DE102017215785A1 - Use of copolymers as hydrophobizing agents - 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 for the hydrophobic finishing of textile surfaces.

Description

The invention relates to the use of certain copolymers of ethylenically unsaturated compounds for the hydrophobic finishing of textile surfaces, and laundry and laundry treatment compositions containing such polymeric active ingredients.

Textiles are often very hydrophilic and can absorb significant amounts of water within seconds. Moreover, it is observed that the hydrophilicity of even low hydrophilic textiles increases by washing with conventional detergents in an aqueous liquor. For special applications, such as for example as functional textiles, it is desirable to have a finish which makes the textiles hydrophobic and, ideally, rainproof.

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 leads to the hydrophobicization of textile surfaces or the use of laundry or laundry treatment agents leads to a lower hydrophilization of the textile, when the agent such a copolymer contain.

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 hydrophoben Ausrüstung textiler Oberflächen.An object of the invention is therefore the use of copolymers obtainable by free-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 of 3 to 120, more preferably a number in the range of 5 to 50, and particularly preferred a number in the range of 7 to 46, wherein 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 the A ^{- represents} an anion, in particular selected from halides such as fluoride, chloride, bromide, iodide, sulfate, hydrogen sulfate, alkyl sulfate such as methyl sulfate and mixtures thereof, for the hydrophobic finishing of textile surfaces.

Another object of the invention is the use of these polymers to reduce occurring by the use of laundry or laundry treatment agents in aqueous liquor increasing the hydrophilicity of textiles.

The polymers essential to the invention can be obtained by basically known radical polymerization processes. In this case, a mixture of compound of general formula (I) and compound of general formula (II) 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 hydroxymethylsulfinate to random copolymers. Alternatively, the monomer of the general formula (I) or the monomer of the general formula (II) can first be subjected to free-radical polymerization and then free-radically polymerized onto the monomer of the general formula (II) or the monomer of the general formula (I), such that Copolymers receives. According to the invention, preference is given to random copolymers. In the polymerization, about 0.01 wt .-% to 5 wt .-% radical initiator, based on the total amount of monomers used, is usually present.

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. 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 Apart from components derived from radical initiator or terminator compounds, the polymers used according to the invention preferably contain no moieties derived from monomers other than the compounds of the general formulas (I) and (II). However, part of the amount of compounds of general formula (II), preferably not more than 60 mol%, may be represented by the corresponding non-quaternized compound of formula (III),

be replaced. In the preparation of the polymers used according to the invention it is also possible to start from the monomer compound (III) and to react the copolymer obtained after reaction with the compound of the general formula (I) with a methylating agent.

The average molecular weight (weight average) of the polymers 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.

The use according to the invention can be carried out in a simple manner by a process for the hydrophobic finishing of textile surfaces or to reduce the increase in the hydrophilicity of textiles occurring by the use of washing or laundry treatment agents in aqueous liquor such that the copolymer, in bulk or as part of a liquid preparation, such as a solution, suspension or dispersion (in, for example, acetone) on the textile surface, in particular of textiles made of polyester or polyester, applied, for example by casting or spraying, and if desired, excess material, for example by means of a cloth or Sponge, removed from the textile surface. In this case, preferably 0.01 ml to 1 ml, in particular 0.1 ml of a 1 weight percent to 10 weight percent, in particular 2 weight percent liquid preparation, in particular solution, of the copolymer per cm ^{2 of} the surface, and leaves this act at least 30 minutes, wherein the solvent, dispersant or suspending agent of the liquid preparation may optionally, completely or partially, evaporate. Also, the immersion of the textile in a liquid preparation is possible. In a preferred embodiment of the invention, the polymer essential to the invention is applied to textiles by spraying an aqueous polymer-containing preparation, for example by means of a spray can (compressed gas can, pressurized gas package, aerosol package) or mechanically operated pump sprayer (pump spray), from which the polymer preparation is formed, for example of a spray, foam, paste or jet of liquid.

However, the use according to the invention can also be carried out by the use of a washing or laundry treatment containing the copolymer, and embodiments of the method according to the invention, in particular the method for reducing the increase in the hydrophilicity of textiles by the use of laundry or laundry treatment agents in aqueous liquor can be exercised using such a laundry or laundry treatment.

Preferably, the agent contains 0.001 wt .-% to 10 wt .-%, in particular 0.05 wt .-% to 5 wt .-% of the copolymer, wherein here and below the information of wt .-% to the total agent unless otherwise stated. In this case, a laundry treatment agent is to be understood as meaning a means in whose use the removal of dirt is not in the foreground, as in the case of a laundry detergent, but which primarily serves laundry care, such as, for example, a fabric softener used in the laundry aftertreatment step, or one on the Washable ironing aid.

Through the use of the washing or laundry treatment agent, a hydrophobing of the surface takes place, which leads to a lasting reduction in the wettability of the surface. As a result, water droplets emanate from the surface and can not deposit any constituents contained in them, for example dirt particles, on the surface, so that the appearance of the cleaned textile surface is clean for a prolonged period of time. These effects are preferably observed over an extended period of time after application of the agent, for example for three weeks. This is a permanent Equipment of the surface, however, not aimed. Finally, the laundry treating agent to be used in a preferred embodiment is transparent and is also suitable for spraying.

The use according to the invention can be carried out as part of a washing process by adding the textile-hydrophobicizing agent to a detergent-containing liquor or, preferably, introducing the active ingredient into the liquor as a constituent of a detergent containing the textile to be treated or contacted with it.

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

The washing process is preferably carried out at a temperature of 15 ° C to 60 ° C, more preferably at a temperature of 20 ° C to 40 ° C. The washing process is furthermore 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 0.03 g / l to 1 g / l, in particular from 0.3 g / l to 0.5 g / l.

Within the context of the use according to the invention and the process according to the invention, it is possible to use the textile-hydrophobicizing active substance as such; However, the active ingredient can also be present in a laundry treatment agent for use by the user in an easier form of preparation, for example in admixture or granulated with vehicles, binders, coating materials, extrusion aids, flowability improvers, stabilizers, solvents, rheology modifiers and / or emulsifiers. This embodiment of the invention makes it possible for the consumer in a simple manner, the benefits of the invention by using the textile hydrophobing agent in addition to conventional washing and / or laundry aftertreatment only to bear, if they are desirable.

Agents which contain an active ingredient to be used according to the invention in the form of said copolymer or used together or used in the process according to the invention may contain all other conventional ingredients of such agents which do not undesirably interact with the active ingredient of the invention, in particular surfactant. It is preferred if such agents 1 wt .-% to 60 wt .-%, in particular 5 wt .-% to 40 wt .-% surfactant.

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

Another embodiment of such agents comprises the presence of sulfate and / or sulfonate synthetic anionic surfactant, in particular fatty alkyl sulfate, fatty alkyl ether sulfate, sulfo fatty acid ester and / or sulfo fatty acid salt, in particular in an amount in the range from 2% 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 content of compounds having longer-chain radicals in the range from 16 to 18 carbon atoms is more than 20% by weight.

Suitable nonionic surfactants 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 C atoms, preferably 12 to 18 C atoms. The degree of alkoxylation of the alcohols is generally between 1 and 20, preferably between 3 and 10. They can be prepared in a known manner by reacting the corresponding alcohols with the corresponding alkylene oxides. Particularly suitable are the derivatives of fatty alcohols, although their branched-chain Isomers, especially so-called oxo alcohols, can be used to prepare useful alkoxylates. Useful are accordingly the alkoxylates, in particular the ethoxylates, primary alcohols with linear, in particular dodecyl, tetradecyl, hexadecyl or octadecyl radicals and mixtures thereof. In addition, suitable alkoxylation products of alkylamines, vicinal diols and carboxamides, which correspond to the said alcohols with respect to the alkyl part, usable. In addition, the ethylene oxide and / or propylene oxide insertion products of fatty acid alkyl esters and Fettsäurepolyhydroxyamide into consideration. Suitable so-called alkylpolyglycosides for incorporation into the compositions are compounds of the general formula (G) _n -OR ¹² in which R ^{12 is} an alkyl or alkenyl radical having 8 to 22 C atoms, G is a glycose unit and n is a number between 1 and 10 , The glycoside component (G) _n are oligomers or polymers of naturally occurring aldose or ketose monomers, in particular glucose, mannose, fructose, galactose, talose, gulose, altrose, allose, idose, ribose, arabinose, Include xylose and lyxose. The oligomers consisting of such glycosidically linked monomers are characterized not only by the nature of the sugars contained in them by their number, the so-called Oligomerisierungsgrad. The mean degree of oligomerization n assumes as the value to be determined analytically generally broken numerical values; it is between 1 and 10, with the glycosides preferably used below a value of 1.5, in particular in the range of 1.2 to 1.4. Preferred monomer building block is glucose because of its good availability. The alkyl or alkenyl moiety R ^{12 of} the glycosides preferably also originates from readily available derivatives of renewable raw materials, in particular from fatty alcohols, although their branched-chain isomers, in particular so-called oxoalcohols, can also be used for the preparation of useful glycosides. Accordingly, the primary alcohols having linear octyl, decyl, dodecyl, tetradecyl, hexadecyl or octadecyl radicals and mixtures thereof are particularly suitable. Particularly preferred alkyl glycosides contain a Kokosfettalkylrest, that is, mixtures having substantially R ¹² = dodecyl and R ¹² = tetradecyl.

Nonionic surfactant is used in compositions containing a soil release agent used in the invention, used according to the invention or used in the process according to the invention, preferably in amounts of 1 wt .-% to 30 wt .-%, in particular from 1 wt .-% to 25 Wt .-%, with amounts in the upper part of this range are more likely to be found in liquid detergents and particulate detergents preferably contain rather lower amounts of up to 5 wt .-%.

The agents may instead or additionally contain other 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. %, in each case based on total resources. Suitable synthetic anionic surfactants which are particularly suitable for use in such compositions are the alkyl and / or alkenyl sulfates having 8 to 22 C atoms which carry an alkali, ammonium or alkyl or hydroxyalkyl-substituted ammonium ion as counter cation. Preference is given to the derivatives of the fatty alcohols having in particular 12 to 18 carbon atoms and their branched-chain analogs, the so-called oxo alcohols. The alkyl and alkenyl sulfates can be prepared in a known manner by reaction of the corresponding alcohol component with a conventional sulfating reagent, in particular sulfur trioxide or chlorosulfonic acid, and subsequent neutralization with alkali metal, ammonium or alkyl or hydroxyalkyl-substituted ammonium bases. Sulfur-type surfactants which can be used also include the sulfated alkoxylation products of the alcohols mentioned, known as ether sulfates. Such ether sulfates preferably contain from 2 to 30, in particular from 4 to 10, ethylene glycol groups per molecule. Suitable anionic surfactants of the sulfonate type include the α-sulfoesters obtainable by reaction of fatty acid esters with sulfur trioxide and subsequent neutralization, in particular those of fatty acids having 8 to 22 C atoms, preferably 12 to 18 C atoms, and linear alcohols having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, derivative sulfonation, as well as the formal saponification resulting from these sulfo fatty acids.

Other optional surface-active ingredients are soaps, suitable being 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. In particular, those soap mixtures are preferred which are composed of 50% to 100% by weight of saturated C ₁₂ -C ₁₈ fatty acid soaps and up to 50% by weight of oleic acid soap. Preferably, soap is included in amounts of from 0.1% to 5% by weight. However, especially in liquid compositions containing a polymer used according to the invention, higher amounts of soap, as a rule up to 20% by weight, can also be present.

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

An agent which contains or is used together with an active substance to be used according to the invention or which is used in the process according to the invention preferably contains peroxygen-based bleaching agents, in particular in amounts ranging from 5% by weight to 70% by weight, and optionally However bleach activator, especially in amounts ranging from 0.3% to 10% by weight, may in another preferred embodiment also be free of bleach and bleach activator. The bleaches in question are preferably the peroxygen compounds generally used in detergents, such as percarboxylic acids, for example dodecanedioic acid or phthaloylaminoperoxicaproic acid, hydrogen peroxide, alkali metal perborate, which may be present as tetra- or monohydrate, percarbonate, perpyrophosphate and persilicate, which are generally used as alkali metal salts, in particular as sodium salts. Such bleaching agents are in detergents containing an active ingredient according to the invention, preferably in amounts of up to 25 wt .-%, in particular up to 15 wt .-% and particularly preferably from 5 wt .-% to 15 wt .-%, each based on total agent, present, in particular percarbonate is used. The optionally present component of the bleach activators comprises the commonly used N- or O-acyl compounds, for example polyacylated alkylenediamines, in particular tetraacetylethylenediamine, acylated glycolurils, in particular tetraacetylglycoluril, N-acylated hydantoins, hydrazides, triazoles, urazoles, diketopiperazines, sulphurylamides and cyanurates, and also carboxylic anhydrides , in particular phthalic anhydride, carboxylic acid esters, in particular sodium nonanoyl and -isononanoylphenolsulfonat, and acylated sugar derivatives, in particular pentaacetylglucose, as well as cationic nitrile derivatives such as trimethylammonium acetonitrile salts. In order to avoid the interaction with the peroxygen compounds, the bleach activators may have been coated or granulated in known manner with encapsulating substances, granulated tetraacetylethylenediamine having weight-average particle sizes of from 0.01 mm to 0.8 mm, granulated 1.5% by means of carboxymethylcellulose. Diacetyl-2,4-dioxohexahydro-1,3,5-triazine, and / or formulated in particulate trialkylammonium acetonitrile 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 agent.

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

The agent preferably contains from 20% to 55% by weight of water-soluble and / or water-insoluble, organic and / or inorganic builders. The water-soluble organic builder substances include, in particular, those from the class of polycarboxylic acids, in particular citric acid and sugar acids, as well as the polymeric (poly) carboxylic acids, in particular the polycarboxylates obtainable by oxidation of polysaccharides, polymeric acrylic acids, methacrylic acids, maleic acids and mixed polymers thereof, which also small amounts of polymerizable substances without carboxylic acid functionality may contain polymerized. The relative molecular mass 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 molecular weight of 50,000 g / mol to 100,000 g / mol. Suitable, although less preferred, compounds of this class are copolymers of acrylic or methacrylic acid with vinyl ethers, such as vinylmethyl ethers, vinyl esters, ethylene, propylene and styrene, in which the acid content is at least 50% by weight. Terpolymers which contain two carboxylic acids and / or salts thereof as monomers and also vinyl alcohol and / or a vinyl alcohol derivative or a carbohydrate as the third monomer may 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, with maleic acid being particularly preferred. The third monomeric unit is formed in this case of vinyl alcohol and / or preferably an esterified vinyl alcohol. In particular, preferred are vinyl alcohol derivatives which are an ester of short-chain carboxylic acids, for example C ₁ -C ₄ carboxylic acids, with vinyl alcohol. Preferred terpolymers contain from 60% by weight to 95% by weight, in particular from 70% by weight to 90% by weight, of (meth) acrylic acid and / or (meth) acrylate, particularly preferably acrylic acid and / or acrylate, and maleic acid and / or maleate and 5 wt .-% to 40 wt .-%, preferably 10 wt .-% to 30 wt .-% of vinyl alcohol and / or vinyl acetate. Very particularly preferred are 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 from 40% by weight to 60% by weight, in particular from 45 to 55% by weight, of (meth) acrylic acid and / or (meth) acrylate, particularly preferably acrylic acid and / or acrylate, 10% by weight to 30 wt .-%, preferably 15 wt .-% to 25 wt .-% methallylsulfonic acid and / or Methallylsulfonat and as the third monomer 15 wt .-% to 40 wt .-%, preferably 20 wt .-% to 40 wt. % of a carbohydrate. This carbohydrate may be, for example, a mono-, di-, oligo- or polysaccharide, mono-, di- or oligosaccharides being preferred, sucrose being particularly preferred. The use of the third monomer presumably incorporates predetermined breaking points in the polymer which are responsible for the good biodegradability of the polymer. These terpolymers generally have a molecular weight between 1000 g / mol and 200000 g / mol, preferably between 3000 g / mol and 10000 g / mol. They can be used, in particular for the preparation of liquid agents, in the form of aqueous solutions, preferably in the form of 30 to 50 percent 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.

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 stated upper limit are preferably used in pasty or liquid, in particular hydrous, agents.

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, are used as water-insoluble, water-dispersible inorganic builder materials. used. Among these, the detergent-grade crystalline aluminosilicates, especially zeolite NaA and optionally NaX, are preferred. Amounts near the above upper limit are preferably used in solid, particulate agents. In particular, suitable aluminosilicates have no particles with a particle size greater than 30 .mu.m and preferably consist of at least 80% by weight of particles having a size of less than 10 .mu.m. Their calcium binding capacity, according to the information of the German Patent DE 24 12 837 can be determined ranges from 100 to 200 mg CaO per gram. Suitable substitutes or partial substitutes for the said aluminosilicate are crystalline alkali silicates which may be present alone or in a mixture with amorphous silicates. The alkali metal silicates useful as builders in the compositions preferably have a molar ratio of alkali metal oxide to SiO ₂ below 0.95, in particular from 1: 1.1 to 1:12, and may be present in amorphous or crystalline form. Preferred alkali metal silicates are the sodium silicates, in particular the amorphous sodium silicates, with a molar ratio of 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®. They are preferably added in the course of the production as a solid and not in the form of a solution. The crystalline silicates which may be present alone or in admixture with amorphous silicates, are crystalline layer silicates with the general formula Na ₂ Si _x O _{2x + 1} · are used yH ₂ O, in which x, the so-called module, a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4. Preferred crystalline phyllosilicates are those in which x in the abovementioned general formula 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. Also prepared from amorphous alkali metal silicates, practically anhydrous crystalline alkali silicates of the above general formula in which x is a number from 1.9 to 2.1, can be used in agents which contain an active ingredient to be used according to the invention. In a further preferred embodiment of the composition according to the invention, a crystalline sodium layer silicate with a modulus of 2 to 3 is used, as can be prepared from sand and soda. Crystalline sodium silicates with a modulus in the range from 1.9 to 3.5 are used in a further preferred embodiment of detergents containing an active ingredient used according to the invention. Their content of alkali metal silicates is preferably 1 wt .-% to 50 wt .-% and in particular 5 wt .-% to 35 wt .-%, based on anhydrous active substance. If alkali metal aluminosilicate, in particular zeolite, is present as an additional builder substance, the content of alkali silicate 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, in each case based on anhydrous active substances, is then preferably 4: 1 to 10: 1. In agents containing both amorphous and crystalline alkali metal silicates, the weight ratio of amorphous alkali metal silicate to crystalline alkali metal silicate is preferably 1: 2 to 2: 1 and especially 1: 1 to 2: 1.

In addition to the said inorganic builder, other water-soluble or water-insoluble inorganic substances may be contained in the compositions which contain an active substance to be used according to the invention together with it or used in the process according to the invention. Suitable in this context are the alkali metal carbonates, alkali metal bicarbonates and alkali metal sulfates and mixtures thereof. Such additional inorganic material may be present in amounts up to 70% by weight.

In addition, the agents may contain other ingredients customary in detergents and cleaners. These optional ingredients include, in particular, enzymes, enzyme stabilizers, complexing agents for heavy metals, for example aminopolycarboxylic acids, aminohydroxypolycarboxylic acids, polyphosphonic acids and / or aminopolyphosphonic acids, foam inhibitors, for example organopolysiloxanes or paraffins, solvents and optical brighteners, for example stilbene disulfonic acid derivatives. Preferably, in agents which contain an active substance used according to the invention, up to 1% by weight, in particular 0.01% by weight to 0.5% by weight, of optical brighteners, in particular compounds from the class of the substituted 4,4 ' -Bis (2,4,6-triamino-s-triazinyl) -stilbene-2,2'-disulfonic acids, up to 5 wt .-%, in particular 0.1 wt .-% to 2 wt .-% complexing agent for Heavy metals, in particular Aminoalkylenphosphonsäuren and their salts and up to 2 wt .-%, in particular 0.1 wt .-% to 1 wt .-% foam inhibitors, wherein said weight percentages in each case refer to the total agent.

Solvents which can be used in particular for liquid agents are, in addition to water, preferably those which are water-miscible. These include the lower alcohols, for example, ethanol, propanol, isopropanol, and the isomeric butanols, glycerol, lower glycols, such as ethylene and propylene glycol, and the derivable from said classes of compounds ether. In such liquid agents, the active compounds used in the invention are usually dissolved or in suspended form.

Optionally present enzymes are preferably selected from the group comprising protease, amylase, lipase, cellulase, hemicellulase, oxidase, peroxidase or mixtures thereof. First and foremost, proteases derived from microorganisms, such as bacteria or fungi, come into question. It can be obtained in a known manner by fermentation processes from suitable microorganisms. 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 usable cellulase may be a recoverable from bacteria or fungi enzyme, which has a pH optimum, preferably in the weakly acidic to slightly alkaline range of 6 to 9.5. Such cellulases are commercially available under the names Celluzyme®, Carezyme® and Ecostone®.

The customary enzyme stabilizers present, if appropriate, 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, especially behenic soap, fatty acid amides, paraffins, waxes, microcrystalline waxes, organopolysiloxanes and mixtures thereof, which moreover can contain microfine, optionally silanated or otherwise hydrophobicized silica. For use in particulate agents, such foam inhibitors are preferably bound to granular, water-soluble carrier substances.

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

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

Preferred laundry aftertreatment compositions which comprise an active substance to be used according to the invention have, as a laundry softening active ingredient, a so-called esterquat, that is to say a quaternized ester of carboxylic acid and aminoalcohol. These are known substances which can be obtained by the relevant methods of preparative organic chemistry, for example by partially esterifying triethanolamine in the presence of hypophosphorous acid with fatty acids, 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.Ester quats preferred in the compositions are quaternized fatty acid triethanolamine ester salts which follow formula (IV),

in the R ¹ CO for an acyl radical having 6 to 22 carbon atoms, R ² and R ^{3 are} independently hydrogen or R ¹ CO, R ^{4 is} an alkyl radical having 1 to 4 carbon atoms or a (CH ₂ CH ₂ O) _q H Group, m, n and p in total are 0 or numbers from 1 to 12, q is numbers from 1 to 12 and X is a charge-balancing anion such as halide, alkyl sulfate or alkyl phosphate. Typical examples of esterquats which can be used in the context 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, arachidic acid, behenic acid and erucic acid and their technical mixtures, such as They occur, for example, in the pressure splitting of natural fats and oils. Preferably, technical C _12/18 coconut _fatty acids and, in particular, partially hydrogenated C _16/18 tallow or palm oil fatty acids and also elaidic acid-rich C _16/18 fatty acid cuts are 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. In view of the performance properties of the esterquats, an employment ratio of 1.2: 1 to 2.2: 1, preferably 1.5: 1 to 1.9: 1 has proven to be particularly advantageous. The preferred esterquats used are technical mixtures of mono-, di- and triesters having an average degree of esterification of 1.5 to 1.9 and are derived from technical C _16/18 tallow or palm oil 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 is} R ¹ CO, R ^{3 is} hydrogen, R ^{4 is} a methyl group, m, n and p is 0 and X is Methyl sulfate is, have proven 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, suitable esterquats are quaternized ester salts of carboxylic acids with diethanolalkylamines of the formula (V),

in the R ¹ CO for an acyl radical having 6 to 22 carbon atoms, R ^{2 is} hydrogen or R ¹ CO, R ⁴ and R ^{5 are} independently alkyl radicals having 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.

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, the quaternized ester salts of carboxylic acids with 1,2-dihydroxypropyldialkylamines of the formula (VI) should be mentioned as a further group of suitable esterquats.

in the R ¹ CO for an acyl radical having 6 to 22 carbon atoms, R ^{2 is} hydrogen or R ¹ CO, R ⁴ , R ⁶ and R ^{7 are} independently alkyl radicals having 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 data given for (IV) apply mutatis mutandis to the esterquats of the formulas (V) and (VI). Usually, the esterquats are marketed in the form of 50 to 90 weight percent alcoholic solutions, which can also be easily diluted with water, with ethanol, propanol and isopropanol being the usual alcoholic solvents.

Esterquats are preferably used in amounts of from 5% by weight to 25% by weight, in particular from 8% by weight to 20% by weight, in each case based on the total laundry aftertreatment agent. If desired, the laundry aftertreatment agents used in the present invention may additionally contain detergent ingredients listed above, unless they unduly interact negatively with the esterquat. It is preferably a liquid, water-containing agent.

Examples

The wicking speed of fabrics of the materials shown in Table 2 was determined according to the riser height method according to DIN 53 924 (measuring length 100 mm) after 10 minutes. In Table 2, the height of rise of water in the fabric after 3 washes with the respective detergent whose composition is listed in Table, at 30 ° C and, for comparison, that of unwashed fabric is given. Table 1: Detergent compositions (% by weight): V1 M1 C _12-18 fatty alcohol 7 EO 2 2 C _12-18 - fatty alcohol 7 EO sulphate, sodium salt 1.5 1.5 Linear alkyl benzene sulfonate, sodium salt 10 10 sodium 20 20 sodium 6.5 6.5 sodium disilicate 4 4 sodium 17 17 TAED 4 4 sodium polyacrylate 3 3 carboxymethylcellulose 1 1 sodium phosphonate 1 1 enzyme mixture 1 1 Polymer* - 1 sodium sulphate on 100 * prepared according to Example 1 of the European patent application EP 3 196 283 Table 2: Rising height (mm) after 10 minutes Textile / Medium - V1 M1 Cotton / Polyester 65:35 94 105 93 polyester 122 117 99 cotton 89 102 88

It can be seen that the use of the polymer essential to the invention (in the mean M1) restricts the increase in the hydrophilicity caused by the detergent (V1) and increases the hydrophobicity of the textile.

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been 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.

Cited patent literature

• DE 2412837 [0029]
• EP 3196283

Claims (10)

Use of copolymers obtainable by free-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 of 3 to 120, more preferably a number in the range of 5 to 50, and particularly preferred a number in the range of 7 to 46, wherein 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 the A ^{- represents} an anion, in particular selected from halides such as fluoride, chloride, bromide, iodide, sulfate, hydrogen sulfate, alkyl sulfate such as methyl sulfate and mixtures thereof, for the hydrophobic finishing of textile surfaces. Use of copolymers obtainable by free-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 of 3 to 120, more preferably a number in the range of 5 to 50, and particularly preferred a number in the range of 7 to 46, wherein 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 the 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 thereof, to reduce occurring by the use of laundry or laundry treatment agents in aqueous liquor Increasing the hydrophilicity of textiles. Process for the hydrophobic finishing of textile surfaces or for the reduction of hydrophilicity caused by the use of laundry detergents or laundry detergents in aqueous liquors of textiles, wherein a copolymer obtainable by free-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 of 3 to 120, more preferably a number in the range of 5 to 50, and particularly preferred a number in the range of 7 to 46, wherein 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 the A ^{- represents} an anion, in particular selected from halides such as fluoride, chloride, bromide, iodide, sulfate, hydrogen sulfate, alkyl sulfate such as methyl sulfate and mixtures thereof, in bulk or as part 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. Method according to Claim 3 , characterized in that 0.01 ml to 1 ml, in particular 0.1 ml of a 0.001 weight percent to 10 weight percent, in particular 0.02 weight percent liquid preparation, in particular solution, of the copolymer per cm ^{2 of} the surface applied to the surface. Method according to Claim 3 , characterized in that one uses a washing or laundry treatment agent containing the copolymer. Use after Claim 1 or 2 or method according to one of Claims 4 to 5 , characterized in that the copolymer is in a laundry treatment agent in the use by the user facilitating confectioning form, especially in admixture or granulated with vehicles, binders, wrapping materials, extrusion aids, flowability improvers, stabilizers, solvents, rheology modifiers and / or emulsifiers. Use or method according to Claim 6 , characterized in that the agent contains 0.001 wt .-% to 10 wt .-%, in particular 0.05 wt .-% to 5 wt .-% of the copolymer. Use or process according to one of the preceding claims, characterized in that in the compound of general formula (I) n is a number in the range of 3 to 120, in particular a number in the range of 5 to 50 and particularly preferably a number in Range from 7 to 46 stands. Use or process according to one of the preceding claims, characterized in that a part of the amount of compounds of general formula (II), in particular not more than 60 mol%, by the corresponding non-quaternized compound of formula (III),

is replaced. Use or process according to one of the preceding claims, characterized in that the weight average molecular weight 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 ,