EP4370635A1 - Use of film-forming organopolysiloxanes for reducing the microfiber release of textiles - Google Patents

Abstract

The invention relates to a process for reducing the microfiber release during the washing process of textiles, which are pre-treated prior to the washing process with composition (Z), containing (A) at least 0.1 parts by weight and not more than 10.0 parts by weight of film-forming organopolysiloxanes, (B) at least 1 part by weight and not more than 20 parts by weight of cationic surfactants, and (C) at least 30 parts by weight and not more than 99 parts by weight of water.

Description

Use of film-forming organopolysiloxanes to reduce microfiber release from textiles

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

Many formulations are used in "consumer products" in order to achieve a specific benefit. Examples are special softness, improved haptics or the reduction of wrinkles.

Typically, such formulations contain water-insoluble, quaternary ammonium compounds usually having 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 carboxy groups have gained interest. Such compounds have been known for a long time and are described, for example, in US3915867.

Also known are formulations with combinations of cationic emulsifiers and functionalized polydiorganosiloxanes, for example amino-functionalized polydiorganosiloxanes, polydiorganosiloxanes with quaternary functionalizations or hydroxypropylamino-functionalized polydiorganosiloxanes. Such formulations are described, for example, in WO2011/123727A2.

The release of microplastics into the environment is one of the most pressing environmental issues. A significant proportion of microplastics are made up of microfibers, eg from polyester fabrics, which are released during everyday wear, but above all during the washing process. The problems described and also possible solutions are, inter alia, by NJ Lant et al. summarized in PLoS ONE 15(6): e0233332.https://doi.org/10.1371/journal.pone.0233332 (June 5, 2020). This article demonstrates that fabric softeners have no direct impact on microfiber release.

The invention relates to a method for reducing the release of microfibers during the washing process of textiles which are pretreated with composition (Z) before the washing process

(A) at least 0.1 parts 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 water.

It was surprisingly found that the compositions (Z) containing film-forming organopolysiloxanes and cationic surfactants have a positive, ie reducing, effect on microfiber release in the washing process.

Compositions are preferably 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).

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). The composition preferably 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).

The film-forming organopolysiloxanes (A) are preferably used in the form of their aqueous emulsions.

The composition (Z) preferably contains an oil-in-water emulsion of film-forming organopolysiloxanes (A) containing (i) 100 parts by weight of polyorganosiloxane (P) which is liquid at 20° C. and has aminoalkyl groups and contains at least 80 mol % of units, selected from units of the general formulas Ia, Ib, Ha and IIb

R ¹ ₂ SiO _(2/2) (Ia),

R1a R2 ^SlO (3- _a )/ ² (Ib),

R ³ ₃ SiO _(i/ 2 ₎ (Ha),

R ³ ₂ R ⁴ SiO _(i/2) (H b), in which a is 0 or 1,

R ¹ means unsubstituted alkyl radicals with 1-40 carbon atoms,

R ² is an aminoalkyl radical of the general formula III - R ⁵ -NR ⁶ R ⁷ (III), where

R ⁵ divalent hydrocarbon radical with 1-40 carbon atoms, R ⁶ is a monovalent hydrocarbon radical having 1-40 carbon atoms, hydrogen or an alkanoyl radical and R ⁷ is a radical of the general formula IV

- (R ⁸ -NR ⁶ ) _X R ⁶ (IV), where x is an integer from 0 to 40 and

R ⁸ is 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 is hydrogen or a hydrocarbon radical with 1-40 carbon atoms,

R ³ are unsubstituted alkyl radicals with 1-40 carbon atoms,

R ⁴ are radicals -OR or -OH and,

R is unsubstituted alkyl radicals having 1-40 carbon atoms, the average ratio of units of the general formulas Ia and Ib to the sum of units of the general formulas Ha and IIb being 0.5 to 500 in the polyorganosiloxane (P) and polyorganosiloxane (P) has an average amine number of at least 0.1 mequiv/g,

(ii) 1 to 80 parts by weight of the silicon compound (D) (based on 100 parts by weight of the polyorganosiloxane (P)) selected from a

Silicate compound (DI), the tetraalkoxy silicate of the general formula VI ^R10O4Si ( _VI ),

Polysilicate compound (D2) containing at least 80 mol % of units of the general formulas VII and VIII and at least 2 units of the general formula VII

_{R10O3Sii /2} ⁽ VII),

R ¹⁰ O ₂ Si _2/2 (VIII), wherein

R ¹⁰ are unsubstituted hydrocarbon radicals with 1-18 carbon atoms,

MQ silicone resin (D3) containing at least 80 mol%, preferably at least 95 mol%, of units of general formula IX and X

R ¹¹ ₃ SiOi _/2 (IX),

S1O4/2 (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 is 1.0 and not more than 10% by weight, preferably not more than 3% by weight, preferably not more than 2.5% by weight, of the radicals R ¹¹ are -OR and -OH, and mixtures of any proportions (DI), (D2) and (D3).

In the process, preferably oil-in-water emulsions film-forming organopolysiloxanes (A) are used, which also (iii) protonating agent (S),

(iv) water (W),

(v) not more than 5 parts by weight of emulsifier (E), and

(vi) may contain at least 5 parts by weight of an organic solvent or solvent mixture (L).

The composition (Z) preferably contains cationic surfactants (B) selected from the group of

(Bl) quaternary alkyl, alkenyl, hydroxyalkyl and alkylbenzene ammonium salts, in particular those whose alkyl groups have 6 to 24 carbon 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 carbon atoms, specifically 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, the alkyl groups of which have 6 to 24 carbon atoms, in particular the halides, sulfates, phosphates and acetates.

Ester/amido containing quaternary ammonium surfactants (B3) are preferred. The cationic surfactants used in the compositions (Z) can be one type of surfactant, but also several types of surfactants.

Examples of surfactants (Bl) are

(a) monoalkyl quaternary ammonium salts, e.g.

- behenyltrimethylammonium salt,

- the stearyltrimethylammonium salt

- cetyltrimethylammonium salt and

- the hydrogenated tall oil alkyltrimethylammonium salt and

(b) dialkyl quaternary ammonium salts, e.g.

- dialkyl(C14-C18)dimethylammonium chloride,

- ditallow alkyl dimethyl ammonium chloride,

- Distearyldimethylammonium chloride and

- Dicetyldimethylammonium chloride

- dioleyldimethylammonium chloride

(available from Witco Corporation under the tradename Adogen (R) 472).

An example of surfactants of formula (B2) is

- 1-Methyl-1-stearoylamidoethyl-2-stearoylimidazolinium methyl sulfate (available from Witco Corporation under the trade name Varisoft (R)).

Examples of surfactants (B3) are

- N,N-bis(stearoyl-oxyethyl)-N,N-dimethyl ammonium chloride,

- N,N-bis(talloyl-oxyethyl)-N,N-dimethyl ammonium chloride,

- N,N-bis(stearoyl-oxyethyl)-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 - (eg, a product available from Witco Corporation under the brand name Varisoft(R) 222 LT).

The release of microfibers can be significantly reduced in the case of textiles, in particular polyester-containing textiles, by using the preferred compositions (Z). At the same time, the use of the preferred compositions (Z) achieves a significant improvement in the soft hand and improved dirt repellency of the treated textiles.

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, in particular 1 to 6 carbon atoms, with a methyl radical or ethyl radical being particularly preferred. A particularly preferred radical R, R ¹ and R ³ is the methyl radical.

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, particular preference being given to alkylene radicals, in particular propylene.

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, particular preference being given to alkyl radicals or alkanoyl radicals having 1 to 6 carbon atoms. Particularly preferred substituents R ⁶ are hydrogen, the methyl, ethyl, cyclohexyl radical and acetyl radical.

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, particular preference is given to alkyl radicals having 1 to 6 carbon atoms. Particularly preferred substituents R ⁹ are hydrogen, the methyl, the ethyl and the cyclohexyl radical.

x preferably has a value of 0 to 18, particularly preferably 0 to 6, in particular 1 to 3.

Particularly preferred R ² radicals 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.

The polyorganosiloxane (P) is preferably built up from 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, Ha and IIb.

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

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 101/s).

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

The polyorganosiloxane (P) preferably has either exclusively units of the formula H a , exclusively units of the formula IIb or a combination of units of the formula Ha and IIb.

The polyorganosiloxane (P) is prepared by known chemical processes such as. B. hydrolysis or equilibration.

The monovalent hydrocarbon radicals R ¹⁰ of the tetraalkoxy silicate (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 alkyl radicals and phenyl radicals being particularly preferred. Particularly preferred radicals R ¹⁰ are methyl, ethyl and propyl.

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

The remaining units of the polysilicate compound (D2) can, for example, be units of the general formulas XI and XII

R ¹⁰ OSiO _3/2 (XI),

S1O4/2 (XII), where R ¹⁰ has the above meanings.

The MQ silicone resins (D3) preferably have a viscosity at 25° C. of more than 1000 mPas or are solids. The weight-average molecular weight (based on a polystyrene standard) of these resins, determined using gel permeation chromatography, is preferably from 200 to 200,000 g/mol, in particular from 1000 to 20,000 g/mol. The MQ silicone resins (D3) used according to the invention are preferably at least 100 g/l soluble in benzene at a temperature of 25° C. and a pressure of 101.325 kPa.

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

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

Suitable protonating agents (S) are, 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. Es acetic acid is particularly preferred.

The protonating agent is usually added neat or in the form of an aqueous solution.

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 .

The protonating agent is preferably added in an amount such that the oil-in-water emulsions have a pH in the range 3.5 to 7.0, preferably a pH between 3.5 and 6.0 and especially preferably reach a pH between 3.5 and 5.0. In the context of the present invention, the pH is preferably measured at 20° C. using an electrode in accordance with US Pharmacopeia USP 33.

The water is deionized or saline water, preferably deionized water.

The oil-in-water emulsions of the film-forming organopolysiloxanes (A) preferably used in the process 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)).

Emulsifiers (E) which can be used are all previously known ionic and nonionic emulsifiers, both individually and as mixtures of various emulsifiers with which aqueous dispersions, in particular aqueous emulsions, of organopolysiloxanes (A) could previously be prepared.

Examples of anionic emulsifiers are:

1. Alkyl sulfates, especially 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, especially alkyl sulfonates having 8 to 18 carbon atoms, alkylaryl 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; if appropriate, these alcohols or alkylphenols can also be ethoxylated with 1 to 40 EO units.

3. Alkali metal and ammonium salts of carboxylic acids having 8 to 20 carbon atoms in the alkyl, aryl, alkaryl or aralkyl radical. 4. Phosphoric acid partial esters and their alkali metal and ammonium salts, especially alkyl and alkaryl phosphates with 8 to 20 carbon atoms in the organic radical, alkyl ether or alkaryl ether phosphates with 8 to 20 carbon atoms in the alkyl or alkaryl radical and 1 to 40 EO Units .

Examples of nonionic emulsifiers are:

5. Polyvinyl alcohol which still has 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 having 5 to 40 EO units and alkyl radicals of 8 to 20 carbon atoms.

7. Alkylarylpolyglycolether, preferably those with 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 with 8 to 40 EO or PO units.

9. Addition products of alkylamines having alkyl radicals of 8 to 22 carbon atoms with ethylene oxide or propylene oxide.

10. Fatty acids with 6 to 24 carbon atoms.

11. Alkyl polyglycosides of the general formula R*-0-Z0, in which R* is a linear or branched, saturated or unsaturated alkyl radical having an average of 8-24 carbon atoms and ZO is an oligoglycoside radical having an average of o=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 carboxyalkyl cellulose whose alkyl groups each have up to 4 carbon atoms.

13. Polar groups, containing in particular the elements 0, N, C, S, P, Si, containing linear organo (poly) siloxanes, in particular those with alkoxy groups with up to 24 carbon atoms and/or up to 40 EO and/or PO groups.

Examples of cationic emulsifiers are:

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. Quarternary alkyl and alkylbenzeneammonium salts, in particular those whose alkyl groups have 6 to 24 carbon atoms, in particular the halides, sulfates, phosphates and acetates.

16. Alkylpyridinium, alkylimidazolinium and alkyloxazolinium salts, in particular those whose alkyl chain has up to 18 carbon atoms, specifically the halides, sulfates, phosphates and acetates.

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 having a C8-C18 acyl radical and alkyl imidazolium betaines.

Preferred emulsifiers are nonionic emulsifiers, in particular the alkyl polyglycol ethers and cationic emulsifiers listed under 6. above, in particular the quaternary alkyl and alkylbenzeneammonium salts listed under 15. above. The emulsifier can consist of one of the above emulsifiers or a mixture of two or more of the above emulsifiers; it can be used in pure form or as a solution of one or more emulsifiers in water or organic solvents. 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 trialkoxy-alkyl ethers with alkyl radicals up to 7 carbon atoms.

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 glycerol.

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.

Examples of ethylene glycol ether are

ethylene glycol monomethyl ether (methyl glycol, 2-methoxyethanol, CH ₃ -O-CH ₂ CH ₂ -OH) ,

Ethylene Glycol Monoethyl Ether (Ethyl Glycol, 2-Ethoxyethanol, CH ₃ CH ₂ -O-CH ₂ CH ₂ -OH)

Ethylene glycol monopropyl ether (2-propoxyethanol, CH ₃ CH ₂ CH ₂ -O- CH ₂ CH ₂ -OH)

ethylene glycol monoisopropyl ether (2-isopropoxyethanol,

(CH3)2CH-O- _CH2CH2 -OH)

Ethylene glycol mono-n-butyl ether (2-butoxyethanol, CH ₃ CH ₂ CH ₂ CH ₂ -O-CH ₂ CH ₂ -OH

ethylene glycol monophenyl ether (2-phenoxyethanol, _C6H5 -O- _CH2CH2 - _{OH )}

Ethylene glycol monohexyl ether (2-hexyloxyethanol, C ₆ H _II -0-CH ₂ CH ₂ -0H)

Ethylene Glycol Monobenzyl Ether (2-Benzyloxyethanol, C6H5CH2-O-CH2CH2-OH)

Diethylene glycol monomethyl ether [2-(2-Methoxyethoxy)ethanol, methyl carbitol, CH ₃ -O-CH ₂ CH ₂ -O-CH ₂ CH ₂ -OH]

Diethylene glycol monoethyl ether [2-( ₂ -Ethoxyethoxy)ethanol, Carbitol Cellosolve, CH3 _CH2 -O- _{CH2 CH2} -O- _{CH2 CH2} -OH] - Diethylene glycol mono-n-butyl ether [2-(2-Butoxyethoxy)ethanol , _{CH3 CH2 CH2 CH2} -O- _{CH2 CH2} -O- _{CH2 CH2} -OH]

Triethylene glycol mono-n-butyl ether (butyl triglycol)

Diethylene glycol diethyl ether (diethylcarbitol)

Dibutylene Glycol Dibutyl Ether (Dibutylcarbitol)

Examples of propylene glycol ethers are

Propylene glycol monomethyl ether (l-Methoxy-2-propanol) Propylene glycol monoethyl ether (Ethoxypropanol) Propylene glycol mono-n-butyl ether (l-Butoxy-2-propanol) - Propylene glycol monohexyl ether (l-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 Examples of butylene glycol ether are

butylene glycol monomethyl ether (l-methoxy-2-propanol)

Butylene Glycol Monobutyl Ether (Ethoxypropanol)

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.

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.

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)).

The oil-in-water emulsions preferably used in the process are prepared by mixing the combination of polyorganosiloxane (P), silicate compound (DI), polysilicate compound (D2) or MQ resin (D2), protonating agent (S), water (W), where appropriate emulsifier (E), organic solvent (L) and where appropriate with other components. The 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, the mixing can also be carried out at higher or lower pressures.

In a preferred procedure, the polyorganosiloxane (P) and the silicate compound (DI), polysilicate compound (D2) or MQ resin (D2) are premixed. This premix is then worked into a mixture of protonating agent (S), water (W), optionally emulsifier (E), organic solvent (L) and optionally with further components and then with further water to form an oil-in-water emulsion diluted.

Production can be discontinuous or continuous.

Technologies for producing emulsions of organopolysiloxanes are known. For example, intensive mixing and dispersing can take place in rotor-stator stirring devices, colloid mills, high-pressure homogenizers, microchannels, membranes, jet nozzles and the like, or by means of ultrasound.

The oil-in-water emulsions can be diluted with water in all proportions. The emulsions can 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.

Regardless of the water content, the oil-in-water emulsions are clear to opaque liquids with a viscosity of preferably 5 to 10000 mPas, particularly preferably 5 to 1000 mPas, in particular 10 to 500 mPas (at 25°C and at a shear rate of 101/s). The treatment and impregnation of any fibers, in particular natural and synthetic textiles and functional materials, is particularly preferred.

The compositions (Z) are preferably used during the washing process in a commercial washing machine, in particular by adding them to the softener compartment. The laundry is cleaned in a washing cycle and brought into contact with the composition (Z) in the softening cycle. As a result, the textiles are impregnated with the film-forming organopolysiloxanes (A), so that in the subsequent washing process there is a reduced release of microfibers from textiles, in particular from textiles containing polyester.

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

At the same time, the use of the compositions (Z) achieves a significant improvement in the soft hand and improved dirt repellency of the treated textiles.

In the examples below, all parts and percentages are by weight unless otherwise specified.

Unless otherwise stated, the following examples are at a pressure of the surrounding atmosphere, ie at about 1000 hPa, and at room temperature, ie about 20 ° C or a Temperature that occurs when the reactants are combined at room temperature without additional heating or cooling performed.

The viscosities were measured on an "MCR 302" rheometer from Anton Paar according to DIN EN ISO 3219: 1994 and DIN 53019, using a cone-plate system (cone CP50-2) with an opening angle of 2°. The device was calibrated using standard oil from the Physikalisch-Technische Bundesanstalt with standard oil 10000. The measurement temperature is 25.00°C +/- 0.05°C, the measurement time is 3 minutes The measurement uncertainty of the dynamic viscosity is 1.5% The shear rate gradient was selected as a function of the viscosity and is shown separately for each viscosity specification.

The amine number indicates how many mmol of KOH are equivalent to one gram of the substance to be determined. The amine number is determined according to DIN 16945 version 1989-03.

Examples :

The polydimethylsiloxane (P-1) containing aminoalkyl groups 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.

The silicate compound (Dl) used in the test example is a mixture of tetraethoxysilicate of general formula VI and a polysilicate compound having 2 units of general formula VII and 1 to 7 units of general formula VIII, where R ¹⁰ is an ethyl radical with a SiC ^ content of 40 wt .-%.

The MQ silicone resin (D-2) used in the test example is a silicone resin that 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).

Making the different formulations:

Example 1 Oil-in-water emulsion of a film-forming organopolysiloxane El

17.0 g of a mixture of 13.6 g aminoalkyl polydimethylsiloxane (P-1) and 3.4 g MQ silicone resin (D-2) are added with stirring at room temperature to 7.0 g demineralized water, 7.0 g 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% strength aqueous solution available from Brenntag) are then added 65.97 g demineralized water stirred in. A clear, colorless emulsion (E_1) is obtained. Emulsion E_1 contains 17% by weight of the film-forming organopolysiloxane Al.

Example 2 Oil-in-water emulsion of a film-forming organopolysiloxane E2

7.0 g demineralized water, 12.0 g n-butyl glycol (available under the trade name ethylene glycol butyl ether from Sigma-Aldrich) and 0.4 g acetic acid (80% aqueous solution available from Brenntag ) are at room temperature presented and mixed. 17.0 g of a mixture of 16.1 g of polydimethylsiloxane (PI) containing aminoalkyl groups and 0.9 g of silicate compound (DI) and 63.6 g of demineralized water are stirred in successively. A translucent, colorless emulsion (E2) is obtained.

Emulsion E2 contains 17% by weight of the film-forming organopolysiloxane A2.

Example 3: Oil-in-water emulsion (not according to the invention) of a linear organopolysiloxane VE3:

7.0 g demineralized water, 4.0 g isotridecyl octaethoxylate, commercially available under the trade name Lutensol TO 8 (BASF), 2.0 g isotridecyl pentaethoxylate, commercially available under the trade name Lutensol TO 5 (BASF) and 0 4 g of acetic acid (80% strength aqueous solution available from Brenntag) are introduced at room temperature and mixed. 34.0 g of the aminoalkyl-containing polydimethylsiloxane (P-I) and 52.6 g of demineralized water are stirred in gradually. A translucent, whitish emulsion (VE3) is obtained.

Emulsion VE3 does not contain any film-forming organopolysiloxane.

Example 4:

Compositions Zl_, Z2 (according to the invention) containing

(A) film-forming organopolysiloxanes,

(B) cationic surfactants and

(C) Water and compositions VZ3 and VZ (not according to the invention). Table 1: Aqueous formulations ZI, Z2, VZ3, VZ4

*) according to the invention

**) not according to the invention

* * *) Bl: N,N-bis[ethyl(tallowate)]-N-(2-hydroxyethyl)-N-methylammonium methyl sulfate (90% solution in isopropanol), commercially available under the trade name Stepantex® VK90 ( Stepan)

The formulations (both according to the invention and those not according to the invention) are produced by heating the water to 50.degree. The cationic surfactant previously melted at 50° C. and stirred intensively is added at this temperature with intensive stirring. Stirring is continued until a homogeneous mixture results. The mixture is cooled to 30° C. and the oil-in-water emulsion E_1, E2 or VE3 and other ingredients are added. At VZ4, only the cationic surfactant and other ingredients are formulated. Example 5:

For the following experiments, 50 ml of the compositions ZI, Z2, VZ3 and VZ4 are diluted with demineralized water to 2000 ml of the use concentration.

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

The fabric is pretreated by being prewashed in a washing machine (Miele Softtronic W 1935) at 40° C., main wash program without a detergent. It is then punched out into circles with a diameter of 113 mm. The edges are melted off with a flame to prevent fraying.

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

In order to simulate a wash cycle, the tests are carried out in a Linitest device (from Hanau). To do this, 200 ml of a washing liquid (4 g of Ariel liquid detergent are dissolved in one liter of water), 20 steel balls and a pretreated polyester fabric are placed in a metal beaker and treated for 90 minutes at 60° C. in the Linitester device.

The washing liquid is filtered off through a Büchner filter with a round paper filter (from VWR, 55 mm in 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.

The filter paper is photographed and the number of microfibers filtered off is evaluated electronically (Image editing software ImageJ); Output as area occupied by the microfibers on the filter paper.

The result is the average of twelve individual measurements.

Table 2: Microfibers released

*) according to the invention

**) not according to the invention Table 2 clearly shows that when compositions Z1_ and Z2 are used, the release of microfibers from the polyester fabric is reduced compared to the blank value BL (no finish) or VZ4 (finish with only the cationic surfactant). When using the formulation VZ3, which contains no film-forming polysiloxane, significantly more microfibers are released compared to the blank value BL and when using the compositions ZI and Z2.

Claims

patent claims 1. Method for reducing the release of microfibers during the washing process of textiles which are pretreated with composition (Z) before the washing process (A) at least 0.1 parts 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 water. 2. The method according to claim 1, in which the film-forming organopolysiloxanes (A) are used in the form of their aqueous emulsions. 3. The method according to any one of the preceding claims, wherein the composition (Z) contains an oil-in-water emulsion film-forming dender organopolysiloxanes (A), which (i) 100 parts by weight of polyorganosiloxane (P) which is liquid at 20° C. and has aminoalkyl groups and contains at least 80 mol % of units selected from units of the general formulas Ia, Ib, Ha and IIb R ¹ ₂ SiO( ₂ /2 ₎ (Ia), R1a R2 SiO( ³ - _a )/ ² (Ib), R ³ ₃ SiO _(i/2) (H a), R ³ ₂ R ⁴ SiO _(i/2) (Hb), contains, in which a means the value 0 or 1, R ¹ means unsubstituted alkyl radicals with 1-40 carbon atoms, R ² is an aminoalkyl radical of the general formula III - R ⁵ -NR ⁶ R ⁷ (III), where R ⁵ divalent hydrocarbon radical with 1-40 carbon atoms, R ⁶ is a monovalent hydrocarbon radical having 1-40 carbon atoms, hydrogen or an alkanoyl radical and R ⁷ is a radical of the general formula IV - (R ⁸ -NR ⁶ ) _X R ⁶ (IV), where x is an integer from 0 to 40 and R ⁸ is 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 is hydrogen or a hydrocarbon radical with 1-40 carbon atoms, R ³ are unsubstituted alkyl radicals with 1-40 carbon atoms, R ⁴ are radicals -OR or -OH and, R are unsubstituted alkyl radicals with 1-40 carbon atoms, where 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 Ila and IIb is 0.5 to 500 and the polyorganosiloxane (P) has an average amine number of at least 0.1 mequiv/ has 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 (DI), the tetraalkoxy silicate of the general formula VI ^R10O4Si ( _VI ), Polysilicate compound (D2) containing at least 80 mol % of units of the general formulas VII and VIII and at least 2 units of the general formula VII _{R10O3Sii /2} ⁽ VII), R ¹⁰ O ₂ Si _2/2 (VIII), wherein R ¹⁰ are unsubstituted hydrocarbon radicals with 1-18 carbon atoms, MQ silicone resin (D3) containing at least 80 mol% units of general formula IX and X R ¹¹ ₃ SiOi _/2 (IX), Si0 _{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 and at most 10% by weight of the radicals R ¹¹ are -OR and -OH, and Mixtures of any proportions (Dl), (D2) and (D3) contains. 4. The method according to claim 3, wherein the radicals R ¹ and R ³ are methyl radicals. 5. The method according to claim 3 or 4, wherein the radical R is a methyl radical. 6. The method according to claim 3, 4 or 5, wherein the Polysili catverbindungen (D2) contains at least 90 mol% units of the general formulas VII and VIII my and the remaining units a units of the general formulas XI and XII R ¹⁰ OSiO ₃ /2 (XI), S1O4/2 (XII), where R ¹⁰ is as defined in claim 10. 7. The process as claimed in claim 3, 4 or 5, in which the MQ silicone resins (D3) have a viscosity greater than 1000 mPas at 25° C. (measured at 25° C. and at a shear rate of 101/s) or are solids. 8. The method according to any one of the preceding claims, wherein the cationic surfactants (B) are selected from the group of (Bl) quaternary alkyl, alkenyl, hydroxyalkyl and alkylbenzene ammonium salts, (B2) alkyl pyridinium, alkyl imidazolinium and alkyl oxazolinium salts and (B3) ester/amido containing quaternary ammonium salts. 9. The method according to any one of claims 2 to 8, wherein the oil-in-water emulsions of the film-forming organopolysiloxanes (A) contain organic solvents or solvent mixtures (L) selected from monoalcohols or polyalcohols, aprotic ethers or mono, di- or Trialkoxy-alkyl ethers with alkyl radicals up to 7 carbon atoms.