Use of film-forming organopolysiloxanes for reducing the release of ultrafine fibers from textile products

Abstract

Providing a method for reducing emission of microfibers from textile products [Solution] The method includes pretreating a textile product before a washing step with a composition (Z) containing (A) at least 0.1 parts by weight and at most 10.0 parts by weight of a film-forming organopolysiloxane, (B) at least 1 part by weight and at most 20 parts by weight of a cationic surfactant, and (C) at least 30 parts by weight and at most 99 parts by weight of water.

Description

Technical Field

[0001] The present invention relates to a method for reducing the release of ultrafine fibers in the washing process of textile products by pretreatment with a film-forming organopolysiloxane.

Background Art

[0002] Many formulations are used in "consumer products" to obtain specific benefits. For example, specific softness, improvement of touch, reduction of wrinkles, etc.

[0003] Typically, this type of formulation generally consists of a water-insoluble quaternary ammonium compound having at least two long-chain alkyl or alkenyl chains. Due to better biodegradability, there is an increasing interest in quaternary ammonium compounds having long-chain alkyl or alkenyl groups interrupted by functional groups such as carboxyl groups. This type of compound has been known for a long time and is described, for example, in US3915867.

[0004] Also, formulations consisting of a combination of a cationic emulsifier and a functionalized polydiorganosiloxane, such as an amino-functionalized polydiorganosiloxane, a quaternary-functionalized polydiorganosiloxane or a hydroxypropylamino-functionalized polydiorganosiloxane, are known. This type of formulation is described, for example, in WO2011 / 123727A2.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0006] The release of microplastics into the environment is one of the most urgent environmental problems. A significant portion of microplastics consists of ultra-fine fibers of, for example, polyester fabric and is released during daily wearing, especially during washing.

[0007] Regarding the described problems and possible solutions, they are summarized, in particular, by N.J. Lant et al. in PLoS ONE 15(6): e0233332. https: / / doi.org / 10.1371 / journal.pone.0233332 (June 5, 2020). This paper shows that softeners do not have a direct impact on the release of ultra-fine fibers.

Means for Solving the Problem

[0008] The present invention is a method for reducing the release of ultra-fine fibers during the washing process of textile products, wherein the textile product is (A) at least 0.1 part by mass and at most 10.0 parts by mass of a film-forming organopolysiloxane, (B) at least 1 part by mass and at most 20 parts by mass of a cationic surfactant, and (C) at least 30 parts by mass and at most 99 parts by mass of water and is pretreated with a composition (Z) containing the same before the washing process.

Advantages of the Invention

[0009] Surprisingly, the composition (Z) containing a film-forming organopolysiloxane and a cationic surfactant has been found to be beneficial, i.e., to have a reducing effect, on the release of ultra-fine fibers during the washing process.

Embodiments for Carrying Out the Invention

[0010] (Composition (Z)) It is preferable to use a composition containing at least 0.25 part by mass, more preferably at least 0.4 part by mass, preferably at most 5 parts by mass, and more preferably at most 3 parts by mass of a film-forming organopolysiloxane (A).

[0011] The composition preferably contains at least 1.5 parts by mass, more preferably at least 2.5 parts by mass, and preferably at most 15 parts by mass, more preferably at most 10 parts by mass of a cationic surfactant (B).

[0012] The composition preferably contains at least 45 parts by mass, more preferably at least 60 parts by mass, and preferably at most 97 parts by mass, more preferably at most 95 parts by mass of water (C).

[0013] (Film-forming organopolysiloxane (A)) The film-forming organopolysiloxane (A) is preferably used in the form of an aqueous emulsion.

[0014] The composition (Z) preferably contains an oil-in-water emulsion of a film-forming organopolysiloxane (A), and the organopolysiloxane (A) is (i) 100 parts by mass of an aminoalkyl group-containing polyorganosiloxane (P) which is liquid at 20°C and contains at least 80 mol% of units selected from the units of general formulas (Ia), (Ib), (IIa) and (IIb) aminoalkyl group-containing polyorganosiloxane (P) R 1 2SiO (2 / 2) (Ia), R 1 a R 2 SiO (3-a) / 2 (Ib), R 3 3SiO (1 / 2) (IIa), R 3 2R 4 SiO (1 / 2) (IIb), [In the formula, a is 0 or 1, R 1 is an unsubstituted alkyl group having 1 to 40 carbon atoms, R 2 is an aminoalkyl group of the general formula (III), -R 5 -NR 6 R 7 (III), {wherein, R 5 is a divalent hydrocarbon group having 1 to 40 carbon atoms, R 6 is a monovalent hydrocarbon group having 1 to 40 carbon atoms, hydrogen, or an alkanoyl group, R 7 is a group of the general formula (IV), -(R 8 -NR 6 ) x R 6 (IV), (wherein, x is an integer from 0 to 40, R 8 is a divalent group of the general formula (V), -(CR 9 R 9 -) y (V), wherein, y is an integer from 1 to 6, R 9 is hydrogen or a hydrocarbon group having 1 to 40 carbon atoms,)} R 3 is an unsubstituted alkyl group having 1 to 40 carbon atoms, R 4 is -OR or -OH group, R is an unsubstituted alkyl group having 1 to 40 carbon atoms, However, in the polyorganosiloxane (P), the average ratio of the units of the general formulas (Ia) and (Ib) to the total of the units of the general formulas (IIa) and (IIb) is 0.5 to 500, and the polyorganosiloxane (P) has an average amine value of at least 0.1 mequiv / g.]、 (ii) 1 to 80 parts by mass of a silicon compound (D) based on 100 parts by mass of the polyorganosiloxane (P), a silicate compound (D1) which is a tetraalkoxysilicate of the general formula (VI), R 10 O4Si (VI), a polysilicate compound (D2) containing at least 80 mol% of the units of the general formulas (VII) and (VIII) and containing at least two units of the general formula (VII), R 10 O3Si 1 / 2 (VII), R 10 O2Si 2 / 2 (VIII), (wherein, R 10 is an unsubstituted hydrocarbon group having 1 to 18 carbon atoms.) an MQ silicone resin (D3) containing at least 80 mol%, preferably at least 95 mol% of the units of the general formulas (IX) and (X), R 11 3SiO 1 / 2 (IX), SiO 4 / 2 (X), (wherein, 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 in the range of 0.5 to 2.0, preferably 0.5 to 1.5, particularly preferably 0.6 to 1.0, and at most 10% by mass, preferably at most 3% by mass, more preferably at most 2.5% by mass of the groups R 11 are -OR and -OH groups.) and a mixture of (D1), (D2) and (D3) in any desired ratio from which the silicon compound (D) is selected is included.

[0015] Preferably used in this method is an oil-in-water emulsion of the film-forming organopolysiloxane (A), and this emulsion further (iii) Protonating agent (S), (iv) Water (W), (v) At most 5 parts by mass of emulsifier (E), and (vi) At least 5 parts by mass of organic solvent or solvent mixture (L) may be included.

[0016] (Cationic surfactant (B)) The composition (Z) preferably (B1) Quaternary alkyl-, alkenyl-, hydroxyalkyl- and alkylbenzeneammonium salts, especially those having an alkyl group with 6 to 24 carbon atoms, especially halides, sulfates, phosphates and acetates, (B2) Alkylpyridinium salts, alkylimidazolinium salts and alkyloxazolinium salts, especially those having an alkyl chain with up to 18 carbon atoms, especially halides, sulfates, phosphates and acetates, (B3) Ester / amide-containing quaternary ammonium salts, especially those having an alkyl ester group, alkenyl ester group, alkylamide group or alkenylamide group and having an alkyl group with 6 to 24 carbon atoms, especially halides, sulfates, phosphates and acetates. contains a cationic surfactant (B) selected from the group of

[0017] The ester / amide-containing quaternary ammonium surfactant (B3) is preferred.

[0018] The cationic surfactant used in the composition (Z) may be one type of surfactant, or may be a plurality of types of surfactants.

[0019] Examples of the surfactant (B1) include (a) Monoalkyl-quaternary ammonium salts, for example - 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 - Dialkyldimethylammonium chloride - Distearyldimethylammonium chloride, and - Dicetyldimethylammonium chloride - Dioleyldimethylammonium chloride (available under the trade name Adogen(R) 472 from Witco Corporation) is.

[0020] An example of the surfactant of formula (B2) is - 1 - Methyl - 1 - stearoylamidoethyl - 2 - stearoylimidazolinium methyl sulfate (available under the trade name Varisoft(R) from Witco Corporation) is.

[0021] Examples of the surfactant (B3) include - N,N - Bis(stearoyloxyethyl) - N,N - dimethylammonium chloride, - N,N - Bis(taloyloxyethyl) - N,N - dimethylammonium chloride, - N,N - Bis(stearoyloxyethyl) - N - (2 - hydroxyethyl) - N - methylammonium methyl sulfate, - N,N - Bis[ethyl(talate)] - N - (2 - hydroxyethyl) - N - methylammonium methyl sulfate, - Difatty acid amide amine - based products, for example [alkyl / alkenyl - C(O) - NH - CH2CH2 - N(CH3)(CH2CH2OH) - CH2CH2 - NH - C(O) - alkyl / alkenyl] + CH3SO4 - (For example, a product available under the trade name Varisoft(R) 222 LT from Witco Corporation) is as follows.

[0022] By using the preferred composition (Z), in the case of textile products, particularly those containing polyester, it is possible to significantly reduce the release of microfibers. At the same time, the use of the preferred composition (Z) achieves not only an improvement in the stain resistance of the treated textile products but also a remarkable improvement in softness.

[0023] The alkyl groups R, R 1 and R 3 may be linear, cyclic, branched, saturated or unsaturated. Preferably, the alkyl groups R, R 1 and R 3 independently have 1 to 18 carbon atoms, particularly 1 to 6 carbon atoms, and particularly preferably are a methyl group or an ethyl group. Particularly preferred groups R, R 1 and R 3 are methyl groups.

[0024] The divalent hydrocarbon group R 5 may be linear, cyclic, branched, aromatic, saturated or unsaturated. The group R 5 preferably has 1 to 6 carbon atoms and particularly preferably is an alkylene group, particularly a propylene group.

[0025] The monovalent hydrocarbon group R 6 may be linear, cyclic, branched, aromatic, saturated or unsaturated. The group R 6 preferably has 1 to 6 carbon atoms and particularly preferably is an alkyl group or an alkanoyl group having 1 to 6 carbon atoms. Particularly preferred substituent R 6 is hydrogen, a methyl group, an ethyl group, a cyclohexyl group and an acetyl group.

[0026] The monovalent hydrocarbon group R 9 may be linear, cyclic, branched, aromatic, saturated or unsaturated. The group R 9is preferably an alkyl group having 1 to 6 carbon atoms, particularly preferably an alkyl group having 1 to 6 carbon atoms. Particularly preferred substituent R 9 is hydrogen, a methyl group, an ethyl group and a cyclohexyl group.

[0027] x preferably has a value of 0 to 18, particularly preferably 0 to 6, especially 1 to 3.

[0028] Particularly preferred group R 2 is -CH2N(R 6 )2, -(CH2)3N(R 6 )2, -(CH2)3N(R 6 )(CH2)2N(R 6 )2, particularly an aminopropyl group, an aminoethylaminopropyl group and a cyclohexylaminopropyl group.

[0029] The polyorganosiloxane (P) is preferably composed of at least 3 units, particularly at least 10 units, preferably at most 1000 units, particularly at most 500 units of the formulas (Ia), (Ib), (IIa) and (IIb). The polyorganosiloxane (P) preferably has a chain length of 3 to 1000 repeating units, particularly 10 to 500 repeating units.

[0030] The viscosity of the polyorganosiloxane (P) is preferably 1 to 100,000 mPa·s, particularly 10 to 10,000 mPa·s (25 °C, shear rate 10 (1 / s)).

[0031] The ratio of the number of units (Ia) to the number of units (Ib) is selected such that the polyorganosiloxane (P) has an amine value of at least 0.1 mequiv / g of polyorganosiloxane (P), preferably at least 0.15 mequiv / g of polyorganosiloxane (P). The amine value of the polyorganosiloxane (P) is preferably at most 7 mequiv / g, particularly preferably at most 2 mequiv / g, especially at most 0.6 mequiv / g.

[0032] The polyorganosiloxane (P) preferably has only units of formula (IIa), only units of formula (IIb), or any combination of units of formula (IIa) and (IIb).

[0033] The polyorganosiloxane (P) is produced by known chemical methods such as hydrolysis and equilibration.

[0034] The monovalent hydrocarbon group R of the tetraalkoxysilicate (D1) and the polysilicate compound (D2) 10 may be linear, cyclic, branched, aromatic, saturated or unsaturated. The group R 10 preferably has 1 to 6 carbon atoms, and particularly preferably is an alkyl group and a phenyl group. Particularly preferred groups R 10 are methyl, ethyl and propyl.

[0035] The polysilicate compound (D2) preferably contains at least 90 mol%, particularly at least 95 mol% of the units of general formulas (VII) and (VIII).

[0036] The remaining units of the polysilicate compound (D2) may be, for example, units of general formulas (XI) and (XII). R 10 OSiO 3 / 2 (XI), SiO 4 / 2 (XII), (wherein R 10 has the above meaning.)

[0037] Preferably, the MQ silicone resin (D3) has a viscosity greater than 1000 mPa·s at 25°C or is solid. The weight average molecular weight measured by gel permeation chromatography (based on polystyrene standards) of these resins is preferably 200 to 200000 g / mol, particularly 1000 to 200000 g / mol.

[0038] The MQ silicone resin (D3) used according to the present invention is preferably soluble in benzene in a range of at least 100 g / l at a temperature of 25 °C and a pressure of 101.325 kPa.

[0039] Based on 100 parts by mass of the polyorganosiloxane (P), the oil-in-water emulsion of the film-forming organopolysiloxane (P) preferably consists of 3 to 50 parts by mass, particularly preferably 5 to 30 parts by mass, of the silicate compound (D1) or (D2) or the organopolysiloxane resin (D3).

[0040] (Protonating agent (S)) The protonating agent (S) is preferably a monoprotic or polyprotic, water-soluble or water-insoluble, organic or inorganic acid.

[0041] Examples of suitable protonating agents (S) are 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. Particularly preferred is acetic acid. The protonating agent is generally added as a stock solution or in the form of an aqueous solution. The protonating agent is preferably added in an amount of 0.05 to 2 mol of protons per mol of the basic nitrogen atom of the group R 2 . The protonating agent is preferably added in an amount such that the oil-in-water emulsion reaches a pH in the range of 3.5 to 7.0, preferably in the range of 3.5 to 6.0, particularly preferably in the range of 3.5 to 5.0.

[0042] In the context of the present invention, the pH is preferably measured at 20 °C using an electrode compliant with the United States Pharmacopeia USP 33.

[0043] (Water (C)) The water is demineralized water or salt-containing water, preferably demineralized water.

[0044] (Emulsifier (E)) The oil-in-water emulsion of the film-forming organopolysiloxane (A) preferably used in the present method contains preferably at most 3 parts by mass, particularly preferably at most 1 part by mass, and particularly at most 0.1 part by mass of an emulsifier based on 100 parts by mass of the organopolysiloxane (A). The emulsifier (E) used may be any of all the ionic emulsifiers and non-ionic emulsifiers known to date, and can be used alone or as a mixture of various emulsifiers. It has also been possible to date to produce an aqueous dispersion, particularly an aqueous emulsion of the organopolysiloxane (A), using these emulsifiers.

[0045] Examples of anionic emulsifiers are as follows: 1. Alkyl sulfates, particularly those having a chain length of 8 to 18 carbon atoms, alkyl and aryl ether sulfates having 8 to 18 carbon atoms in the hydrophobic group and 1 to 40 ethylene oxide (EO) or propylene oxide (PO) units. 2. Sulfonates, particularly alkyl sulfonates having 8 to 18 carbon atoms, alkyl aryl sulfonates having 8 to 18 carbon atoms, taurides, esters and monoesters of sulfosuccinic acid with monohydric alcohols or alkylphenols having 4 to 15 carbon atoms; these alcohols or alkylphenols may optionally be ethoxylated with 1 to 40 EO units. 3. Alkali metal salts and ammonium salts of carboxylic acids having 8 to 20 carbon atoms in the alkyl, aryl, aralkyl or aralkyl group. 4. Phosphoric acid partial esters and their alkali metal salts and ammonium salts, particularly alkyl and aryl phosphates having 8 to 20 carbon atoms in the organic group, alkyl ether and aryl ether phosphates having 8 to 20 carbon atoms and 1 to 40 EO units in the alkyl or aryl group.

[0046] Examples of non-ionic emulsifiers are as follows: 5. Polyvinyl alcohol having a degree of polymerization of 500 to 3000 and containing 5% to 50%, preferably 8% to 20%, of vinyl acetate units. 6. Alkyl polyglycol ethers, preferably those having 5 to 40 EO units and an alkyl group with 8 to 20 carbon atoms. 7. Alkyl aryl polyglycol ethers, preferably those having 5 to 40 EO units and alkyl and aryl groups with 8 to 20 carbon atoms. 8. Ethylene oxide / propylene oxide (EO / PO) block copolymers, preferably those having 8 to 40 EO or PO units. 9. Addition products of alkylamines having an alkyl group with 8 to 22 carbon atoms and ethylene oxide or propylene oxide. 10. Fatty acids having 6 to 24 carbon atoms. 11. General formula R * -O-ZO alkyl polyglycoside (wherein R * is a linear or branched saturated or unsaturated alkyl group having an average of 8 to 24 carbon atoms, and ZO is an oligoglycoside group having an average of o = 1 to 10 hexose units or pentose units or a mixture thereof). 12. Natural substances and their derivatives, such as lecithin, lanolin, saponin, cellulose, cellulose alkyl ether, carboxyalkyl cellulose, where the 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, Si, especially those having an alkoxy group with up to 24 carbon atoms and / or an EO group and / or a PO group with up to 40 carbon atoms.

[0047] Examples of cationic emulsifiers are as follows: 14. Salts of primary, secondary, and tertiary fatty amines having 8 to 24 carbon atoms with acetic acid, sulfuric acid, hydrochloric acid, and phosphoric acid. 15. Quaternary alkyl and alkylbenzene ammonium salts, especially those having an alkyl group with 6 to 24 carbon atoms, especially halides, sulfates, phosphates, and acetates. 16. Alkylpyridinium salts, alkylimidazolinium salts, alkyloxazolinium salts, especially those having up to 18 carbon atoms in the alkyl chain, especially halides, sulfates, phosphates, acetates.

[0048] Particularly preferred amphoteric emulsifiers are as follows: 17. Amino acids having long-chain substitutions, such as N-alkyldi(aminoethyl)glycine or N-alkyl-2-aminopropionate. 18. Betaines, such as N-(3-acylamidopropyl)-N,N-dimethylammonium salts having a C8-C18 acyl group and alkylimidazolium betaines.

[0049] Preferred as the emulsifier are nonionic emulsifiers, especially the alkyl polyglycol ethers mentioned in 6. above, and cationic emulsifiers, especially the quaternary alkyl- and alkylbenzeneammonium salts mentioned in 15. above. The emulsifier may be composed of one of the above emulsifiers or a mixture of two or more of the above emulsifiers and can be used in pure form or as a solution of one or more emulsifiers in water or an organic solvent.

[0050] (organic solvent or solvent mixture (L)) The oil-in-water emulsion of the film-forming organopolysiloxane (A) preferably used in the method according to the invention contains an organic solvent or solvent mixture (L) selected from monoalcohols or polyalcohols, aprotic ethers, or mono-, di- or tri-alkoxyalkyl ethers having an alkyl group with up to 7 carbon atoms.

[0051] Examples of monoalcohols or polyalcohols include methanol, ethanol, n-propanol, isopropanol, butanol, n-amyl alcohol, isoamyl alcohol, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butyl glycol, hexylene glycol, heptylene glycol, octylene glycol, glycerol, and the like.

[0052] Examples of aprotic ethers include dioxane, tetrahydrofuran, diethyl ether, diisopropyl ether, and the like.

[0053] Mono-, di- or trialkoxyalkyl ethers are glycol ethers such as ethylene glycol ether, propylene glycol ether or butylene glycol ether. Examples of ethylene glycol ethers are as follows. - Ethylene glycol monomethyl ether (methyl glycol, 2-methoxyethanol, CH3-O-CH2CH2-OH), - Ethylene glycol monoethyl ether (ethyl glycol, 2-ethoxyethanol, CH3CH2-O-CH2CH2-OH) - Ethylene glycol monopropyl ether (2-propoxyethanol, CH3CH2CH2-O-CH2CH2-OH) - Ethylene glycol monoisopropyl ether (2-isopropoxyethanol, (CH3)2CH-O-CH2CH2-OH) - Ethylene glycol mono-n-butyl ether (2-butoxyethanol, CH3CH2CH2CH2-O-CH2CH2-OH) - Ethylene glycol monophenyl ether (2-phenoxyethanol, C6H5-O-CH2CH2-OH) - Ethylene glycol monohexyl ether (2-hexyloxyethanol, C6H 11 -O-CH2CH2-OH) - Ethylene glycol monobenzyl ether (2-benzyloxyethanol, C6H5CH2-O-CH2CH2-OH) - Diethylene glycol monomethyl ether [2-(2-methoxyethoxy)ethanol, methyl carbitol, CH3-O-CH2CH2-O-CH2CH2-OH] - Diethylene glycol monoethyl ether [2-(2-ethoxyethoxy)ethanol, carbitol cellosolve, CH3CH2-O-CH2CH2-O-CH2CH2-OH] - Diethylene glycol mono-n-butyl ether [2-(2-butoxyethoxy)ethanol, CH3CH2CH2CH2-O-CH2CH2-O-CH2CH2-OH] - Triethylene glycol mono-n-butyl ether (butyl triglycol) - Diethylene glycol diethyl ether (diethyl carbitol) - Dibutylene glycol dibutyl ether (dibutyl carbitol)

[0054] Examples of propylene glycol ethers are as follows. - 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

[0055] Examples of butylene glycol ethers are as follows. - Butylene glycol monomethyl ether (1-methoxy-2-propanol) - Butylene glycol monobutyl ether (ethoxypropanol)

[0056] Preferred examples of the solvent or solvent mixture (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.

[0057] Particularly preferred examples of the solvent or solvent mixture (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.

[0058] The oil-in-water emulsion of the film-forming organopolysiloxane (A) preferably used in this method contains preferably 10 to 150 parts by mass, particularly preferably 20 to 120 parts by mass, 40 to 100 parts by mass of a solvent or solvent mixture (L) based on 100 parts by mass of the organopolysiloxane (A).

[0059] [Production method] The oil-in-water emulsion preferably used in the present method is produced by mixing a combination of a polyorganosiloxane (P), a silicate compound (D1), a polysilicate compound (D2) or an MQ resin (D3), a protonating agent (S), water (W), optionally an emulsifier (E), an organic solvent (L), and optionally further components. The mixing is preferably carried out at a temperature of 10 to 80 °C, particularly preferably 15 to 40 °C and at a pressure of preferably 900 to 1100 hPa. However, the mixing can also be carried out at a higher or lower pressure. In a preferred procedure, the polyorganosiloxane (P) is premixed with the silicate compound (D1), the polysilicate compound (D2) or the MQ resin (D3). This premix is incorporated into a mixture of a protonating agent (S), water (W), optionally an emulsifier (E), an organic solvent (L), and optionally further components, and then further diluted with water to form an oil-in-water emulsion. The production may be batchwise or continuous.

[0060] Techniques for producing emulsions of organopolysiloxanes are known. Thus, strong mixing and dispersion can be carried out using a rotor - stator stirrer, a colloid mill, a high - pressure homogenizer, a microchannel, a membrane, a jet nozzle, etc., or using ultrasonic waves.

[0061] The oil-in-water emulsion can be diluted with water in any ratio. The emulsion can preferably contain water in an amount of at least 10.0 parts by mass, particularly at least 100.0 parts by mass, preferably at most 5000 parts by mass, particularly at most 1000 parts by mass.

[0062] Regardless of the water content, the oil-in-water emulsion is a liquid ranging from transparent to opaque and has a viscosity of preferably 5 to 10000 mPa·s, particularly preferably 5 to 1000 mPa·s, especially 10 to 500 mPa·s at 25 °C and a shear rate of 10 (1 / s).

[0063] [Use] Treatment and impregnation of any desired fibers, especially natural fibers, synthetic fibers, and functional materials are particularly preferred.

[0064] The composition (Z) is preferably used by adding it, especially to the fabric softener compartment, during the washing process in a commercially available washing machine. This includes washing the laundry in a washing cycle and bringing it into contact with the composition (Z) in a fabric softening cycle. Thereby, the fiber product is impregnated with the film-forming organopolysiloxane (A), and as a result, in subsequent washing processes, the release of microfibers from the fiber product, especially a fiber product containing polyester, is reduced.

[0065] Furthermore, the composition (Z) can be used not only to impregnate fiber products, especially fiber products containing polyester, so as to reduce the release of microfibers in the washing process. Rather, the composition (Z) can also achieve resistance to other effects, such as environmental influences like heat, sunlight, especially ultraviolet irradiation, oxidizing agents, or an acidic environment, and as a result, the release of microfibers is also reduced when wearing the fabric. At the same time, the use of the composition (Z) achieves a remarkable improvement in softness as well as an improvement in the stain resistance of the treated fiber product.

Examples

[0066] In the following examples, all numerical values of parts and percentages are by mass unless otherwise specified. Unless otherwise stated, the examples that follow are carried out at the pressure of the ambient atmosphere, i.e., about 1000 hPa, at room temperature, i.e., about 20 °C, or at the temperature established by combining the reactants at room temperature without additional heating or cooling.

[0067] Viscosity was measured using a cone-plate system (CP50-2 cone) with an opening angle of 2° on a rheometer “MCR 302” manufactured by Anton Paar, in accordance with DIN EN ISO 3219:1994 and DIN 53019. The device was calibrated with the standard oil 10000 of the Physikalisch-Technischen Bundesanstalt (German National Metrology Institute). The measurement temperature was 25.00 °C ± 0.05 °C, and the measurement time was 3 minutes. The viscosity value is the arithmetic mean of three individual measurements carried out independently. The measurement uncertainty of the dynamic viscosity is 1.5%. The shear rate gradient was selected as a function of viscosity and is given individually for each viscosity value.

[0068] The amine value indicates how many mmol of KOH are equivalent to 1 g of the substance to be measured. The amine value is determined in accordance with DIN 16945 - Version 1989 - 03.

[0069] Example: The aminoalkyl group-containing polydimethylsiloxane (P-1) used in the test example is a mixed hydroxy- / methoxydimethylsilyl-terminated copolymer consisting of aminoethylaminopropylmethylsiloxane units and dimethylsiloxane units, having a viscosity of 982 mPa·s (25 °C, shear rate 10 (1 / s)) and an amine value of 0.287 mmol / g.

[0070] 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 - 7 units of the general formula (VIII) (where R 10 is an ethyl group), and the SiO2 content is 40% by mass.

[0071] The MQ silicone resin (D-3) used in the test example is solid at 20 °C, contains units of the general formula (IX) and (X) in a ratio of 0.37 - 0.63, and has a silicone resin with a molecular weight Mn = 2700 g / mol (weight average molecular weight based on polystyrene standard by gel permeation chromatography).

[0072] Production of various formulations:

[0073] [Example 1: Oil-in-water emulsion E1 of film-forming organopolysiloxane] 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) was added to 7.0 g of demineralized water, 7.0 g of ethylene glycol monobutyl ether (commercially available from BASF), 2.9 g of ethylene glycol monohexyl ether (commercially available from BASF), and 0.13 g of acetic acid (80% aqueous solution commercially available from Brenntag) while stirring at room temperature, and then 65.97 g of demineralized water was further added and stirred. A colorless and transparent emulsion (E1) was obtained. Emulsion E1 contains 17% by mass of film-forming organopolysiloxane A1 .

[0074] [Example 2: Oil-in-water emulsion of film-forming organopolysiloxane E2 7.0 g of demineralized water, 12.0 g of n-butyl glycol (available under the trade name of Ethylene glycol butyl ether from Sigma-Aldrich), and 0.4 g of acetic acid (80% aqueous solution available from Brenntag) were first charged and mixed at room temperature. 17.0 g of a mixture of 16.1 g of aminoalkyl group-containing polydimethylsiloxane (P-1) and 0.9 g of silicate compound (D-1) and 63.6 g of demineralized water were sequentially stirred. A translucent and colorless emulsion ( E2 ) was obtained. Emulsion E2 contains 17% by mass of film-forming organopolysiloxane A2 .

[0075] [Example 3: (Non-invention) Oil-in-water emulsion of linear organopolysiloxane VE3 ​​7.0 g of deionized water, 4.0 g of isotridecyl octaethoxylate (manufactured by BASF, commercially available under the trade name Lutensol TO 8), 2.0 g of isotridecyl pentaethoxylate (manufactured by BASF, commercially available under the trade name Lutensol TO 5), and 0.4 g of acetic acid (80% aqueous solution available from Brenntag) are initially charged and mixed at room temperature. 34.0 g of aminoalkyl group-containing polydimethylsiloxane (P-1) and 52.6 g of deionized water are sequentially stirred. A translucent and whitish emulsion ( VE3 ) is obtained. The emulsion ( VE3 ) does not contain film-forming organopolysiloxane.

[0076] [Example 4] (A) Film-forming organopolysiloxane, (B) Cationic surfactant, and (C) Water A composition containing Z1 , Z2 (the present invention), and composition VZ3 , VZ4 (non-invention).

Table 1

[0077] (The formulations of the present invention and non-invention) are manufactured by heating water to 50°C. A cationic surfactant that has been melted in advance at 50°C and stirred vigorously is added while stirring vigorously at this temperature. Stirring is continued until a homogeneous mixture is obtained. The mixture is cooled to 30°C, and an oil-in-water emulsion E1 , E2 or VE3 and additional components are added. VZ4 For

[0078] [Example 5] For the following experiments, 50 ml of the composition Z1 , Z2 , VZ3 and VZ4Dilute it with deionized water to make 2000 ml of the working concentration.

[0079] Use a black 100% polyester woven fabric with a basis weight of 270 g / m 2 . Pre-wash this woven fabric in a washing machine (Miele Softtronic W 1935) at 40 °C, main wash program, without detergent. Then, punch it out into a circle with a diameter of 113 mm. To prevent fraying, melt the edges with a flame. The punched-out polyester woven fabric is pretreated with the diluted composition Z1 , Z2 , VZ3 or VZ4 . This pretreatment is carried out in each case by placing one piece of the woven fabric flat in a beaker, stirring it by hand with 19 ml of the diluted composition Z1 , Z2 , VZ3 , VZ4 or water as a blank value ( BL ), squeezing it between two rollers, and air-drying it overnight. Finally, iron it using a commercially available iron (about 20 seconds, synthetic program).

[0080] To simulate the washing cycle, the experiment is carried out using a Linitester device (manufactured by Hanau). For this purpose, 200 ml of washing liquid (4 g of Ariel liquid detergent dissolved in 1 liter of water), 20 steel balls, and the pretreated polyester woven fabric are placed in a metal beaker and processed at 60 °C for 90 minutes in the Linitester device. Filter the washing liquid using a Büchner funnel equipped with a round filter paper (manufactured by VWR, diameter 55 mm, pore size 31 - 50 μm). Rinse the woven fabric with 100 ml of water and filter the rinsing water through the same filter. Take a photograph of the filter paper and electronically evaluate the number of microfibers filtered (image processing software ImageJ); output the area occupied by the microfibers on the filter paper. The results are the average of 12 individual measurements.

Table 2

[0081] As is clear from Table 2, the composition Z1 and Z2 when used, the blank value BL (without finishing) or VZ4 (finishing with only cationic surfactant), the release of ultrafine fibers from the polyester woven fabric is reduced. Formulations without film-forming polysiloxane VZ3 when used, the blank value BL and the composition Z1 and Z2 when used, significantly more ultrafine fibers are released compared to the case where they are used.

Claims

1. A method for reducing the release of ultrafine fibers during the washing process of a textile product, wherein the textile product is (A) at least 0.1 part by mass and at most 10.0 parts by mass of a film-forming organopolysiloxane, (B) at least 1 part by mass and at most 20 parts by mass of a cationic surfactant, and (C) at least 30 parts by mass and at most 99 parts by mass of water is pretreated with a composition (Z) before the washing process, the composition (Z) contains an oil-in-water emulsion of the film-forming organopolysiloxane (A), and the film-forming organopolysiloxane (A) is (i) 100 parts by mass of an aminoalkyl group-containing polyorganosiloxane (P) which is liquid at 20 °C and contains at least 80 mol% of units selected from the units of general formulas (Ia), (Ib), (IIa) and (IIb) R12SiO(2 / 2) (Ia), R1aR2SiO(3-a) / 2 (Ib), R33SiO(1 / 2) (IIa), R32R4SiO(1 / 2) (IIb), [wherein, a is 0 or 1, R1 is an unsubstituted alkyl group having 1 to 40 carbon atoms, R2 is an aminoalkyl group of general formula (III), -R5-NR6R7 (III), {wherein, R5 is a divalent hydrocarbon group having 1 to 40 carbon atoms, R6 is a monovalent hydrocarbon group having 1 to 40 carbon atoms, hydrogen, or an alkanoyl group, R7 is a group of general formula (IV), -(R8-NR6)xR6 (IV), (wherein, x is an integer of 0 to 40, R8 is a divalent group of general formula (V), -(CR9R9-)y (V), wherein, y is an integer of 1 to 6, R9 is hydrogen or a hydrocarbon group having 1 to 40 carbon atoms,)} R3 is an unsubstituted alkyl group having 1 to 40 carbon atoms, R4 is -OR or -OH group, R is an unsubstituted alkyl group having 1 to 40 carbon atoms, provided that in the polyorganosiloxane (P), the average ratio of the units of general formulas (Ia) and (Ib) to the total of the units of general formulas (IIa) and (IIb) is 0.5 to 500, and the polyorganosiloxane (P) has an average amine value of at least 0.1 mequiv / g. ] (ii) 1 to 80 parts by mass of a silicon compound (D) based on 100 parts by mass of the polyorganosiloxane (P), a silicate compound (D1) which is a tetraalkoxysilicate of the general formula (VI), R10O4Si (VI), a polysilicate compound (D2) containing at least 80 mol% of the units of the general formulas (VII) and (VIII) and containing at least two units of the general formula (VII), R10O3Si1 / 2 (VII), R10O2Si2 / 2 (VIII), (wherein, R10 is an unsubstituted hydrocarbon group having 1 to 18 carbon atoms), an MQ silicone resin (D3) containing at least 80 mol% of the units of the general formulas (IX) and (X), R113SiO1 / 2 (IX), SiO4 / 2 (X), (wherein, R11 has the meaning given for R1 or R4, the ratio of the units of the general formulas (IX) and (X) is 0.5 to 2.0, and at most 10% by mass of the group R11 is an -OR and -OH group), and a mixture of (D1), (D2) and (D3) in any desired ratio a silicon compound (D) selected from A method comprising.

2. The method according to claim 1, wherein the film-forming organopolysiloxane (A) is used in the form of an aqueous emulsion.

3. The group R １ and R ３ The method according to claim 1 or 2, wherein is a methyl group.

4. The method according to claim 1 or 2, wherein the group R is a methyl group.

5. The polysilicate compound (D2) contains at least 90 mol% of the units of the general formulas (VII) and (VIII), and the remaining units are of the general formulas (XI) and (XII) R １０ OSiO ３／２ (XI), SiO ４／２ (XII), (wherein R １０ has the meaning given in claim 1) The method according to claim 1 or 2, which is a unit of

6. The method according to claim 1 or 2, wherein the MQ silicone resin (D3) has a viscosity greater than 1000 mPa·s at 25°C (measured at 25°C and a shear rate of 10 (1 / s)) or is solid.

7. The cationic surfactant (B) is (B1) quaternary alkyl-, alkenyl-, hydroxyalkyl- and alkylbenzeneammonium salts, (B2) alkylpyridinium salts, alkylimidazolinium salts, and alkyloxazolinium salts, and (B3) ester / amide-containing quaternary ammonium salts The method according to claim 1 or 2, which is selected from the group of

8. The method according to claim 1 or 2, wherein the oil-in-water emulsion of the film-forming organopolysiloxane (A) contains an organic solvent or solvent mixture (L) selected from a monoalcohol or polyalcohol, an aprotic ether, or a mono-, di- or trialkoxyalkyl ether having an alkyl group with up to 7 carbon atoms.

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