substituted. Preferred terpolymers contain 40 wt% to 60 wt%, in particular 45 to 55 wt% (meth) acrylic acid and / or (meth) acrylate, particularly preferably acrylic acid and / or acrylate, 10 wt% to 30% by weight, preferably 15% by weight to 25% by weight methallylsulfonic acid and / or methallylsulfonate and, as the third monomer, 15% by weight to 40% by weight, preferably 20% by weight to 40% by weight % of a carbohydrate. This carbohydrate can be, for example, a mono-, di-, oligo- or polysaccharide, mono-, di- or oligosaccharides being preferred, sucrose being particularly preferred. By using the third monomer, predetermined breaking points are presumably built into the polymer, which are responsible for the good biodegradability of the polymer. These terpolymers generally have a relative molecular weight between 1000 g / mol and 200,000 g / mol, preferably between 3000 g / mol and 10,000 g / mol. In particular for the production of liquid agents, they can be used 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, in particular their alkali metal salts.

Such organic builder substances are preferably present in amounts of up to 40% by weight, in particular up to 25% by weight and particularly preferably from 1% by weight to 5% by weight. Quantities close to the upper limit mentioned are preferably used in paste-like or liquid, in particular water-containing, agents.

The water-insoluble, water-dispersible inorganic builder materials used are in particular crystalline or amorphous alkali metal aluminosilicates, in amounts of up to 50% by weight, preferably not more than 40% by weight and in liquid agents in particular from 1% by weight to 5% by weight used. Among these, the crystalline aluminosilicates in detergent quality, in particular zeolite NaA and optionally NaX, are preferred. Quantities close to the upper limit mentioned are preferably used in solid, particulate compositions. Suitable aluminosilicates in particular do not have any particles with a particle size of more than 30 μm and preferably consist of at least 80% by weight of particles with a size of less than 10 μm. Their calcium binding capacity is in the range from 100 to 200 mg CaO per gram.Suitable substitutes or partial substitutes for said aluminosilicate are crystalline alkali silicates, which can be present alone or in a mixture with amorphous silicates. The alkali silicates which can be used as builders in the agents preferably have a molar ratio of alkali oxide to SiO ₂ below 0.95, in particular from 1: 1.1 to 1:12, and can be amorphous or crystalline. Preferred alkali silicates are the sodium silicates, in particular the amorphous sodium silicates, with a molar ratio Na ₂ O: SiO ₂ of 1: 2 to 1: 2.8. Such amorphous alkali silicates are commercially available, for example, under the name Portil®. In the course of production, they are preferably added as a solid and not in the form of a solution. The crystalline silicates used alone or in a mixture with amorphous silicates are preferably crystalline _{sheet silicates of the general formula Na 2} Si _x O _{2x + 1} · yH ₂ O, in which x, the so-called modulus, is a number of 1.9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4. Preferred crystalline sheet silicates are those in which x in the general formula mentioned assumes the values 2 or 3. In particular, both β- and δ-sodium _{disilicates (Na 2} Si ₂ O ₅ · yH ₂ O) are preferred. Virtually anhydrous crystalline alkali silicates of the above general formula, in which x is a number from 1.9 to 2.1, produced from amorphous alkali silicates, can also be used in agents which contain an active ingredient to be used according to the invention. In a further preferred embodiment of agents according to the invention, a crystalline layered sodium silicate with a module of 2 to 3, as can be produced from sand and soda, is used. 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 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 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 anhydrous active substance. The weight ratio of aluminosilicate to silicate, based in each case on anhydrous active substances, is then preferably 4: 1 to 10: 1. In agents which contain 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.

In addition to the inorganic builder mentioned, further water-soluble or water-insoluble inorganic substances can be contained in the agents which contain an active ingredient to be used according to the invention, used together with this or used in the method according to the invention. In this context, the alkali metal carbonates, alkali metal hydrogen carbonates and alkali metal sulfates and mixtures thereof are suitable. Such additional inorganic material can be present in amounts up to 70% by weight.

In addition, the agents can contain other constituents that are customary in detergents and cleaning agents. These optional components 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, up to 1 wt .-%, in particular 0.01 wt .-% to 0.5 wt .-% optical brighteners, in particular compounds from the class of the substituted 4,4 'are in agents which contain an active ingredient used according to the invention -Bis- (2,4,6-triamino-s-triazinyl) -stilbene-2,2'-disulfonic acids, up to 5% by weight, in particular 0.1% by weight to 2% by weight, of complexing agents for Contain heavy metals, in particular aminoalkylenephosphonic acids and their salts, and up to 2% by weight, in particular 0.1% by weight to 1% by weight, foam inhibitors, the stated percentages by weight referring to the total agent.

Solvents that can be used in particular with liquid agents are, in addition to water, preferably those that are water-miscible. These include the lower alcohols, for example ethanol, propanol, iso-propanol, and the isomeric butanols, glycerol, lower glycols, for example ethylene and propylene glycol, and the ethers which can be derived from the cited classes of compounds. The active ingredients used according to the invention are generally dissolved or in suspended form in such liquid agents.

Any enzymes present are preferably selected from the group comprising protease, amylase, lipase, cellulase, hemicellulase, oxidase, peroxidase or mixtures of these. Primarily protease obtained from microorganisms such as bacteria or fungi comes into question. It can be obtained in a known manner from suitable microorganisms by fermentation processes. Proteases are commercially available, for example, under the names BLAP®, Savinase®, Esperase®, Maxatase®, Optimase®, Alcalase®, Durazym® or Maxapem®. The lipase which can be used can be obtained, for example, from Humicola lanuginosa, from Bacillus species, from Pseudomonas species, from Fusarium species, from Rhizopus species or from Aspergillus species. Suitable lipases are commercially available, for example, under the names Lipolase®, Lipozym®, Lipomax®, Lipex®, Amano®-Lipase, Toyo-Jozo®-Lipase, Meito®-Lipase and Diosynth®-Lipase. Suitable amylases are commercially available, for example, under the names Maxamyl®, Termamyl®, Duramyl® and Purafect® OxAm. The cellulase which can be used can be an enzyme which can be obtained from bacteria or fungi and which has a pH optimum, preferably in the weakly acidic to weakly alkaline range of 6 to 9.5. Such cellulases are commercially available under the names Celluzyme®, Carezyme® and Ecostone®. It is particularly preferred if an agent used in the context of the invention contains 0.001% by weight to 1% by weight, in particular 0.005% by weight to 0.3% by weight, cellulase.

The customary enzyme stabilizers optionally present, in particular in liquid agents, include amino alcohols, for example mono-, di-, triethanol- and propanolamine and mixtures thereof, lower carboxylic acids, boric acid or 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.

Suitable foam inhibitors include long-chain soaps, in particular behen soap, fatty acid amides, paraffins, waxes, microcrystalline waxes, organopolysiloxanes and mixtures thereof, which can also contain microfine, optionally silanized or otherwise hydrophobized silica. For use in particulate agents, foam inhibitors of this type are preferably bound to granular, water-soluble carrier substances.

In a preferred embodiment, an agent into which the active ingredient to be used according to the invention is incorporated is particulate and contains up to 25% by weight, in particular 5% by weight to 20% by weight bleach, in particular alkali percarbonate, up to 15% by weight. -%, in particular 1% by weight to 10% by weight bleach activator, 20% by weight to 55% by weight inorganic builder, up to 10% by weight, in particular 2% by weight to 8% by weight % water-soluble organic builder, 10% by weight to 25% by weight synthetic anionic surfactant, 1% by weight to 5% by weight nonionic surfactant and up to 25% by weight, in particular 0.1% by weight to 25% by weight of inorganic salts, in particular alkali metal carbonate and / or hydrogen carbonate.

In a further preferred embodiment, an agent into which the active ingredient to be used according to the invention is incorporated is liquid and contains 1% by weight to 25% by weight, in particular 5% by weight to 15% by weight nonionic surfactant, up to 10% by weight, in particular 0.5% by weight to 8% by weight synthetic anionic surfactant, 3% by weight to 15% by weight, in particular 5% by weight to 10% by weight soap, 0 , 5% by weight to 5% by weight, in particular 1% by weight to 4% by weight of organic builder, in particular polycarboxylate such as citrate, up to 1.5% by weight, in particular 0.1% by weight % to 1% by weight complexing agent for heavy metals, such as phosphonate, and in addition to any enzyme, enzyme stabilizer, color and / or fragrance contained, water and / or water-miscible solvent.

Preferred laundry aftertreatment agents which contain an active ingredient to be used according to the invention have a so-called esterquat, that is to say a quaternized ester of carboxylic acid and amino alcohol, as the fabric softening active ingredient. These are known substances that can be obtained by the relevant methods of preparative organic chemistry, for example by partially esterifying triethanolamine with fatty acids in the presence of hypophosphorous acid, passing air through and then quaternizing with dimethyl sulfate or ethylene oxide. The production of solid ester quats is also known, in which the quaternization of triethanolamine esters is carried out in the presence of suitable dispersants, preferably fatty alcohols.

in der R¹CO für einen Acylrest mit 6 bis 22 Kohlenstoffatomen, R² und R³ unabhängig voneinander für Wasserstoff oder R¹CO, R⁴ für einen Alkylrest mit 1 bis 4 Kohlenstoffatomen oder eine (CH₂CH₂O)_qH-Gruppe, m, n und p in Summe für 0 oder Zahlen von 1 bis 12, q für Zahlen von 1 bis 12 und X für ein ladungsausgleichendes Anion wie Halogenid, Alkylsulfat oder Alkylphosphat steht. Typische Beispiele für Esterquats, die im Sinne der Erfindung Verwendung finden können, sind Produkte auf Basis von Capronsäure, Caprylsäure, Caprinsäure, Laurinsäure, Myristinsäure, Palmitinsäure, Isostearinsäure, Stearinsäure, Ölsäure, Elaidinsäure, Arachinsäure, Behensäure und Erucasäure sowie deren technische Mischungen, wie sie beispielsweise bei der Druckspaltung natürlicher Fette und Öle anfallen. Vorzugsweise werden technische C_12/18-Kokosfettsäuren und insbesondere teilgehärtete C_16/18-Talg- beziehungsweise Palmfettsäuren sowie elaidinsäure-reiche C_16/18-Fettsäureschnitte eingesetzt. Zur Herstellung der quaternierten Ester können die Fettsäuren und das Triethanolamin in der Regel im molaren Verhältnis von 1,1 : 1 bis 3 : 1 eingesetzt werden. Im Hinblick auf die anwendungstechnischen Eigenschaften der Esterquats hat sich ein Einsatzverhältnis von 1,2 : 1 bis 2,2 : 1, vorzugsweise 1,5 : 1 bis 1,9 : 1 als besonders vorteilhaft erwiesen. Die bevorzugt eingesetzten Esterquats stellen technische Mischungen von Mono-, Di- und Triestern mit einem durchschnittlichen Veresterungsgrad von 1,5 bis 1,9 dar und leiten sich von technischer C_16/18-Talg- bzw. Palmfettsäure (lodzahl 0 bis 40) ab. Quaternierte Fettsäuretriethanolaminestersalze der Formel (IV), in der R¹CO für einen Acylrest mit 16 bis 18 Kohlenstoffatomen, R² für R¹CO, R³ für Wasserstoff, R⁴ für eine Methylgruppe, m, n und p für 0 und X für Methylsulfat steht, haben sich als besonders vorteilhaft erwiesen.Esterquats preferred in the agents are quaternized fatty acid triethanolamine ester salts which follow the formula (IV),

in which R ¹ CO stands for an acyl radical with 6 to 22 carbon atoms, R ² and R ³ independently of one another for hydrogen or R ¹ CO, R ⁴ for an alkyl radical with 1 to 4 carbon atoms or a (CH ₂ CH ₂ O) _q H- Group, m, n and p in total for 0 or numbers from 1 to 12, q for numbers from 1 to 12 and X for a charge-balancing anion such as halide, alkyl sulfate or alkyl phosphate. Typical examples of esterquats that can be used for the purposes of the invention are products based on caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, isostearic acid, stearic acid, oleic acid, elaidic acid, arachic acid, behenic acid and erucic acid and their technical mixtures, such as they arise, for example, from the pressure splitting of natural fats and oils. Technical C _12/18 coconut fatty acids and in particular partially hydrogenated C _16/18 tallow or palm fatty acids and elaidic acid-rich C _{16/18 fatty acid cuts are preferably used.} To prepare the quaternized esters, the fatty acids and the triethanolamine can generally be used in a molar ratio of 1.1: 1 to 3: 1. With regard to the application properties of the esterquats, a use ratio of 1.2: 1 to 2.2: 1, preferably 1.5: 1 to 1.9: 1, has proven to be particularly advantageous. The esterquats used with preference are technical mixtures of mono-, di- and triesters with an average degree of esterification of 1.5 to 1.9 and are derived from technical C _16/18 tallow or palm fatty acid (iodine number 0 to 40) . Quaternized fatty acid triethanolamine ester salts of the formula (IV) in which R ^{1 is} CO for an acyl radical having 16 to 18 carbon atoms, R ² for R ¹ CO, R ³ for hydrogen, R ⁴ for a methyl group, m, n and p for 0 and X for Methyl sulfate has been found to be particularly advantageous.

in der R¹CO für einen Acylrest mit 6 bis 22 Kohlenstoffatomen, R² für Wasserstoff oder R¹CO, R⁴ und R⁵ unabhängig voneinander für Alkylreste mit 1 bis 4 Kohlenstoffatomen, m und n in Summe für 0 oder Zahlen von 1 bis 12 und X für ein ladungsausgleichendes Anion wie Halogenid, Alkylsulfat oder Alkylphosphat steht.In addition to the quaternized carboxylic acid triethanolamine ester salts, quaternized ester salts of carboxylic acids with diethanolalkylamines of the formula (V) are also suitable as ester quats,

in which R ¹ CO for an acyl radical with 6 to 22 carbon atoms, R ² for hydrogen or R ¹ CO, R ⁴ and R ⁵ independently of one another for alkyl radicals with 1 to 4 carbon atoms, m and n in total for 0 or numbers from 1 to 12 and X stands for a charge-balancing anion such as halide, alkyl sulfate or alkyl phosphate.

in der R¹CO für einen Acylrest mit 6 bis 22 Kohlenstoffatomen, R² für Wasserstoff oder R¹CO, R⁴, R⁶ und R⁷ unabhängig voneinander für Alkylreste mit 1 bis 4 Kohlenstoffatomen, m und n in Summe für 0 oder Zahlen von 1 bis 12 und X für ein ladungsausgleichendes Anion wie Halogenid, Alkylsulfat oder Alkylphosphat steht.Finally, a further group of suitable ester quats are the quaternized ester salts of carboxylic acids with 1,2-dihydroxypropyldialkylamines of the formula (VI),

in which R ¹ CO for an acyl radical with 6 to 22 carbon atoms, R ² for hydrogen or R ¹ CO, R ⁴ , R ⁶ and R ⁷ independently of one another for alkyl radicals with 1 to 4 carbon atoms, m and n in total for 0 or numbers from 1 to 12 and X is a charge-balancing anion such as halide, alkyl sulfate or alkyl phosphate.

With regard to the selection of the preferred fatty acids and the optimum degree of esterification, the exemplary details given for (IV) also apply mutatis mutandis to the esterquats of the formulas (V) and (VI). The esterquats are usually sold in the form of 50 to 90 percent strength by weight alcoholic solutions, which can also be diluted with water without any problems, with ethanol, propanol and isopropanol being the usual alcoholic solvents.

Esterquats are preferably used in amounts of 5% by weight to 25% by weight, in particular 8% by weight to 20% by weight, based in each case on the total laundry aftertreatment agent. If desired, the laundry aftertreatment agents used according to the invention can additionally contain the detergent ingredients listed above, provided they do not interact negatively with the ester quat in an unreasonable manner. It is preferably a liquid, water-containing agent.

Examples

The following detergents were prepared by mixing those in Tables 1 (liquid detergents) and 2 (solid detergents), the agents M1 and M2 being embodiments of the invention and the agents V1 and V2 being used as reference. Table 1: detergent compositions (% by weight) P1 V1 Boric acid 0.5 0.5 citric acid 0.23 0.23 Glycerin 0.5 0.5 Anionic surfactants 5.5 5.5 Nonionic surfactants 3.1 3.1 NaOH 0.7 0.7 Soap 0.5 0.5 Preservatives 0.05 0.05 Phosphonate DTPMP 0.2 0.2 Brightener 0.1 0.1 Cellulase 0.01 0.01 Enzyme mixture (without cellulase) 0.99 0.99 Perfume 0.5 0.5 dye 0.003 0.003 Copolymer * 0 0.05 water to 100 * produced according to example 1 of the European patent application EP 3 196 283 Table 2: Detergent compositions (% by weight): V2 M2 C _12-18 fatty alcohol 7 EO 2 2 C _12-18 fatty alcohol 7 EO sulfate, sodium salt 1.5 1.5 Linear alkyl benzene sulfonate, sodium salt 10 10 sodium 20th 20th Sodium bicarbonate 6.5 6.5 Sodium disilicate 4th 4th Sodium percarbonate 17th 17th TAED 4th 4th Sodium polyacrylate 3rd 3rd Na carboxymethyl cellulose 1 1 Sodium phosphonate 1 1 Enzyme mixture (with cellulase) 1 1 Copolymer * - 0.02 Sodium sulfate to 100 * produced according to example 1 of the European patent application EP 3 196 283

To determine the tear strength of textiles after repeated wash cycles, the undamaged textiles specified in Table 3 were washed in a Miele Novotronic® W1514 washing machine with the liquid detergents specified in Table 1 in the easy-care program at 40 ° C, 16 ° DH, 1200 rpm with one dosage of 60 ml of the respective detergent and a load of 2.5 kg washed ten times in the presence of an SBL 2004 cloth and then dried on the line. The textiles tested were commercially available fabrics for clothing textiles made from 100% viscose.

The tear strength of the washed textiles was determined using the Elmendorf method ( DIN EN ISO 13937-1: 2000 ) with the ballistic pendulum (Textest FX 3750 Elmendorf tester, Textest AG, Schwerzenbach, Switzerland). For this purpose, a test sample was placed in clamping clamps, cut to a depth of 20 mm (± 0.5 mm) so that a tear path of 43 mm (± 0.5 mm) remained. The pendulum was then released and stopped after a full swing of the pendulum. The tear strength in centinewtons was displayed on a digital display of the measuring device and statistically evaluated in such a way that the arithmetic mean value of the tear strength was calculated from 5 individual measurements.

The results for the tear propagation test in the warp direction are shown in Table 3. Table 5: Results of the tear propagation test (cN) Medium / textile Zander® CV Karstadt® CV 100% viscose 100% viscose V1 981 1082 M1 1048 1154

It can be seen that the addition of the copolymer, which is essential to the invention, achieves higher measured values than for textiles that were washed with the reference detergent without the copolymer. These higher measured values represent an improved tear resistance of the textiles.

QUOTES INCLUDED IN THE DESCRIPTION

This list of the documents listed by the applicant was generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Patent literature cited

• EP 3196283 A1 [0007]
• EP 3196283 [0045]

Non-patent literature cited

• DIN EN ISO 13937-1: 2000 [0047]

Claims (10)

Use of copolymers obtainable by radical copolymerization of at least one compound of the formula (I),

in which n is a number equal to or greater than 3, in particular a number in the range from 3 to 120, more preferably a number in the range from 5 to 50 and particularly preferably a number in the range from 7 to 46, in one embodiment n is selected from the group comprising the numbers 7, 23 and 46, with at least one compound of the formula (II),

in which A ^{- stands} for an anion, in particular selected from halides such as fluoride, chloride, bromide, iodide, sulfate, hydrogen sulfate, alkyl sulfate such as methyl sulfate and mixtures of these, for increasing the tensile strength of textiles. Process for increasing the tensile strength of textiles, wherein a copolymer obtainable by radical copolymerization of at least one compound of the formula (I),

in which n is a number equal to or greater than 3, in particular a number in the range from 3 to 120, more preferably a number in the range from 5 to 50 and particularly preferably a number in the range from 7 to 46, in one embodiment n is selected from the group comprising the numbers 7, 23 and 46, with at least one compound of the formula (II),

in which A ^{- stands} for an anion, in particular selected from halides such as fluoride, chloride, bromide, iodide, sulfate, hydrogen sulfate, alkyl sulfate such as methyl sulfate and mixtures of these, in substance or as a component of a liquid preparation such as a solution, suspension or Dispersion, applied to the textile surface and, if desired, excess material removed from the surface. Procedure according to Claim 2 , characterized in that 0.01 ml to 1 ml, in particular 0.1 ml of a 0.001 percent by weight to 10 percent by weight, in particular 0.02 percent by weight liquid preparation, in particular solution, of the copolymer per cm ^{2 of} the surface is applied to the surface. Procedure according to Claim 2 , characterized in that a detergent or laundry aftertreatment agent is used which contains the copolymer. Use after Claim 1 or method according to one of the Claims 2 to 4th , characterized in that the copolymer is present in a detergent or laundry treatment agent in a packaging form which makes it easier for the user to use it, in particular mixed or granulated with carrier substances, binders, coating materials, extrusion aids, flow improvers, stabilizers, solvents, rheology modifiers and / or emulsifiers. Procedure or use according to Claim 5 , characterized in that the agent contains 0.0006% by weight to 6% by weight, in particular 0.006% by weight to 0.6% by weight of the copolymer. Procedure or use according to Claim 5 or 6th , characterized in that the agent contains 0.001% by weight to 1% by weight, in particular 0.005% by weight to 0.3% by weight cellulase. Use or method according to one of the preceding claims, characterized in that in the compound of the general formula (I) n stands for a number in the range from 3 to 120, in particular for a number in the range from 5 to 50 and particularly preferably for a number im Range from 7 to 46 stands. Use or method according to one of the preceding claims, characterized in that part of the amount of compounds of the general formula (II), in particular not more than 60 mol%, is replaced by the corresponding non-quaternized compound of the formula (III),

is replaced. Use or method according to one of the preceding claims, characterized in that the mean molecular weight (weight average) of the polymer is in the range from 10,000 g / mol to 100,000 g / mol, in particular from 20,000 g / mol to 70,000 g / mol .