EP2977506A1 - Siloxane group-containing copolymers as hydrophobizing agents for the finishing of textile materials and washing composition comprising the same - Google Patents

Abstract

Proposed is the use of siloxane-containing copolymers for the hydrophobic finishing of textile surfaces, in particular textiles made of cotton or cotton, and laundry or laundry treatment compositions containing such siloxane-containing copolymers.

Description

The invention relates to the use of certain polymeric siloxane-containing active ingredients for the hydrophobic finishing of textile surfaces, in particular textiles made of cotton or cotton, and laundry and laundry treatment compositions containing such polymeric active ingredients.

Cotton and textiles made from or containing cotton are very hydrophilic and can absorb significant amounts of water within seconds. For special applications, such as, for example, as functional textiles, it is desirable to use a cotton finish which makes the textiles hydrophobic and, ideally, rainproof.

Out ACS Appl. Mater. Interfaces, 2011, 3, 2179-2183 It is known that superhydrophobic surfaces can be generated by spraying solutions of poly (SiMA-co-MMA) onto substrates.

in denen

• R¹ für -(CH₂)_nSi(OSi(CH₃)₃)_m(OH)_p(R₅)_q,
• R², R³ und R⁴ unabhängig voneinander für H oder eine Alkylgruppe mit 1 bis 3 C-Atomen,
• R⁵ für eine Alkylgruppe mit 1 bis 5 C-Atomen,
• n für eine Zahl von 1 bis 3, und
• m, p und q unabhängig voneinander für eine Zahl von 0 bis 3, wobei die Summe m+p+q = 3 beträgt, stehen,
• zur hydrophoben Ausrüstung textiler Oberflächen, insbesondere von Textilien aus Baumwolle oder mit Baumwollanteil.

The invention relates to the use of copolymers with the monomer unit of the general formula I and the monomer unit of the general formula II,

in which

• R ^{1 is} - (CH ₂ ) _n Si (OSi (CH ₃ ) ₃ ) _m (OH) _p (R ₅ ) _q ,
• R ² , R ³ and R ⁴ independently of one another are H or an alkyl group having 1 to 3 C atoms,
• R ^{5 is} an alkyl group having 1 to 5 C atoms,
• n is a number from 1 to 3, and
• m, p and q independently of one another represent a number from 0 to 3, the sum being m + p + q = 3,
• for the hydrophobic finishing of textile surfaces, in particular of cotton or cotton textiles.

Preferably, the surface after the equipment has a contact angle to water of at least 120 °, in particular from 140 ° to 180 °.

in denen R¹, R², R³ und R⁴ die vorgenannte Bedeutung aufweisen und x und y unabhängig voneinander für Zahlen von 2 bis 2000, insbesondere 10 bis 1000 stehen.The copolymers mentioned are accessible by radical polymerization of ethylenically unsaturated precursor compounds of the monomer units of the general formulas I and II. They may contain the two monomer units of the general formulas I and II in statistical distribution, or they have blocks I 'and II' composed of the monomer units I or II,

in which R ¹ , R ² , R ³ and R ^{4 have} the abovementioned meaning and x and y independently of one another represent numbers from 2 to 2000, in particular from 10 to 1000.

If desired, the siloxane-containing copolymers may contain, in addition to the monomer units I and II, further monomer units derived from ethylenically unsaturated compounds. Apart from components derived from conventional free-radical initiator and terminator compounds, they preferably consist only of the monomer units I and II.

In preferred copolymers, the molar ratio of monomer unit I to monomer unit II is in the range from 10: 1 to 1:10, in particular from 3: 1 to 1: 3 and particularly preferably 1: 1. The average molecular weight (here and hereinafter: weight average) of the copolymer is preferably in the range from 1000 g / mol to 5 000 000 g / mol, in particular from 2000 g / mol to 500 000 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 such that the copolymer, in bulk or as a constituent of a liquid preparation, such as a solution, suspension or dispersion (in, for example, acetone) on the textile surface, especially of textiles made of cotton or cotton, 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 0.001% by weight to 10% by weight, in particular 0.02% by weight liquid preparation, in particular solution, of the copolymer per _CM ^{2 of} the surface, and leaves them for at least 30 minutes acting, wherein the solvent, dispersant or suspending agent of the liquid preparation optionally, completely or partially, can evaporate. Also, the immersion of the textile in a liquid preparation is possible. However, the use of the present invention can be also carried out by the use of a laundry or laundry treating agent containing the siloxane group-containing copolymer, and embodiments of the process of the present invention can be practiced using such a laundry or laundry treating agent.

Another object of the invention is therefore an especially liquid laundry or laundry treatment composition containing a above-defined siloxane-containing copolymer. The agent preferably contains from 0.01% by weight to 10% by weight, in particular from 0.05% by weight to 1% by weight, of the siloxane-containing copolymer, with the details of% by weight being given here and below. % to the total amount. 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. However, a permanent equipment of the surface is not sought. Finally, the laundry treatment agent to be used in a preferred Be transparent embodiment and are also suitable for spraying; the detergent to be used should have a good cleaning performance.

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 carboxylic acid ester defined above 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 siloxane-containing copolymer or are used together or used in the process according to the invention may contain all customary other constituents of such agents which are not undesirable with the invention essential Active substance interact, in particular surfactant. The active substance defined above is preferably used in amounts of from 0.1% by weight to 80% by weight, particularly preferably from 5% by weight to 20% by weight, these and the following quantities being based on the total Obtain funds unless stated otherwise.

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 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, in particular 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, in particular so-called oxo alcohols, can be used for the preparation of usable 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 is preferably also derived from readily available derivatives of renewable raw materials, in particular from fatty alcohols, although also their branched-chain isomers, in particular so-called oxo alcohols, can 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 include soaps, saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid or stearic acid, as well as natural fatty acid mixtures, for example coconut, palm kernel or tallow fatty acids derived Soaps are suitable. 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.

In a further 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 wt .-%.

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 while 60 wt .-% to 95 wt .-%, in particular 70 wt .-% to 90 wt .-% of (meth) acrylic acid and / or (meth) acrylate, particularly preferably acrylic acid and / or acrylate, and maleic acid and / or Maleinate and 5 wt .-% to 40 wt .-%, preferably 10 wt .-% to 30 wt .-% of vinyl alcohol and / or vinyl acetate. Very particular preference is given to 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.

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 particularly suitable 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, lies in the range 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 .beta.- and δ-sodium (Na ₂ Si ₂ O ₅ · _y H ₂ O) is 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.

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 with 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 value 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 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.

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 Example 1: Preparation of polymer P1

6.00 g of methyl methacrylate, 8.6 g of 3- [tris (trimethylsiloxy) silyl] propyl methacrylate and 0.06 g of azobis (isobutyronitrile) were dissolved in 50 ml of toluene, and the reaction solution was degassed for 30 minutes while introducing nitrogen in an ultrasonic bath and then heated to 70 ° C for 24 hours. Subsequently, a further 0.06 g of azobis (isobutyronitrile) was added and the reaction solution was kept at 70 ° C. for a further 6.5 hours

Mol Weight (Mw) Polymer P1: 700,000 g / mol (measured by GPC in THF (polystyrene calibration).

Example 2

Cotton test fabrics were immersed in a 2% by weight solution of the polymer P1 prepared in Example 1. The measurement of the contact angle of the textile surface coated with the polymer was carried out after a drying time of 1 hour by means of a contact angle measuring device DSA 10 (Krüss, Hamburg). For this purpose, a drop of water with a volume of 10 μl was applied to the coated surface by means of a capillary. It resulted in a contact angle of greater than 180 °.

Claims (10)

Use of copolymers with the monomer unit of the general formula I and the monomer unit of the general formula II,

in which R ^{1 is} - (CH ₂ ) _n Si (OSi (CH ₃ ) ₃ ) _m (OH) _p (R ₅ ) _q , R ² , R ³ and R ⁴ independently of one another are H or an alkyl group having 1 to 3 C atoms, R ^{5 is} an alkyl group having 1 to 5 C atoms, n is a number from 1 to 3, and m, p and q independently of one another represent a number from 0 to 3, the sum being m + p + q = 3, for the hydrophobic finishing of textile surfaces, in particular of cotton or cotton textiles. Washing or laundry treatment compositions containing a copolymer with the monomer building block of the general formula I and the monomer building block of the general formula II,

in which R ^{1 is} - (CH ₂ ) _n Si (OSi (CH ₃ ) ₃ ) _m (OH) _p (R ₅ ) _q , R ² , R ³ and R ⁴ independently of one another are H or an alkyl group having 1 to 3 C atoms, R ^{5 is} an alkyl group having 1 to 5 C atoms, n is a number from 1 to 3, and m, p and q independently represent a number from 0 to 3, the sum being m + p + q = 3. Composition according to claim 2, characterized in that it contains 0.1 wt .-% to 80 wt .-%, in particular 5 wt .-% to 20 wt .-% of the copolymer. Process for the hydrophobic finishing of textile surfaces, wherein a copolymer with the monomer building block of the general formula I and the monomer building block of the general formula II,

in which R ^{1 is} - (CH ₂ ) _n Si (OSi (CH ₃ ) ₃ ) _m (OH) _p (R ₅ ) _q , R ² , R ³ and R ⁴ independently of one another are H or an alkyl group having 1 to 3 C atoms, R ^{5 is} an alkyl group having 1 to 5 C atoms, n is a number from 1 to 3, and m, p and q independently of one another represent a number from 0 to 3, the sum being m + p + q = 3, in substance or as a constituent of a liquid preparation, such as a solution, suspension or dispersion, on the textile surface, in particular of textiles made of cotton or cotton content, applying and, if desired, excess material removed from the surface. A method according to claim 4, 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 on the Surface applies. Use according to claim 1 or method according to claim 4 or 5, characterized in that the copolymer is present in a laundry treatment agent in the use by the user facilitating confectioning form, in particular in admixture or granulated with vehicles, binders, wrapping materials, extrusion aids, free-flow improvers, stabilizers, solvents , Rheology Modifiers and / or Emulsifiers. Use according to Claim 1 or 6 or agent according to Claim 2 or 3 or Process according to one of Claims 4 to 6, characterized in that the copolymer comprises blocks I 'and II' composed of the monomer units I or II,

in which x and y independently of one another represent numbers from 2 to 2000, in particular from 10 to 1000. Use, means or method according to one of the preceding claims, characterized in that the copolymer consists only of the monomer units I and II. Use, means or method according to one of the preceding claims, characterized in that in the copolymer, the molar ratio of monomer unit I to monomer II in the range of 10: 1 to 1:10, in particular from 3: 1 to 1: 3. Use, agent or process according to any one of the preceding claims, characterized in that the average molecular weight of the copolymer in the range of 1000 g / mol to 5,000,000 g / mol, in particular from 2000 g / mol to 500 000 g / mol.