USE OF FILM-FORMING ORGANOPOLYSILOXANES TO REDUCE MICROFIBER RELEASE FROM TEXTILES

Description

[0001] The invention relates to a method for reducing the release of microfibers during the washing process of textiles by pretreatment with film-forming organopolysiloxanes.

[0002] Many formulations are used in consumer products to achieve a specific benefit. Examples include extra softness, improved feel, or wrinkle reduction.

[0003] Typically, such formulations contain water-insoluble, quaternary ammonium compounds with at least two long-chain alkyl or alkenyl chains. Due to their better biodegradability, quaternary ammonium compounds containing long-chain alkyl or alkenyl groups interrupted by functional groups, such as carboxyl groups, have gained interest. Such compounds have been known for a long time and are described, for example, in US Pat. No. 3,915,867.

[0004] Formulations with combinations of cationic emulsifiers and functionalized polydiorganosiloxanes, for example, amino-functionalized polydiorganosiloxanes, polydiorganosiloxanes with quaternary functionalizations, or hydroxypropylamino-functionalized polydiorganosiloxanes, are also known. Such formulations are described, for example, in WO2011 / 123727A2 and WO 2017 / 191462 A1.

[0005] The release of microplastics into the environment is one of the most pressing environmental problems. A significant portion of these microplastics are microfibers, such as those from polyester fabrics, which are released during daily wear, but especially during the washing process.

[0006] The described problem and possible solutions are summarized by NJ Lant et al. in PLoS ONE 15(6): e0233332.https: / / doi.org / 10.1371 / journal.pone.0233332 (June 5, 2020). This article shows that fabric softeners have no direct influence on microfiber release.

[0007] The invention relates to a method according to claim 1 for reducing the release of microfibers during the washing process of textiles which are pretreated before the washing process with composition (Z) containing (A) at least 0.1 part by weight and at most 10.0 parts by weight of film-forming organopolysiloxanes, (B) at least 1 part by weight and at most 20 parts by weight of cationic surfactants and (C) at least 30 parts by weight and at most 99 parts by weight of water.

[0008] Surprisingly, it was found that the compositions (Z) containing film-forming organopolysiloxanes and cationic surfactants have a positive, i.e. reducing, effect on microfiber release in the washing process.

[0009] Preferably, compositions are used which contain at least 0.25 parts by weight, preferably at least 0.4 parts by weight, and preferably at most 5 parts by weight, preferably at most 3 parts by weight, of film-forming organopolysiloxanes (A).

[0010] The composition preferably contains at least 1.5 parts by weight, preferably at least 2.5 parts by weight, and preferably at most 15 parts by weight, preferably at most 10 parts by weight of cationic surfactants (B).

[0011] Preferably, the composition contains at least 45 parts by weight, preferably at least 60 parts by weight, and preferably at most 97 parts by weight, preferably at most 95 parts by weight of water (C).

[0012] According to the invention, the film-forming organopolysiloxanes (A) are used in the form of their aqueous emulsions.

[0013] According to the invention, the composition (Z) contains an oil-in-water emulsion of film-forming organopolysiloxanes (A) which (i) 100 parts by weight of polyorganosiloxane (P) which is liquid at 20 °C and contains aminoalkyl groups and at least 80 mol% of units selected from units of the general formulas Ia, Ib, IIa and IIb R 1< 2 SiO (2 / 2) (Ia), R 1< a R 2< SiO (3-a) / 2 (Ib), R 3< 3 SiO (1 / 2) (IIa), R 3< 2 R 4< SiO (1 / 2) (IIb), in which a means the value 0 or 1, R 1< unsubstituted alkyl radicals with 1-40 carbon atoms, R 2< Aminoalkyl radical of the general formula III - R 5< -NR 6< R 7< (III), where R 5< divalent hydrocarbon residue with 1-40 carbon atoms, R 6< monovalent hydrocarbon residue with 1-40 carbon atoms, hydrogen or alkanoyl residue and R 7< a radical of the general formula IV -(R 8< -NR 6< ) x R 6< (IV), where x an integer value from 0 to 40 and R 8< a divalent radical of the general formula V -(CR 9< R 9< -) y (V), where y an integer value from 1 to 6, R 9< hydrogen or hydrocarbon residue with 1-40 carbon atoms, R 3< unsubstituted alkyl radicals with 1-40 carbon atoms, R 4< residues -OR or -OH and, Runsubstituted alkyl radicals having 1-40 carbon atoms, wherein in the polyorganosiloxane (P) the average ratio of the units of the general formulas Ia and Ib to the sum of units of the general formulas IIa and IIb is 0.5 to 500 and the polyorganosiloxane (P) has an average amine number of at least 0.1 mequiv / g, (ii) 1 to 80 parts by weight of silicon compound (D) (based on 100 parts by weight of the polyorganosiloxane (P)), which is selected from a silicate compound (D1), the tetraalkoxysilicate of the general formula VI R 10< O 4 Si (VI), polysilicate compound (D2) which contains at least 80 mol% of units of the general formulas VII and VIII and at least 2 units of the general formula VII R 10< O 3 Si 1 / 2 (VII), R 10< O 2 Si 2 / 2 (VIII), wherein R 10< unsubstituted hydrocarbon radicals having 1-18 carbon atoms, MQ silicone resin (D3) containing at least 80 mol%, preferably at least 95 mol%, units of the general formula IX and X R 11< 3 SiO 1 / 2 (IX), SiO 4 / 2 (X), where R 11< has the meaning given for R 1< or R 4< and the ratio of the units of the general formulas IX and X is 0.5 to 2.0, preferably 0.5 to 1.5, particularly preferably in the range from 0.6 to 1.0, and at most 10 wt.%, preferably at most 3 wt.%, preferably at most 2.5 wt.% of the radicals R 11< are -OR and -OH, and mixtures of any proportions (D1), (D2) and (D3). The process preferably uses oil-in-water emulsions of film-forming organopolysiloxanes (A) which further contain (iii) protonating agent (S), (iv) water (W), (v) at most 5 parts by weight of emulsifier (E), and (vi) at least 5 parts by weight of an organic solvent or solvent mixture (L). may contain.

[0014] The composition (Z) preferably contains cationic surfactants (B) selected from the group of (B1) Quaternary alkyl, alkenyl, hydroxyalkyl and alkylbenzeneammonium salts, in particular those whose alkyl groups have 6 to 24 C atoms, in particular the halides, sulfates, phosphates and acetates, (B2) alkylpyridinium, alkylimidazolinium and alkyloxazolinium salts, in particular those whose alkyl chain has up to 18 C atoms, especially the halides, sulfates, phosphates and acetates, (B3) ester / amido-containing quaternary ammonium salts, in particular those with alkyl ester, alkenyl ester, alkylamido or alkenylamido groups, whose alkyl groups have 6 to 24 C atoms, in particular the halides, sulfates, phosphates and acetates.

[0015] Ester / amido-containing quaternary ammonium surfactants (B3) are preferred.

[0016] The cationic surfactants used in the compositions (Z) may be one type of surfactant or several types of surfactants.

[0017] Examples of surfactants (B1) are (a) monoalkyl quaternary ammonium salts, such as behenyltrimethylammonium salt, stearyltrimethylammonium salt, cetyltrimethylammonium salt and hydrogenated tall oil alkyltrimethylammonium salt and (b) dialkyl quaternary ammonium salts, such as dialkyl (C 14 -C 18 )dimethylammonium chloride, dialkylalkyldimethylammonium chloride, distearyldimethylammonium chloride and dicetyldimethylammonium chloride, dioleyldimethylammonium chloride (available from Witco Corporation under the brand name Adogen(R) 472). An example of surfactants of formula (B2) is 1-methyl-l-stearoylamidoethyl-2-stearoylimidazolinium methylsulfate (available from Witco Corporation under the brand name Varisoft(R)). Examples of surfactants (B3) are N,N-bis(stearoyloxyethyl)-N,N-dimethyl ammonium chloride, N,N-bis(talloyloxyethyl)-N,N-dimethyl ammonium chloride, N,N-bis(stearoyloxyethyl)-N-(2-hydroxyethyl)-N-methyl ammonium methyl sulfate, N,N-bis[ethyl(tallowate)]-N-(2-hydroxyethyl)-N-methylammonium methyl sulfate, difatty acid amidoamine-based products such as [alkyl / alkenyl-C(O)-NH-CH 2 CH 2 -N(CH 3 )(CH 2 CH 2 OH)-CH 2 CH 2 -NH-C(O)-alkyl / alkenyl]+ CH 3 SO 4 - (e.g. a product available from Witco Corporation under the brand name Varisoft(R) 222 LT).

[0018] By using the preferred compositions (Z), the release of microfibers from textiles, especially polyester-containing textiles, can be significantly reduced. At the same time, the use of the preferred compositions (Z) achieves a significant improvement in the softness and improved soil repellency of the treated textiles.

[0019] The alkyl radicals R, R 1< , and R 3< can be linear, cyclic, branched, saturated, or unsaturated. The alkyl radicals R, R 1< , and R 3< independently of one another preferably have 1-18 carbon atoms, especially 1 to 6 carbon atoms, particularly preferably methyl or ethyl. A particularly preferred radical R, R 1< , and R 3< is the methyl radical.

[0020] The divalent hydrocarbon radicals R 5< can be linear, cyclic, branched, aromatic, saturated, or unsaturated. The radicals R 5< preferably have 1 to 6 carbon atoms, with particular preference given to alkylene radicals, especially propylene.

[0021] The monovalent hydrocarbon radicals R 6 can be linear, cyclic, branched, aromatic, saturated, or unsaturated. The radicals R 6 preferably have 1 to 6 carbon atoms, with particular preference given to alkyl or alkanoyl radicals having 1 to 6 carbon atoms. Particularly preferred substituents R 6 are hydrogen, methyl, ethyl, cyclohexyl, and acetyl.

[0022] The monovalent hydrocarbon radicals R 9< can be linear, cyclic, branched, aromatic, saturated, or unsaturated. The radicals R 9< preferably have 1 to 6 carbon atoms, with particular preference given to alkyl radicals having 1 to 6 carbon atoms. Particularly preferred substituents R 9< are hydrogen, methyl, ethyl, and cyclohexyl.

[0023] Preferably x a value of 0 to 18, particularly preferably 0 to 6, in particular 1 to 3.

[0024] Particularly preferred radicals R 2< are -CH 2 N(R 6< ) 2 , -(CH 2 ) 3 N(R 6< ) 2 , - (CH 2 ) 3 N(R 6< )(CH 2 ) 2 N(R 6< ) 2 , in particular the aminopropyl radical, aminoethylaminopropyl radical and cyclohexylaminopropyl radical.

[0025] The polyorganosiloxane (P) is preferably composed of at least 3, in particular at least 10 units and preferably at most 1000 units, in particular at most 500 units of the formula Ia, Ib, IIa and IIb.

[0026] The polyorganosiloxane (P) preferably has a chain length of 3 to 1000 repeating units, in particular of 10 to 500 repeating units.

[0027] The viscosity of the polyorganosiloxane (P) is preferably 1 to 100,000 mPa·s, in particular 10 to 10,000 mPa·s (at 25°C and at a shear rate of 10 1 / s).

[0028] The ratio of the number of units Ia to the number of units Ib is selected such that the polyorganosiloxane (P) has an amine number of at least 0.1 mequiv / g of polyorganosiloxane (P), preferably at least 0.15 mequiv / g of polyorganosiloxane (P). The amine number of the polyorganosiloxane (P) is preferably at most 7 mequiv / g, more preferably at most 2 mequiv / g, in particular at most 0.6 mequiv / g.

[0029] The polyorganosiloxane (P) preferably has either exclusively units of formula IIa, exclusively units of formula IIb or a combination of units of formula IIa and IIb.

[0030] The polyorganosiloxane (P) is produced by known chemical processes such as hydrolysis or equilibration.

[0031] The monovalent hydrocarbon radicals R 10< of the tetraalkoxysilicate (D1) and of the polysilicate compound (D2) can be linear, cyclic, branched, aromatic, saturated, or unsaturated. The radicals R 10< preferably have 1 to 6 carbon atoms, with particular preference given to alkyl radicals and phenyl radicals. Particularly preferred radicals R 10< are methyl, ethyl, and propyl.

[0032] The polysilicate compound (D2) preferably contains at least 90, in particular at least 95 mol% of units of the general formulas VII and VIII.

[0033] The remaining units of the polysilicate compound (D2) can be, for example, units of the general formulas XI and XII R 10< OSiO 3 / 2 (XI), SiO 4 / 2 (XII), where R 10< has the above meanings.

[0034] The MQ silicone resins (D3) preferably have a viscosity greater than 1000 mPas at 25°C or are solids. The weight-average molecular weight (based on a polystyrene standard) of these resins, determined by gel permeation chromatography, is preferably 200 to 200,000 g / mol, in particular 1000 to 20,000 g / mol.

[0035] The MQ silicone resins (D3) used according to the invention are preferably soluble in benzene at a temperature of 25°C and a pressure of 101.325 kPa to at least 100 g / l.

[0036] The oil-in-water emulsions of film-forming organopolysiloxanes (A) preferably contain, based on 100 parts by weight of polyorganosiloxane (P), 3 to 50 parts by weight, particularly preferably 5 to 30 parts by weight, of the silicate compounds (D1) or (D2) or of the organopolysiloxane resin (D3).

[0037] The protonating agent (S) is preferably a monoprotic or polyprotic, water-soluble or water-insoluble, organic or inorganic acid.

[0038] Suitable protonating agents (S) include, for example, formic acid, acetic acid, propionic acid, malonic acid, citric acid, hydrochloric acid, sulfuric acid, phosphoric acid, or mixtures thereof. Preferred protonating agents are formic acid, acetic acid, sulfuric acid, or hydrochloric acid. Acetic acid is particularly preferred.

[0039] The protonating agent is usually added undiluted or in the form of an aqueous solution.

[0040] The protonating agent is preferably added in an amount of 0.05 to 2 moles of proton per mole of basic nitrogen atom of the radicals R 2<.

[0041] The protonating agent is preferably added in an amount such that the oil-in-water emulsions reach a pH in a range of 3.5 to 7.0, preferably a pH between 3.5 and 6.0 and particularly preferably a pH between 3.5 and 5.0.

[0042] In the context of the present invention, the pH value is preferably measured with an electrode according to US Pharmacopeia USP 33 at 20°C.

[0043] The water is demineralized or saline water, preferably demineralized water.

[0044] The oil-in-water emulsions of the film-forming organopolysiloxanes (A) preferably used in the process preferably contain at most 3, particularly preferably at most 1, in particular at most 0.1 parts by weight of emulsifier (based on 100 parts by weight of organopolysiloxane (A)).

[0045] All previously known ionic and non-ionic emulsifiers can be used as emulsifiers (E), both individually and as mixtures of different emulsifiers, with which aqueous dispersions, in particular aqueous emulsions of organopolysiloxanes (A), could previously be prepared.

[0046] Examples of anionic emulsifiers are: 1. Alkyl sulfates, particularly those with a chain length of 8 to 18 carbon atoms, alkyl and alkaryl ether sulfates with 8 to 18 carbon atoms in the hydrophobic radical and 1 to 40 ethylene oxide (EO) or propylene oxide (PO) units. 2. Sulfonates, particularly alkylsulfonates with 8 to 18 carbon atoms, alkylarylsulfonates with 8 to 18 carbon atoms, taurides, esters and semiesters of sulfosuccinic acid with monohydric alcohols or alkylphenols with 4 to 15 carbon atoms; these alcohols or alkylphenols can optionally also be ethoxylated with 1 to 40 EO units. 3. Alkali metal and ammonium salts of carboxylic acids with 8 to 20 carbon atoms in the alkyl, aryl, alkaryl, or aralkyl radical. 4. Partial phosphoric acid esters and their alkali and ammonium salts, especially alkyl and alkaryl phosphates with 8 to 20 C atoms in the organic radical, alkyl ether or alkaryl ether phosphates with 8 to 20 C atoms in the alkyl or alkaryl radical and 1 to 40 EO units.

[0047] Examples of non-ionic emulsifiers are:5. Polyvinyl alcohol containing 5 to 50%, preferably 8 to 20%, vinyl acetate units, with a degree of polymerization of 500 to 3000. 6. Alkyl polyglycol ethers, preferably those containing 5 to 40 EO units and alkyl radicals of 8 to 20 carbon atoms. 7. Alkylaryl polyglycol ethers, preferably those containing 5 to 40 EO units and 8 to 20 carbon atoms in the alkyl and aryl radicals. 8. Ethylene oxide / propylene oxide (EO / PO) block copolymers, preferably those containing 8 to 40 EO or PO units. 9. Addition products of alkylamines containing alkyl radicals of 8 to 22 carbon atoms with ethylene oxide or propylene oxide. 10. Fatty acids containing 6 to 24 carbon atoms. 11. Alkyl polyglycosides of the general formula R*-O-ZO, wherein R* is a linear or branched, saturated or unsaturated alkyl radical with an average of 8-24 carbon atoms and ZO is an oligoglycoside radical with an average of 1-10 hexose or pentose units, or mixtures thereof. 12.Natural substances and their derivatives, such as lecithin, lanolin, saponins, cellulose, cellulose alkyl ethers, and carboxyalkylcelluloses, whose alkyl groups each have up to 4 carbon atoms. 13. Linear organo(poly)siloxanes containing polar groups, especially those containing the elements O, N, C, S, P, and Si, especially those with alkoxy groups with up to 24 carbon atoms and / or up to 40 EO and / or PO groups.

[0048] Examples of cationic emulsifiers are: 14. Salts of primary, secondary, and tertiary fatty amines containing 8 to 24 carbon atoms with acetic acid, sulfuric acid, hydrochloric acid, and phosphoric acids. 15. Quaternary alkyl and alkylbenzeneammonium salts, especially those whose alkyl groups have 6 to 24 carbon atoms, especially the halides, sulfates, phosphates, and acetates. 16. Alkylpyridinium, alkylimidazolinium, and alkyloxazolinium salts, especially those whose alkyl chains have up to 18 carbon atoms, especially the halides, sulfates, phosphates, and acetates.

[0049] The following are particularly suitable as ampholytic emulsifiers: 17. Long-chain substituted amino acids, such as N-alkyl-di-(aminoethyl)glycine or N-alkyl-2-aminopropionic acid salts. 18. Betaines, such as N-(3-acylamidopropyl)-N,N-dimethylammonium salts with a C8-C18 acyl residue and alkylimidazolium betaines.

[0050] Preferred emulsifiers are nonionic emulsifiers, in particular the alkyl polyglycol ethers listed above under 6, and cationic emulsifiers, in particular the quaternary alkyl and alkylbenzeneammonium salts listed above under 15. The emulsifier can consist of one of the above-mentioned emulsifiers or of a mixture of two or more of the above-mentioned emulsifiers; it can be used in pure form or as a solution of one or more emulsifiers in water or organic solvents.

[0051] The oil-in-water emulsions of the film-forming organopolysiloxanes (A) preferably used in the process according to the invention contain organic solvents or solvent mixtures (L) selected from monoalcohols or polyalcohols, aprotic ethers or mono-, di- or trialkoxyalkyl ethers having alkyl radicals of up to 7 C atoms.

[0052] Examples of monoalcohols or polyalcohols are methanol, ethanol, n-propanol, isopropanol, butanol, n-amyl alcohol, i-amyl alcohol, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butyl glycol, hexylene glycol, heptylene glycol, octylene glycol and glycerin.

[0053] Examples of aprotic ethers are dioxane, tetrahydrofuran, diethyl ether or diisopropyl ether. Mono-, di- or trialkoxy alkyl ethers are glycol ethers, such as ethylene glycol ether, propylene glycol ether or butylene glycol ether.

[0054] Examples of ethylene glycol ethers are Ethylenglycolmonomethylether (Methylglycol, 2-Methoxyethanol, CH 3 -O-CH 2 CH 2 -OH), Ethylenglycolmonoethylether (Ethylglycol, 2-Ethoxyethanol, CH 3 CH 2 -O-CH 2 CH 2 -OH) Ethylenglycolmonopropylether (2-Propoxyethanol, CH 3 CH 2 CH 2 -O-CH 2 CH 2 -OH) Ethylenglycolmonoisopropylether (2-Isopropoxyethanol, (CH 3 ) 2 CH-O-CH 2 CH 2 -OH) Ethylenglycolmono-n-butylether (2-Butoxyethanol, CH 3 CH 2 CH 2 CH 2 -O-CH 2 CH 2 -OH Ethylenglycolmonophenylether (2-Phenoxyethanol, C 6 H 5 -O-CH 2 CH 2 -OH) Ethylenglycolmonohexylether (2-Hexyloxyethanol, C 6 H 11 -O-CH 2 CH 2 -OH) Ethylenglycolmonobenzylether (2-Benzyloxyethanol, C 6 H 5 CH 2 -O-CH 2 CH 2 -OH) Diethylenglycolmonomethylether [2-(2-Methoxyethoxy)ethanol, Methylcarbitol, CH 3 -O-CH 2 CH 2 -O-CH 2 CH 2 -OH] Diethylenglycolmonoethylether [2-(2-Ethoxyethoxy)ethanol, Carbitolcellosolve, CH 3 CH 2 -O-CH 2 CH 2 -O-CH 2 CH 2 -OH] Diethylenglycolmono-n-butylether [2-(2-Butoxyethoxy)ethanol,CH 3 CH 2 CH 2 CH 2 -O-CH 2 CH 2 -O-CH 2 CH 2 -OH] triethylene glycol mono-n-butyl ether (butyl triglycol) diethylene glycol diethyl ether (diethyl carbitol) dibutethylene glycol dibutyl ether (dibutyl carbitol),

[0055] Examples of propylene glycol ethers are Propylene glycol monomethyl ether (1-methoxy-2-propanol) Propylene glycol monoethyl ether (ethoxypropanol) Propylene glycol mono-n-butyl ether (1-butoxy-2-propanol) Propylene glycol monohexyl ether (1-hexoxy-2-propanol) Dipropylene glycol monoethyl ether Dipropylene glycol mono-n-butyl ether Dipropylene glycol monohexyl ether) Tripropylene glycol monomethyl ether Tripropylene glycol mono-n-butyl ether Tripropylene glycol dimethyl ether

[0056] Examples of butylene glycol ethers are Butylene glycol monomethyl ether (1-methoxy-2-propanol) Butylene glycol monobutyl ether (ethoxypropanol)

[0057] Preferred examples of solvents or solvent mixtures (L) are isopropanol, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butyl glycol, hexylene glycol, heptylene glycol, glycerol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol monohexyl ether, diethylene glycol monomethyl ether, diethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether or dipropylene glycol mono-n-butyl ether.

[0058] Particularly preferred examples of solvents or solvent mixtures (L) are propylene glycol, dipropylene glycol, butyl glycol, ethylene glycol mono-n-butyl ether, ethylene glycol monohexyl ether, diethylene glycol mono-n-butyl ether, propylene glycol mono-n-butyl ether or dipropylene glycol mono-n-butyl ether.

[0059] The oil-in-water emulsions of the film-forming organopolysiloxanes (A) preferably used in the process preferably contain 10 to 150 parts by weight, particularly preferably 20 to 120 parts by weight, 40 to 100 parts by weight of solvent or solvent mixtures (L) (based on 100 parts by weight of organopolysiloxanes (A)).

[0060] The oil-in-water emulsions preferably used in the process are prepared by mixing the combination of polyorganosiloxane (P), silicate compound (D1), polysilicate compound (D2) or MQ resin (D3), protonating agent (S), water (W), optionally emulsifier (E), organic solvent (L), and optionally with other components. Mixing is carried out at a temperature of preferably 10-80 °C, particularly preferably 15-40 °C, and a pressure of preferably 900 to 1100 hPa. However, mixing can also be carried out at higher or lower pressures.

[0061] In a preferred approach, the polyorganosiloxane (P) and the silicate compound (D1), polysilicate compound (D2), or MQ resin (D3) are premixed. This premix is ​​then incorporated into a mixture of protonating agent (S), water (W), optionally an emulsifier (E), organic solvent (L), and optionally other components. The mixture is then diluted with additional water to form an oil-in-water emulsion.

[0062] Production can be discontinuous or continuous.

[0063] Technologies for producing organopolysiloxane emulsions are known. Intensive mixing and dispersing can be carried out in rotor-stator stirrers, colloid mills, high-pressure homogenizers, microchannels, membranes, jet nozzles, and similar devices, or by means of ultrasound.

[0064] The oil-in-water emulsions are dilutable with water in all proportions. The emulsions may contain water in amounts of preferably at least 10.0 parts by weight, in particular at least 100.0 parts by weight, preferably at most 5000 parts by weight, in particular at most 1000 parts by weight.

[0065] The oil-in-water emulsions are, regardless of the water content, clear to opaque liquids with a viscosity of preferably 5 to 10,000 mPa·s, particularly preferably 5 to 1,000 mPa·s, in particular 10 to 500 mPa·s (at 25°C and at a shear rate of 10 1 / s).

[0066] Particularly preferred is the treatment and impregnation of any fibers, especially natural and synthetic textiles and functional materials.

[0067] The compositions (Z) are preferably used during the washing process in a commercially available washing machine, in particular by adding them to the fabric softener compartment. The laundry is cleaned in one wash cycle and brought into contact with the composition (Z) during the fabric softener cycle. This impregnates the textiles with the film-forming organopolysiloxanes (A), resulting in reduced microfiber release from textiles, especially polyester-containing textiles, during the subsequent washing cycle.

[0068] Furthermore, the compositions (Z) can be used not only to impregnate textiles, especially polyester-containing textiles, in such a way that microfiber release is reduced during the washing process. The compositions (Z) can also achieve other effects, such as resistance to environmental influences such as heat, sunlight, especially UV radiation, oxidizing agents, or acidic environments, so that microfiber release is also reduced when the textiles are worn.

[0069] At the same time, the use of compositions (Z) achieves a significant improvement in the softness as well as improved soil repellency of the treated textiles.

[0070] In the following examples, all parts and percentages are by weight unless otherwise stated.

[0071] Unless otherwise stated, the following examples are carried out at ambient atmospheric pressure, i.e., approximately 1000 hPa, and at room temperature, i.e., approximately 20°C or a temperature that occurs when the reactants are combined at room temperature without additional heating or cooling.

[0072] The viscosities were measured on an Anton Paar MCR 302 rheometer according to DIN EN ISO 3219:1994 and DIN 53019, using a cone-and-plate system (CP50-2 cone) with an opening angle of 2°. The instrument was calibrated with Normalöl 10000 from the Physikalisch-Technische Bundesanstalt (PTB). The measurement temperature was 25.00°C + / - 0.05°C, and the measurement time was 3 minutes. The viscosity data represents the arithmetic mean of three independently performed individual measurements. The measurement uncertainty of the dynamic viscosity is 1.5%. The shear rate gradient was selected depending on the viscosity and is shown separately for each viscosity data.

[0073] The amine number indicates how many mmol of KOH are equivalent to one gram of the substance being determined. The amine number is determined according to DIN 16945, version 1989-03. Examples:

[0074] The aminoalkyl group-containing polydimethylsiloxane (P-1) used in the test examples is a mixed hydroxy / methoxydimethylsilyl-terminated copolymer of aminoethylaminopropylmethylsiloxane and dimethylsiloxane units with a viscosity of 982 mPas (at 25°C and at a shear rate of 10 1 / s) and an amine number of 0.287 mmol / g.

[0075] The silicate compound (D-1) used in the test example is a mixture of tetraethoxysilicate of the general formula VI and a polysilicate compound having 2 units of the general formula VII and 1 to 7 units of the general formula VIII, wherein R 10< represents an ethyl radical, with an SiO 2 content of 40 wt%.

[0076] The MQ silicone resin (D-3) used in the test example is a silicone resin which is solid at 20°C and contains units of the general formula IX and X in a ratio of 0.37 to 0.63 with a molecular weight Mn = 2700 g / mol (weight-average molecular weight based on a polystyrene standard determined via gel permeation chromatography).

[0077] Preparation of the different formulations: Example 1: Oil-in-water emulsion of a film-forming organopolysiloxane E1

[0078] 17.0 g of a mixture of 13.6 g of aminoalkyl group-containing polydimethylsiloxane (P-1) and 3.4 g of MQ silicone resin (D-3) are added to 7.0 g of demineralized water, 7.0 g of ethylene glycol monobutyl ether (available from BASF), 2.9 g of ethylene glycol monohexyl ether (available from BASF), and 0.13 g of acetic acid (80% aqueous solution available from Brenntag) while stirring at room temperature. 65.97 g of demineralized water are then stirred in. A clear, colorless emulsion is obtained ( E1 ). Emulsion E1 contains 17 wt.% of the film-forming organopolysiloxane A1 . Example 2: Oil-in-water emulsion of a film-forming organopolysiloxane E2

[0079] 7.0 g of demineralized water, 12.0 g of n-butyl glycol (available under the trade name Ethylene glycol butyl ether from Sigma-Aldrich), and 0.4 g of acetic acid (80% aqueous solution available from Brenntag) are placed at room temperature and mixed. 17.0 g of a mixture of 16.1 g of aminoalkyl-containing polydimethylsiloxane (P-1) and 0.9 g of silicate compound (D-1), as well as 63.6 g of demineralized water, are gradually stirred in. A translucent, colorless emulsion is obtained ( E2 ).

[0080] emulsion E2 contains 17 wt.% of the film-forming organopolysiloxane A2 . Example 3: (Non-inventive) oil-in-water emulsion of a linear organopolysiloxane VE3 :

[0081] 7.0 g of demineralized water, 4.0 g of isotridecyl octaethoxylate, commercially available under the trade name Lutensol TO 8 (BASF), 2.0 g of isotridecyl pentaethoxylate, commercially available under the trade name Lutensol TO 5 (BASF), and 0.4 g of acetic acid (80% aqueous solution available from Brenntag) are placed at room temperature and mixed. 34.0 g of the aminoalkyl-containing polydimethylsiloxane (P-1) and 52.6 g of demineralized water are gradually stirred in. A translucent, whitish emulsion is obtained ( VE3 ).

[0082] emulsion VE3 does not contain film-forming organopolysiloxane. Example 4:

[0083] Compositions Z1 , Z2 (according to the invention) containing (A) film-forming organopolysiloxanes, (B) cationic surfactants and (C) water and compositions VZ3 and VZ4 (not according to the invention). Z1 , Z2 , VZ3 , VZ4 Table 1: Aqueous formulations Oil-in-water emulsion Cationic surfactant B1 ***) Water Electrolytes, perfumes, dyes, preservatives Z1 *) 2,9 g E1 3,8 g 42,6 g 0,7 g Z2 *) 2,9 g E2 3,8 g 42,6 g 0,7 g VZ3 **) 1,5 g VE3 3,8 g 44,0 g 0,7 g VZ4 **) - 3,8 g 45, 7 g 0,5 g *) according to the invention **) not according to the invention ***) B1: N,N-bis[Ethyl(tallowate)]-N-(2-hydroxyethyl)-N-methylammonium methylsulfate (90% solution in isopropanol), commercially available under the trade name Stepantex ®< VK90 (Stepan)

[0084] The formulations (both according to the invention and non-inventive) are prepared by heating the water to 50°C. The cationic surfactant, previously melted at 50°C and vigorously stirred, is added at this temperature with vigorous stirring. Stirring is continued until a homogeneous mixture is obtained. The mixture is cooled to 30°C, and the oil-in-water emulsion is E1 , E2 or VE3 and other ingredients are added. VZ4 Only the cationic surfactant and other ingredients are formulated. Example 5:

[0085] For the following experiments, 50 ml of the compositions Z1 , Z2 , VZ3 and VZ4 diluted with demineralized water to 2000 ml of the application concentration.

[0086] A black, 100% polyester fabric with a grammage of 270 g / m 2 is used.

[0087] The fabric is pretreated by pre-washing it in a washing machine (Miele Softtronic W 1935) at 40°C on the main wash program without detergent. It is then punched into circles with a diameter of 113 mm. The edges are melted with a flame to prevent fraying.

[0088] The punched polyester fabrics are coated with the diluted compositions Z1 , Z2 , VZ3 or VZ4 pretreated by placing one tissue flat in a beaker, with 19 ml of the diluted composition Z1 , Z2 , VZ3 , VZ4 or just water as a blank value ( BL ) is stirred by hand, squeezed between two rollers, and dried overnight on a line. Finally, the fabrics are ironed with a standard iron (approx. 20 seconds, synthetic program).

[0089] To simulate a wash cycle, the tests are conducted in a Linitester device (Hanau). 200 ml of a washing liquid (4 g of Ariel liquid detergent dissolved in one liter of water), 20 steel balls, and a pretreated polyester fabric are placed in a metal beaker and treated in the Linitester device for 90 minutes at 60°C.

[0090] The washing fluid is filtered through a Büchner filter fitted with a paper filter (VWR, 55 mm diameter, pore size: 31-50 µm). The tissue is rinsed with 100 ml of water, and the rinse water is filtered through the same filter.

[0091] The filter paper is photographed, and the number of filtered microfibers is evaluated electronically (ImageJ image processing software); output as the area covered by the microfibers on the filter paper.

[0092] The result is the average of twelve individual measurements. Table 2: Released microfibers composition Released microfibers [mm 2< ] Z1 *) 0.83 mm 2< Z2 *) 0.95 mm 2 VZ3 **) 1.79 mm 2< VZ4 **) 1.10 mm 2< BL **) 1.01 mm 2 *) according to the invention **) not according to the invention

[0093] Table 2 clearly shows that when using the compositions Z1 and Z2 the release of microfibers from the polyester fabric compared to the blank value BL (no equipment) or VZ4 (treatment with only the cationic surfactant) is reduced. When using the formulation VZ3 , which does not contain film-forming polysiloxane are compared with the blank value BL and with the use of the compositions Z1 and Z2 significantly more microfibers are released.

Claims

1. Process for reducing the release of microfibers during the washing process of textiles which are pretreated before the washing process with composition (Z) comprising (A) at least 0.1 parts by weight and at most 10.0 parts by weight of film-forming organopolysiloxanes, which are used in the form of their aqueous emulsions that comprise (i) 100 parts by weight of aminoalkyl group-containing polyorganosiloxane (P) that is liquid at 20°C and comprises at least 80 mol% of units selected from units of the general formulae Ia, Ib, IIa and IIb         R12SiO(2 / 2)     (Ia),         R1aR2SiO(3-a) / 2     (Ib),         R33SiO(1 / 2)     (IIa),         R32R4SiO(1 / 2)     (IIb), in which a is 0 or 1, R1 is unsubstituted alkyl radicals having 1-40 carbon atoms, R2 is an aminoalkyl radical of the general formula III         - R5-NR6R7     (III), where R5 is a divalent hydrocarbon radical having 1-40 carbon atoms, R6 is a monovalent hydrocarbon radical having 1-40 carbon atoms, hydrogen or an alkanoyl radical and R7 is a radical of the general formula IV         -(R8-NR6)xR6     (IV), where x is an integer from 0 to 40 and R8 is a divalent radical of the general formula V         - (CR9R9-)y     (V), where y is an integer from 1 to 6, R9 is hydrogen or a hydrocarbon radical having 1-40 carbon atoms, R3 are unsubstituted alkyl radicals having 1-40 carbon atoms, R4 are -OR or -OH radicals, and R are unsubstituted alkyl radicals having 1-40 carbon atoms, where in the polyorganosiloxane (P) the average ratio of the units of the general formulae Ia and Ib to the sum total of units of the general formulae IIa and IIb is 0.5 to 500 and polyorganosiloxane (P) has an average amine value of at least 0.1 mequiv / g, (ii) 1 to 80 parts by weight of silicon compound (D) (based on 100 parts by weight of the polyorganosiloxane (P)) selected from silicate compound (D1), the tetraalkoxysilicate of the general formula VI         R10O4Si     (VI), polysilicate compound (D2), which comprises at least 80 mol% of units of the general formulae VII and VIII and at least two units of the general formula VII         R10O3Si1 / 2     (VII),         R10O2Si2 / 2     (VIII), where R10 are unsubstituted hydrocarbon radicals having 1-18 carbon atoms, MQ silicone resin (D3), comprising at least 80 mol% of units of the general formulae IX and X         R113SiO1 / 2     (IX),         SiO4 / 2     (X), where R11 has the meaning given for R1 or R4 and the ratio of the units of the general formulae IX and X is 0.5 to 2.0 and at most 10% by weight of the radicals R11 are -OR and -OH, and mixtures of any desired proportions of (D1), (D2) and (D3), (B) at least 1 part by weight and at most 20 parts by weight of cationic surfactants and (C) at least 30 parts by weight and at most 99 parts by weight of water.

2. Process according to Claim 1, in which the radicals R1 and R3 are methyl radicals.

3. Process according to Claim 1 or 2, in which the radical R is a methyl radical.

4. Process according to Claim 1, 2 or 3, in which the polysilicate compound (D2) comprises at least 90 mol% of units of the general formulae VII and VIII and the remaining units are units of the general formulae XI and XII         R10OSiO3 / 2     (XI),         SiO4 / 2     (XII), where R10 has the meanings given in Claim 1.

5. Process according to Claim 1, 2 or 3, in which the MQ silicone resins (D3) have a viscosity at 25°C of greater than 1000 mPas (measured at 25°C and at a shear rate of 10 1 / s) or are solids.

6. Process according to any of the preceding claims, in which the cationic surfactants (B) are selected from the group of the (B1) quaternary alkyl-, alkenyl-, hydroxyalkyl- and alkylbenzeneammonium salts, (B2) alkylpyridinium, alkylimidazolinium and alkyloxazolinium salts and (B3) ester- / amido-containing quaternary ammonium salts.

7. Process according to any of the preceding claims, in which the oil-in-water emulsions of the film-forming organopolysiloxanes (A) comprise organic solvents or solvent mixtures (L), selected from monoalcohols or polyalcohols, aprotic ethers or mono-, di- or trialkoxyalkyl ethers having alkyl radicals of up to 7 carbon atoms.