WO2025144523A1 - The use of aminosiloxane ester copolymers for the treatment of textiles - Google Patents

Abstract

A process for treating a textile to impart hydrophilicity includes applying an aminosiloxane ester copolymer emulsion to the textile and drying the textile. The aminosiloxane ester copolymer emulsion includes a surfactant and water in addition to the aminosiloxane ester copolymer.

Description

THE USE OF AMINOSILOXANE ESTER COPOLYMERS FOR THE TREATMENT OF TEXTILES

CROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of India Provisional Patent Application Serial No. 202341088676 filed on 26 December 2023. India Provisional Patent Application Serial No. 202341088676 is hereby incorporated by reference.

FIELD

[0002] A textile treatment emulsion includes an aminosiloxane ester copolymer. More particularly, the textile treatment emulsion can be used on fibers and fabrics to increase hydrophilicity.

INTRODUCTION

[0003] Silicones have been used for textile treatments. Various amino-functional silicones have been developed and sold commercially under various tradenames. Common problems associated with amino-functional silicones as textile treatments are their yellowing of textiles from oxidation of the amine groups and extensive hydrophobic nature of the polydimethylsiloxane chains. One approach to render amino-functional silicone polymers hydrophilic has been adding hydrophilic functionalities to the polymers, while altering or reducing the amine content to reduce yellowing.

[0004] For example, US Patent 10954342 discloses, “hydrophilic amino-organopolysiloxane softener compositions are prepared . . . The process for preparing the amino-organopolysiloxane comprises: (i) reacting in a first step a hydrogen siloxane . . . with an olefinic unsaturated epoxy compound . . . and optionally an olefinic unsaturated polyether . . . in the presence of a catalyst comprising platinum or its compounds or complexes to form an epoxy functional siloxane . . . (ii) reacting in a second step the resulting epoxy functional siloxane obtained from the first step with a polyetheramine”. Typically in platinum catalyzed hydrosilylation reactions, one reactant is used in excess. Therefore, the above referenced amino-organopolysiloxane will suffer from the drawback that if the hydrogen siloxane is used in excess, residual silyl hydride (SiH) creates shipping and other hazards, and if the olefinic unsaturated epoxy compound, such as allyl glycidyl ether, is used in excess, this can result in a toxin or skin irritant being present in the resulting textile treatment.

[0005] US Patent 1075864 discloses a siloxane polymer. In Example 2, “[a]n amino/methacryloyloxy Michael Adduct functionalized polydimethylsiloxane is produced as follows: A methacryloyloxypropyl terminated polydimethylsiloxane . . . is combined with 1,4- diaminobutane . . . and 2-ethyl-l -hexanol . . . The mixture is heated with stirring for 88 hours at 160° C. to yield a viscous liquid.” This patent suffers from the drawback that unreacted free diamine may be present in a formulation containing the siloxane polymer. Diamine compounds, such as the 1,4-diaminobutane in Example 2, can cause damage to eyes and skin, and these diamine compounds are also known to have undesirable odor. Furthermore, the reaction described in Example 2 is reversible. Therefore, it is thought that one skilled in the art would not wish to treat textiles (such as clothing) with a composition as described in US Patent 1075864 due to potential for heat (such as heat from a clothes dryer) causing reverse reaction generating amine compounds with the undesirable odor and toxicity.

[0006] US Patent 8013097 discloses, “a process to prepare an amine terminal silicone polyether block copolymer comprising: I) reacting; A) a polyoxyalkylene having an unsaturated hydrocarbon group at each molecular terminal B) a SiH terminated organopolysiloxane, C) a hydrosilylation catalyst, D) an optional solvent, . . . II) further reacting the product of step I with; E) an epoxide having at least one aliphatic unsaturated hydrocarbon group to form an epoxide terminal silicone polyether block copolymer, III) reacting the epoxide terminal silicone polyether block copolymer with F) an amine compound to form the amine terminal silicone polyether block copolymer.” In this process a large excess of the amine compound was used to make the copolymer, and the amine compound is known to have an undesirable odor at low threshold, e.g., 2 ppm.

SUMMARY

[0007] A process for treating a textile comprises: i) applying an emulsion comprising an aminosiloxane ester copolymer to the textile, and ii) drying the textile. The process improves hydrophilicity of the textile.

DETAILED DESCRIPTION

[0008] The emulsion useful in the process for treating the textile, introduced above, comprises (A) the aminosiloxane ester copolymer, (B) a surfactant, and (C) water. The starting materials for preparing the emulsion are described in detail, below.

(A) Copolymer

[0009] Starting material (A) in the emulsion is an aminosiloxane ester copolymer. The aminosiloxane ester copolymer comprises formula (Al):

where each R¹ is an independently selected monovalent hydrocarbon group of 1 to 12 carbon atoms, each R^E is independently selected from the group consisting of hydroxyl and an aminofunctional group of formula H2N-R^A-, each R^A is an independently divalent hydrocarbon group of 1 to 12 carbon atoms, each R² is independently selected from the group consisting of hydrogen and methyl, each R^D is an independently selected divalent hydrocarbon group of 2 to 20 carbon atoms, each subscript a independently has a value such that 0 < a < 150; and subscript has a value such that 1 < b < 100.

[0010] Suitable monovalent hydrocarbon groups for R¹ include alkyl, alkenyl, aryl, and combinations thereof (e.g., aralkyl and aralkenyl). For example, suitable alkyl groups include methyl, ethyl, propyl (including iso-propyl and n-propyl), butyl (including iso-butyl, n-butyl, sec-butyl, and tert-butyl), pentyl (including linear pentyl and/or cyclopentyl) and branched alkyl groups with 5 carbon atoms, hexyl (including linear hexyl and/or cyclohexyl) and branched alkyl groups with 6 carbon atoms), octyl (including linear octyl and/or cyclooctyl), branched alkyl groups with 8 carbon atoms), decyl (including linear decyl and/or cyclodecyl) and branched alkyl groups with 10 carbon atoms, and dodecyl (including linear dodecyl and/or cyclododecyl) and branched alkyl groups with 12 carbon atoms. Alternatively, the alkyl group for R¹ may be selected from the group consisting of methyl and ethyl, alternatively methyl. Suitable alkenyl groups for R¹ include vinyl, allyl and hexenyl; alternatively vinyl or allyl; and alternatively vinyl. Suitable aryl groups for R¹ may include cyclopentadienyl, phenyl, naphthyl, and anthracenyl. Suitable aralkyl groups for R¹ include tolyl, xylyl, benzyl, 1 -phenylethyl, and 2- phenylethyl. Alternatively, the aryl group for R¹ may be phenyl. Aralkyl groups such as benzyl, 1 -phenylethyl, and 2-phenylethyl, and aralkenyl groups such as styryl, may also be used for R¹. Alternatively, each R¹ may be selected from the group consisting of methyl and phenyl. Alternatively, each R¹ may be methyl.

[0011] Each R^E is independently selected from the group consisting of a hydroxyl group and an amino-functional group of formula H N-R^A-, where R^A is a divalent hydrocarbon group. Alternatively, each R^E may be hydroxyl. Alternatively, each R^E may be the amino-functional group of formula H2N-R^A-. Each R^A is an independently selected divalent hydrocarbon group of 1 to 12 carbon atoms, alternatively 2 to 12 carbon atoms, alternatively 2 to 5 carbon atoms, and alternatively 2 to 3 carbon atoms. The divalent hydrocarbon groups for R^A may be linear, branched, or cyclic, or combinations thereof. Suitable divalent hydrocarbon groups for R^A include alkylene groups, arylene groups, and combinations thereof (e.g., dialkylarylene groups). The alkylene group is exemplified by ethylene, propylene, or butylene. The arylene group for R^A may be arylene group such as phenylene. Alternatively, R^A may be a dialkylarylene group such as:

is independently 1 to 6, alternatively 1 to 2. Alternatively, each R^A may be an alkylene group such as ethylene, propylene, or butylene; alternatively ethylene.

[0012] Each R² is independently selected from the group consisting of hydrogen and methyl. Alternatively, each R² may be hydrogen.

[0013] Each R^D is an independently selected divalent hydrocarbon group of 2 to 20 carbon atoms, alternatively 2 to 12 carbon atoms, alternatively 3 to 12 carbon atoms, alternatively 4 to 12 carbon atoms, alternatively 4 to 10 carbon atoms, alternatively 4 to 6 carbon atoms, alternatively 6 to 12 carbon atoms, and alternatively 6 to 10 carbon atoms. The divalent hydrocarbon groups for R^D may be linear, branched, cyclic, or combinations thereof. Suitable divalent hydrocarbon groups for R^D include alkylene groups, arylene groups, and combinations thereof. Alternatively, each R^D may be an alkylene group such as propylene, butylene, hexylene, octylene, decylene, or dodecylene; alternatively each R^D may be butylene, hexylene, or decylene. Alternatively, R^D may be a branched alkylene group. The arylene group for R^D may be arylene group such as phenylene. Alternatively, R^D may be a dialkylarylene group such

is independently 1 to 6, alternatively 1 to 2.

[0014] Subscript a has a value such that 0 < a < 150. Alternatively, subscript a may have a value of 2 to 150, alternatively 14 to 145, alternatively 14 to 143, alternatively 42 to 145, alternatively 42 to 143, alternatively 82 to 145, alternatively 82 to 143, and alternatively 42 to 84.

[0015] Subscript b has a value such that 1 < b < 100. Alternatively, subscript b may have a value of 2 to 100, alternatively 2 to 20, alternatively 2 to 10, and alternatively 3 to 4.

[0016] The copolymer described above may have a number average molecular weight (Mn) of > 1 ,000 g/mole to 250,000 g/mole measured by GPC according to the test method described hereinbelow. Alternatively, the copolymer may have a Mn of 4,000 g/mole to 250,000 g/mole, alternatively 4,000 g/mole to 100,000 g/mole, measured by GPC.

[0017] Alternatively, the copolymer described above may have a weight average molecular weight (Mw) of 2,000 g/mol to 400,000 g/mol. Alternatively, Mw may be 10,000 g/mol to 390,000 g/mol; alternatively 12,000 g/mol to 200,000 g/mol; alternatively 15,000 g/mol to 185,000 g/mol; alternatively 19,000 g/mol to 175,000 g/mol; alternatively 20,000 g/mol to 100,000 g/mol; alternatively 21,000 g/mol to 80,000 g/mol; alternatively 22,000 g/mol to 75,000 g/mol; alternatively 25,000 g/mol to 65,000 g/mol; alternatively 30,000 g/mol to 60,000 g/mol; alternatively 35,000 g/mol to 55,000 g/mol; and alternatively 40,000 g/mol to 50,000 g/mol.

The copolymer may be prepared by known methods, and the copolymer may be delivered in an emulsion. The copolymer and the emulsion may be prepared as described in PCT Patent Application Publication WO2023/278918.

[0018] The copolymer described above has both amino- and acrylate- groups in its backbone. The copolymer may have a molar ratio of amino/acrylate groups in its backbone of > 1/1, alternatively at least 1.05/1, alternatively at least 1.1/1, and alternatively at least 1.15/1; while at the same time the molar ratio may be up to 2/1, alternatively up to 1.5/1, and alternatively up to 1.3/1. The copolymer may have a molar ratio of amino/acrylate groups in its backbone of 1/1 to 2/1, alternatively 1.05/1 to 2/1, alternatively 1.1/1 to 2/1, alternatively 1.1/1 to 1.5/1, and alternatively 1.15/1 to 1.3/1.

[0019] The emulsion may comprise: (I) a liquid continuous phase comprising water, and (II) a discontinuous phase dispersed in the liquid continuous phase, where the discontinuous phase comprises the aminosiloxane ester copolymer described above. The amount of copolymer added to the emulsion can vary and is not limited. However, the amount typically may range from a weight ratio of copolymer/emulsion of 1 to 70%, alternatively 2 to 60%. Water, surfactant (and additional starting materials, if present) may constitute the balance of the emulsion to 100%.

Water

[0020] The water is not generally limited, and may be utilized neat (i.e., absent any carrier vehicles/solvents), and/or pure (i.e., free from or substantially free from minerals and/or other impurities). For example, the water may be processed or unprocessed prior to making the emulsion described herein. Examples of processes that may be used for purifying the water include distilling, filtering, deionizing, and combinations of two or more thereof, such that the water may be deionized, distilled, and/or filtered. Alternatively, the water may be unprocessed (e.g. may be tap water, i.e., provided by a municipal water system or well water, used without further purification). Alternatively, the water may be purified before use to make the emulsion. The water is used in addition to the aminosiloxane ester copolymer and the surfactant (and additional starting materials, if any) to a balance of 100 % of the emulsion.

Surfactant

[0021] The emulsion comprising (A) the aminosiloxane ester copolymer further comprises (B) a surfactant. The surfactant may be anionic, cationic, nonionic, or amphoteric, or a combination of two or more thereof. The amount of surfactant may be 2 % to 25%, alternatively 2% to 20%, based on combined weights of all starting materials in the emulsion.

[0022] The anionic surfactant may selected from alkali metal sulfosuccinates, sulfonated glyceryl esters of fatty acids, salts of sulfonated monovalent alcohol esters, amides of amino sulfonic acids, sulfonated products of fatty acids nitriles, sulfonated aromatic hydrocarbons, condensation products of naphthalene sulfonic acids with formaldehyde, sodium octahydroanthracene sulfonate, sodium lauryl sulfate, alkali metal alkyl sulfates, alkyl ether sulfates having at least 8 carbon atoms, alkyl aryl ether sulfates, alkylarylsulfonates having at least 8 carbon atoms, alkylbenzenesulfonic acids, salts of alkylbenzenesulfonic acids, sulfuric esters of polyoxyethylene alkyl ether, amine salts or sodium salts or potassium salts of alkylnaphthylsulfonic acid, and combinations thereof. Suitable anionic surfactants are commercially available from various sources including sodium lauryl sulfate, which is available from Pilot under the tradename CALIMULSE™ SLS. Other anionic surfactants commercially available from The Dow Chemical Company, include alkyldiphenyloxide disulfonate salts, which are available under the tradename DOWFAX™; dioctyl sulfosuccinates, which are available under the tradename TRITON™ GR; phosphate esters, which are available under the tradename TRITON™ H-55, H-65, QS-44, OR XQS-20; sulfates and sulfonates, which are available under the tradename TRITON™ QS-15 and TRITON™ XN-45S.

[0023] The cationic surfactant may be selected from dodecylamine acetate, octadecylamine acetate, acetates of the amines of tallow fatty acids, homologues of aromatic amines having fatty acids, fatty amides derived from aliphatic diamines, fatty amides derived from aliphatic diamines, fatty amides derived from disubstituted amines, derivatives of ethylene diamine, quaternary ammonium compounds, salts of quaternary ammonium compounds, alkyl trimethylammonium hydroxides, dialkyldimethylammonium hydroxides, coconut oil, methylpolyoxyethylene cocoammonium chloride, dipalmitoylethyl hydroxyethylammonium methosulfate, amide derivatives of amino alcohols, amine salts of long chain fatty acids, and combinations thereof. Cationic surfactants are commercially available from various sources including dialkylmethyl quaternary ammonium compounds (e.g., cetrimonium chloride) under the tradename ARQUAD™ from Akzo Nobel; ADOGEN™ cationic surfactants from Evonik; TOMAH™ cationic surfactants from Tomah Products, Inc. of Milton, Wisconsin, USA; and VARIQUAT™ cationic surfactants from Sea-Land Chemical Company of Westlake, Ohio, USA.

[0024] The nonionic surfactant may be selected from alkylphenol alkoxylates, ethoxylated and propoxylated fatty alcohols, alkyl polyglucosides and hydroxyalkyl polyglucosides, sorbitan derivatives, N- alkylglucamides, alkylene oxide block copolymers, such as block copolymers of ethylene oxide, propylene oxide and/or butylene oxide, fatty alcohol polyglycolethers, polyhydroxy and polyalkoxy fatty acid derivatives, amine oxides, silicone polyethers, various polymeric surfactants. Nonionic surfactants are commercially available, for example, alkylphenol alkoxylates are available under the tradename ECOSURF™ EH; secondary alcohol ethoxylates, nonylphenol ethoxylates, and ethylene oxide/propylene oxide copolymers are commercially available under the tradename TERGITOL™; and specialty alkoxylates such as amine ethoxylates and octylphenol ethoxylates are available under the tradename TRITON ™, all from The Dow Chemical Company. Alternatively, the nonionic surfactant may be, e.g., trideceth-6 or trideceth-12, which are available under the tradename SYNPERONIC™, such as SYNPERONIC™ 13/12, from Croda or LUTENSOL™, such as LUTENSOL™ TO 6, from BASF. Alternatively, the nonionic surfactant may be e.g., a fatty alcohol polyglycol ether such as GENAPOL™ UD 050, and GENAPOL™ UDI 10, which are commercially available from Clariant of Frankfurt, Germany.

[0025] The nonionic surfactant may be organic. Alternatively, the organic, nonionic surfactant may have a relatively high hydrophobic - lipophobic balance (HLB) value. For example, organic, nonionic surfactants include those which are commercially available such as (i) 2,6,8-trimethyl-4-nonyloxy polyethylene oxyethanols (6EO) and (10EO) sold under the names TERGITOL™ TMN-6 and TERGITOL™ TMN-10; (ii) the Cn-is secondary alkyl polyoxyethylene ethers (e.g., Cn -is secondary alcohol ethoxylates 7EO, 9EO, and 15EO sold under the names TERGITOL™ 15-S-7, TERGITOL™ 15-S-9, and TERGITOL™ 15-S-15, which has HL value 15.4), other Cn-is secondary alcohol ethoxylates sold under the tradenames ECOSURF™ EH-40 and TERGITOL™ 15-S-12, TERGITOL™ 15-S-30, and TERGITOL™ 15-S-40, by the Dow Chemical Company, of Midland, Michigan, USA; octylphenyl polyoxyethylene (40) ether sold under the name TRITON™ X405 by the Dow Chemical Company; (iii) nonylphenyl polyoxyethylene (10) ether sold under the name MAKON™ 10 by the Stepan Company; (iv) ethoxylated alcohols sold under the name Trycol 5953 by Henkel Corp./Emery Group, of Cincinnati, Ohio, USA; (v) ethoxylated alcohols sold under the name BRIJ™ L23 (with HLB value of 16.9) and BRIJ™ L4 (with HLB value of 9.7) by Croda Inc. of Edison, New Jersey, USA, (vi) polyoxyethylene 23 lauryl ether (Laureth-23) sold commercially under the trademark BRIJ™ 23; and RENEX™ 30, a polyoxyethylene ether alcohol; (vii) alkyl- oxo alcohol polyglycol ethers such as GENAPOL™ UD 050 (with HLB value of 11.4), and GENAPOL™ UDI 10 (with HLB value of 14.4), (viii) alkyl polyethylene glycol ether based on ClO-Guerbet alcohol and ethylene oxide such as LUTENSOL™ XP 79, and (ix) alkyl polyglycosides, such as those sold under the trade name Glucopon™ by BASF, and alkyl glucosides such as decyl glucoside, lauryl glucoside, and coco-glucoside, which are sold under the trade name EcoSense™ by The Dow Chemical Company of Midland, Michigan, USA.

Other commercially available nonionic surfactants include TERGITOL™ 15-S-5, also from The Dow Chemical Company, which has an HLB value of 10.5; Lutensol XP 50 with an HLB value of 10, Lutensol XP 79 (an alcohol ethoxylate), Lutensol XP 100 (an alcohol ethoxylate), and Lutensol XP 140 with an HLB value of 16, each of which is available from BASF. The amount of surfactant in the emulsion may be, for example, 0.03% to 25%, alternatively 0.03% to 4% based on combined weights of all the starting materials in the emulsion described herein.

[0026] Alternatively, the nonionic surfactant may comprise, or may be, a silicone polyether (SPE). The silicone polyether as an emulsifier may have a rake type structure wherein the polyoxyethylene or polyoxyethylene-polyoxypropylene copolymeric units are grafted onto the siloxane backbone, or the SPE can have an ABA block copolymeric structure wherein A represents the polyether portion and B the siloxane portion of an ABA structure. Suitable silicone polyethers include DOWSIL™ OFX-5329 Fluid from The Dow Chemical Company. Alternatively, the nonionic surfactant may be selected from polyoxyalkylene-substituted silicones, silicone alkanolamides, silicone esters and silicone glycosides. Such silicone-based surfactants are known in the art, and have been described, for example, in US Patent 4122029 to Gee et al., US Patent 5387417 to Rentsch, and US Patent 5811487 to Schulz et al.

[0027] Alternatively, the surfactant may comprise an amphoteric surfactant. Suitable amphoteric surfactants include betaines such as alkyl(C12-14)betaine, cocoamidopropylbetaine, cocoamidopropyldimethyl-hydroxysulphobetaine, dodecylbetaine, hexadecylbetaine, and tetradecylbetaine; sultaines such as cocamidopropylhydroxysultaine; lecithin; hydrogenated lecithin; cocoamphodiacetates; cocoiminodipropionate; and dodecyliminodipropionate.

[0028] Alternatively, the surfactant in the emulsion may be a nonionic surfactant. Alternatively, the surfactant may be an organic surfactant. Alternatively, the surfactant may be both organic and nonionic.

[0029] The emulsion may be formed as a water-in-oil emulsion (w/o), which contains a water- in-oil surfactant, (which may subsequently be inverted by addition of more water). The water- in-oil surfactant may be nonionic and may be selected from polyoxyalkylene-substituted silicones, silicone alkanolamides, silicone esters and silicone glycosides, as described above. Alternatively, when the emulsion is an oil-in-water (o/w) emulsion, it may include nonionic surfactants known in the art to prepare o/w emulsions. Suitable nonionic surfactants for this embodiment are exemplified by the polyoxyethylene alkyl ethers, polyoxyethylene alkylphenol ethers, polyoxyethylene lauryl ethers, polyoxyethylene sorbitan monooleates, polyoxyethylene alkyl esters, polyoxyethylene sorbitan alkyl esters, polyethylene glycol, polypropylene glycol, diethylene glycol, ethoxylated trimethylnonanols, and polyoxyalkylene glycol modified polysiloxane surfactants, as described above.

Additional Starting Materials

[0030] The emulsion described above may further comprise an additional starting material selected from the group consisting of an amino-functional polydiorganosiloxane, a co-solvent, an acid compound, an acid anhydride, a thickener, a stabilizer, a preservative, a brightener, a perfume, a perfume delivery system, a pH adjuster (other than the acid compound described above), a solvent (other than the co-solvents described above), a dispersant, a catalytic material, a fabric softener, a processing aid, and a combination of two or more thereof. Suitable additional starting materials are known in the art and are described, for example, as additional ingredients in US Patent 10752864 beginning at col. 7, line 20 and in PCT Patent Publication WO2023278918.

Amino-Functional Polydiorganosiloxane

[0031] The amino-functional polydiorganosiloxane produced as described herein may comprise unit formula: (R⁴3SiOi/2)a(R⁴2SiO2/2)h(R⁸R⁴SiO2/2)c(R⁸R⁴2SiOi/2)d, where each R⁴ is independently selected from a monovalent hydrocarbon group and a monovalent halogenated hydrocarbon group; each R⁸ is independently selected from an endblocking group and an amino-functional group, with the proviso that at least one R⁸ per molecule is the aminofunctional group; and subscripts a, b, c, and d represent average numbers of each unit in the unit formula.

[0032] The monovalent hydrocarbon group for R⁴ may be as described above for R¹, e.g., alkyl, alkenyl, aryl, and combinations thereof (such as aralkyl and aralkenyl). For purposes of this application, “halogenated hydrocarbon group” means a hydrocarbon where one or more hydrogen atoms bonded to a carbon atom have been formally replaced with a halogen atom. Monovalent halogenated hydrocarbon groups include haloalkyl groups, halogenated aryl groups, and haloalkenyl groups. Haloalkyl groups include fluorinated alkyl groups such as trifluoromethyl (CF3), fluoromethyl, trifluoroethyl, 2-fluoropropyl, 3, 3, 3 -trifluoropropyl, 4,4,4- trifluorobutyl, 4,4,4,3,3-pentafluorobutyl, 5,5,5,4,4,3,3-heptafluoropentyl, 6, 6, 6, 5, 5, 4, 4,3,3- nonafluorohexyl, 8,8,8,7,7-pentafluorooctyl, 2,2-difluorocyclopropyl, 2,3-difluorocyclobutyl, 3,4-difluorocyclohexyl, and 3,4-difluoro-5-methylcycloheptyl; and chlorinated alkyl groups such as chloromethyl, 3-chloropropyl 2,2-dichlorocyclopropyl, 2,3-dichlorocyclopentyl. Haloalkenyl groups include chloroallyl. Alternatively, each R⁴ may be selected from alkyl and aryl. Alternatively, each R⁴ may be selected from methyl and phenyl. Alternatively, at least 80% of all R⁴ groups are methyl. Alternatively, each R⁴ is methyl.

[0033] The subscripts a, b, c, and d have values such that: 2 > a > 0, 4000 > b > 0, 4000 > c > 0, and 2 > d > 0, with the provisos that a quantity {a + d) = 2, a quantity (c + d~) > 2, and a quantity ^ < (a + b + c + d) < 8000. Alternatively, ^ < (a + b + c + d) < 4000. Alternatively, 10 < (a + b + c + d) < 100. Alternatively, 1000 > b > 0. Alternatively, 1000 > c > 0.

[0034] The amino-functional group for R⁸ has formula:

subscript q is 0 to 4; R is hydrogen, an alkyl group, or a hydroxy alkyl group having 1 to 4 carbon atoms; and A and A’ are each independently a linear or branched alkylene group having 1 to 6 carbon atoms and optionally containing an ether linkage. In this formula, R³ and R^s are each independently a group -OR’ or an optionally substituted alkyl or aryl group. Alternatively, the group R⁵ may be an alkyl group such as methyl and the group R³ may have the formula -OR’, such as methoxy or ethoxy, where R’ is an alkyl or alkoxyalkyl group having 1 to 6 carbon atoms, for example, methyl, ethyl, butyl or methoxyethyl. Alternatively, 80% to 100% of all groups R⁸ are amino-functional groups of the formula shown above. Without wishing to be bound by theory, when an endblocker is not used for preparing the amino-functional polydiorganosiloxane, all or substantially all of groups R⁸ are amino-functional groups of the formula shown above. Alternatively, one or more of groups R⁸ may have a formula derived from the endblocker, when it is used. For example, when a monoalkoxysilane is used as endblocker during preparation of the amino-functional polydiorganosloxane, some of groups R⁸ may have formula R⁹sSiO-, where each R⁹ is independently a monovalent organic group unreactive with silanol functionality. And, when a silazane is used as endblocker, some of R⁸ may have formula R¹⁰Rⁿ2SiO-, where each R¹⁰ is independently selected from the group consisting of a monovalent hydrocarbon group and a monovalent halogenated hydrocarbon group, each R¹¹ is an independently selected monovalent hydrocarbon group of 1 to 6 carbon atoms, where monovalent hydrocarbon groups and monovalent halogenated hydrocarbon groups are as described above for R⁴.

[0035] Alternatively, in the formula for the amino-functional group above, R may be hydrogen; q may be 0 or 1; and A and A’ (if present) each contain 2 to 4 carbon atoms. Examples of suitable amino-functional groups for R⁸ above include -CXCHs Si- CHz NFE, - O(CH3)2Si-(CH₂)4NH2, -O(CH₃)2Si-(CH₂)3NH(CH2)2NH2, -O(CH₃)2Si- CH₂CH(CH3)CH2NH(CH₂)2NH2, -O(CH₃)2Si-(CH2)3NHCH2CH₂NH(CH2)₂NH2, -O(CH₃)₂Si- CH₂CH(CH3)CH₂NH(CH2)₃NH2, -O(CH₃)2Si-(CH₂)3NH(CH2)4NH2, and -O(CH₃)₂Si- (CH₂)3O(CH₂)₂NH2.

[0036] Suitable amino-functional polydiorganosiloxanes are known in the art and may be prepared by known methods, such as those described, for example, in US Patents 7238768, 11028229, and 11028233. Suitable amino-functional polydiorganosiloxanes are known in the art and are commercially available. For example, XIAMETER™ OFX-8040 Fluid, DOWSIL™ AP-8041 Fluid, XIAMETER™ OFX-8630 Fluid, and XIAMETER™ OFX-8822 Fluid are all commercially available from The Dow Chemical Company of Midland, Michigan, USA. The amount of amino- functional polydiorganosiloxane that may be added to the emulsion described herein depends on various factors including the amount of aminosiloxane ester copolymer in the emulsion, however the amount of the amino- functional polydiorganosiloxane may be 0 to 50% based on weight of (A) the aminosiloxane ester copolymer, alternatively > 0, alternatively at least 1%, alternatively at least 5%, while at the same time, the amount may be up to 50%, alternatively up to 40%, alternatively up to 30%, alternatively up to 20%, alternatively up to 10%, on the same basis.

Co-Solvent

[0037] The co-solvent is optional, and may be present, for example, when the aminosiloxane ester copolymer is prepared in the co-solvent. The co-solvent may be a hydrophilic glycol ether, a monohydric alcohol, or a combination thereof. Examples of suitable glycol ethers include Butyl CARBITOL™ glycol ether and Butyl CELLOSOLVE™ Solvent, which are commercially available from Dow. Examples of suitable monohydric alcohols include ethanol and isopropanol. The amount of co-solvent in the emulsion depends on various factors including the content of aminosiloxane ester copolymer in the emulsion, however, the amount of co-solvent may be 0 to 10%, alternatively > 0, alternatively at least 1%, based on combined weights of all starting materials in the emulsion; while at the same time the amount of co-solvent may be up to 10%, alternatively up to 8%, and alternatively up to 5%, on the same basis.

Acid Compound

[0038] The acid compound may optionally be added to the emulsion for adjusting pH. Suitable acids include acetic acid, formic acid, propionic acid, and combinations thereof. Suitable acids for adjusting pH are disclosed, for example, in US Patent 6180117.

[0039] When selecting starting materials for use in the emulsion described above, there may be overlap between types of starting materials because certain starting materials described herein may have more than one function. When adding additional starting materials to the emulsion, the additional starting materials are distinct from one another and from the aminosiloxane ester copolymer, the surfactant, and the water.

Method for Making the Emulsion

[0040] Emulsions may be prepared in a batch, semi-continuous, or continuous process using conventional equipment. For example, mixing the starting materials to form the emulsion may occur, for example using, batch equipment with high-shear and high-speed dispersers include those made by Charles Ross & Sons (NY), Hockmeyer Equipment Corp. (NJ); batch mixing equipment such as those sold under the tradename Speedmixer™; batch equipment with high shear actions include Banbury-type (CW Brabender Instruments Inc., NJ) and Henschel type (Henschel mixers America, TX). Illustrative examples of continuous mixers/compounders include extruders, such as single-screw, twin-screw, and multi-screw extruders, co-rotating extruders, such as those manufactured by Krupp Werner & Pfleiderer Corp (Ramsey, NJ), and Leistritz (NJ); twin-screw counterrotating extruders, two-stage extruders, twin-rotor continuous mixers, dynamic or static mixers or combinations of these equipment.

[0041] The starting materials described above may be combined under any suitable conditions for forming an emulsion. For example, to simplify the mixing process and keep the emulsion viscosity low while handling, any acid compound may be added at the end of the method, i.e., once the desired dilution level is reached. However, when an optional additional starting material is used, the optional additional starting material may be added by any convenient means. Certain additional starting materials, such as the co-solvent, may be emulsified with the aminosiloxane ester copolymer, for example, when the aminosiloxane ester copolymer is prepared with the co-solvent. Other additional starting materials may be combined by mixing with the emulsion comprising the aminosiloxane ester copolymer after formation of the emulsion, e.g., when an amino- functional polydiorganosiloxane is used, the amino-functional polydiorganosiloxane may be emulsified, and the resulting emulsion may be mixed with an emulsion comprising the aminosiloxane ester copolymer, as described above. For example, 90% ± 5% of the emulsion comprising the aminosiloxane ester copolymer and 10% ± 5% of an aqueous emulsion comprising the amino-functional polydiorganosiloxanes, a surfactant, and water may be combined by mixing to form the emulsion to be used in the process for treating textiles.

Process for Treating Fibers/Textiles

[0042] The emulsion described above may be used in a process for treating textiles, e.g., fibers and/or fabrics. The process comprises: i) applying the emulsion described above to a textile, and ii) drying the textile. [0043] In step i), the emulsion may be applied to the textile by any convenient method. For example, the emulsion may be applied by padding, dipping, spraying or exhausting. The emulsion may be applied to the textile during making the fiber or fabric, or later such as during laundering the textile.

[0044] The amount of emulsion applied to the textile depends on various factors including the type of textile and the amount of aminosiloxane ester copolymer in the emulsion. However, the amount of the emulsion applied to the textile may be sufficient to provide 0.2 % to 15 % of the emulsion on the textile, based on dry weight of the textile, alternatively 0.2 % to 5 %, on the same basis. Alternatively, the amount of the emulsion applied to the textile may be sufficient to deliver 0.1 % to 0.5 % of the aminosiloxane ester copolymer on the textile, based on dry weight of the textile.

[0045] After the emulsion is applied to the textile, it can be dried in step ii) by any convenient means. Drying may be performed at ambient or elevated temperature (with heating). Alternatively, drying in step ii) may comprise heating.

[0046] Suitable fibers may have the form of threads, strands, filaments, tows, or yams, and suitable fabrics include woven and nonwoven materials such as webs, mats, loop-formingly knitted or loop-drawingly knitted. Suitable fibers may be of any natural or synthetic origin. Examples textiles, which can be treated by the process of this invention, include those of natural origin such as cotton, hemp, linen, silk, and wool; synthetics such as polyester, polyamide, polyacrylonitrile, polyolefins such as polyethylene and polypropylene, polyvinyl alcohol; interpolymers of vinyl acetate, rayon, polyurethane; manmade and/or regenerated cellulosics; and combinations and blends of two or more thereof. The textile fabrics can be present in the form of fabric webs or garments or parts of garments.

EXAMPLES

[0047] The following examples are provided to illustrate the invention to one skilled in the art and are not to be interpreted to limit the scope of the invention set forth in the claims. Starting materials used in these examples are described below in Table 1.

Table 1 - Starting Materials

[0048] In this Reference Example 1 , aqueous aminosiloxane ester copolymer emulsions with the starting materials (as described in Table 1) in amounts shown below in Table 3 were prepared as described in PCT Patent Application Publication WO2023/278918 according to the conditions in Table 2. In a plastic dental cup, an aminosiloxane ester copolymer, a surfactant, and a first amount of water were mixed by a high shear mixer. Three aliquots of dilution water were added, with mixing after each addition. The acetic acid solution was added and mixed. SYNPERONIC™ 13/12 was then added at the end of the process. Emulsification Process conditions for each step are shown below in Table 2. Amounts of each starting material (in weight %) are shown below in Table 3.

Table 2 - Emulsification Process

Table 3 - Starting Materials in Working Examples

[0049] In Comparative Examples 1 and 2, aqueous emulsions of commercially available amino-functional polydiorganosiloxanes was prepared using the process conditions shown below in Table 4, and the starting materials in amounts shown below in Table 5 (8800, Comparative Example 1) and Table 6 (8041, Comparative Example 2).

Table 4 - Emulsification Process for DOWSIL™ AP-8041 Fluid & XIAMETER™ OFX-8800

Fluid

Table 5 - Emulsion of XIAMETER™ OFX-8800 Fluid

Table 6 - Starting Materials for Comparative (Aminosiloxane) Emulsion

[0050] In this Reference Example 2, each emulsion was applied on a substrate via an exhaust method and dried, as follows: The exhaust method was a batch wise process wherein an aminosiloxane ester copolymer (active) was transferred to a fabric substrate by desorption and absorption of the active from the emulsion (described in Tables 3, 5, and 6) to the substrate (mainly due to the substantivity of the particular emulsion). The exhaust method was done relatively from a diluted bath on a machine such as jet, overflow or winch. Here the exhaustion rate was relevant to ecological considerations of wastewater loads. The conditions for the Exhaust method are shown below in Table 7.

Table 7: Exhaust Method

1) All samples were tested by exhaust method on 100 RFF terry Towel.

2) Active content 0.4 % maintained on the Towel

3) Application temp - 40 °C

4) Application Time - 30 Min

5) MLR (Material to Liquor Ratio ) - 1 : 10

6) Exhaustion pH - 5.5 to 6

7) All treated samples are dried at RT.

8) Conditioning for 24 Hrs.

9) Surface Handle Evaluation carried out by Control Panel .

I) No of persons in Control Panel : 5

II) Surface Handle rating on a scale of 1 to 5 i.e. Worst :1 Best :5

[0051] In this Reference Example 3, each emulsion was applied on a substrate via a padding method and dried, as follows: The padding method was a continuous process for emulsion application. The aminosiloxane ester copolymer (active) (or the comparative active from a Comparative Example) was applied by forced application (padding) from relatively concentrated emulsions, which transferred the active onto the fabric. The amount of active transfer was controlled by concentration of active and expression on substrate. For example, 60% expression meant 60% active was transferred on to the substrate. Expression was adjusted by controlling the pressure between two rollers of the padding mangle through which the substrate was squeezed. Conditions for padding are shown below in Table 8.

Table 8 - Padding Method

[0052] In this Reference Example 4, performance of the textiles treated according to Reference Examples 2 and 3 were evaluated as follows. Surface handle was tested by the method shown below in Table 9. Table 9 - Surface Handle

[0053] Water Absorbency Testing was performed according to: AATCC 79 - 2000. A water penetration value of less than 10 seconds, alternatively 1 to 2 seconds, indicated good hydrophilicity/quick absorption.

[0054] Contact Angle was measured according to ASTM D5946, as follows: i) The treated textile was sandwiched between 2 untreated cotton fabric pieces. The resulting was ironed. ii) A treated flat fabric piece was kept on a movable platform under the syringe of contact angle goniometer (CAG) in such a way that it was clearly visible in camera frame of CAG. ii) A drop of water was placed on each sample by using syringe connected to CAG. As soon as a water drop fell on fabric surface, the CAG’s camera immediately started capturing images of water drop fallen on fabric and initiated measuring contact angle of it. iii) As time passed, water drops started remaining on fabric, and that change in contact angle of water drop with respect to time, was continuously recorded by contact angle goniometer. iv) Benchmark was set for contact angle at below ~ 10 degrees. v) CAG results for different samples were collected and compared. The results are shown below in Table 10.

Table 10 - Performance Test Results

[0055] In Table 10, ^# denotes that the sample was stable when tested 6 weeks under the conditions tested. Example 5 was a blend prepared by mixing 90 weight parts of the emulsion of Example 2 and 10 weight parts of the emulsion of Comparative Example 2 containing 8041 as the active.

[0056] The results in Table 10 show that 4103 and IE-9100, commercially available emulsions containing silicone acrylates as actives did not provide hydrophilicity to the treated substrate. Silicone acrylate copolymers, such as those present in IE-9100, are typically hydrophobic, as shown by the high value for water penetration. All of the emulsions containing aminosiloxane ester copolymers provided both softness as shown by a handle rating of 4.5, and hydrophilicity as shown by a contact angle < 5 and a water penetration < 10 seconds in Examples 1 to 4. Example 2 demonstrated surprisingly low contact angle and water penetration values, even though the aminosiloxane ester copolymer had a longer DP dimethylsiloxane segment (84) compared to the other aminosiloxane ester copolymers tested (with 44 DP dimethylsiloxane segments) even though lengthening dimethylsiloxane segments would typically be expected to decrease hydrophilicity. And, in Example 5 the inventors surprisingly found that combining emulsions of an aminosiloxane ester copolymer and 8041 as actives produced the lowest contact angle of all samples tested, demonstrating a synergistic effect when combining a hydrophobic amino-functional siloxane and the aminosiloxane ester copolymer described herein.

INDUSTRIAL APPLICABILITY

[0057] The inventors surprisingly found that the aminosiloxane ester copolymers described herein provided hydrophilicity to the fabric tested in the examples above, without polyether functionalities, even though amino-siloxane polymers and silicone - acrylate copolymers are typically hydrophobic. The aminosiloxane ester copolymer described herein may also provide one or more additional benefits, including low content of cyclic polydiorganosiloxanes such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane and dodecamethylcyclohexasiloxane. Without wishing to be bound by theory, it is thought that the aminosiloxane ester copolymer may also provide improved handle, tear strength, and/or crease resistance to the textiles treated according to the process of this invention.

DEFINITIONS AND USAGE OF TERMS

[0058] All amounts, ratios, and percentages herein are by weight, unless otherwise indicated by the context of the specification. The articles ‘a’, ‘an’, and ‘the’ each refer to one or more, unless otherwise indicated by the context of specification. The singular includes the plural unless otherwise indicated by the context of the specification. The SUMMARY and ABSTRACT are hereby incorporated by reference. The amounts of all starting materials in a composition or emulsion total 100%. The transitional phrases “comprising”, “consisting essentially of’, and “consisting of’ are used as described in the Manual of Patent Examining Procedure Ninth Edition, Revision 08.2017, Last Revised January 2018 at section §2111.03 I., II., and III. The use of “for example,” “e.g. " “such as,” and “including” to list illustrative examples does not limit to only the listed examples. Thus, “for example” or “such as” means “for example, but not limited to” or “such as, but not limited to” and encompasses other similar or equivalent examples. The disclosure of ranges includes the range itself and also anything subsumed therein, as well as endpoints. Similarly, the disclosure of Markush groups includes the entire group and also any individual members and subgroups subsumed therein. For example, disclosure of the Markush group a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group, includes the member alkyl individually; the subgroup alkyl and aryl; and any other individual member and subgroup subsumed therein. Any feature or aspect of the invention may be used in combination with any other feature or aspect recited herein. The abbreviations used herein have the definitions in Table 11.

Table 11 - Abbreviations

Claims

CLAIMS:

1. A process for treating a textile, wherein the process comprises: i) applying an emulsion to a textile, and ii) drying the textile, wherein the emulsion comprises:

(A) an aminosiloxane ester copolymer,

(B) a surfactant, and

(C) water.

2. The process of claim 1 , wherein (A) the aminosiloxane ester copolymer comprises formula:

wherein each R¹ is an independently selected monovalent hydrocarbon group of 1 to 12 carbon atoms, each R^E is independently selected from the group consisting of hydroxyl and an aminofunctional group of formula H2N-R^A-, each R^A is an independently divalent hydrocarbon group of 1 to 12 carbon atoms, each R² is independently selected from the group consisting of hydrogen and methyl, each R^D is an independently selected divalent hydrocarbon group of 2 to 20 carbon atoms, each subscript a independently has a value such that 0 < a < 150; and subscript has a value such that 1 < b < 100.

3. The process of claim 2, where each R¹ is methyl, each R^E is the amino-functional group of formula H2N-R^A-, each R^A is an independently divalent hydrocarbon group of 3 carbon atoms, each R² is hydrogen, each R^D is an independently selected divalent hydrocarbon group of 6 to 20 carbon atoms, each subscript a independently has a value such that 42 < a < 150; and subscript has a value such that 2 < b < 100.

4. The process of any one of claims 1 to 3, where (B) the surfactant comprises a nonionic surfactant.

5. The process of any one of claims 1 to 4, where the emulsion further comprises an additional starting material selected from the group consisting of an amino-functional polydiorganosiloxane, a co-solvent, an acid compound, an acid anhydride, a thickener, a stabilizer, a preservative, a brightener, a perfume, a perfume delivery system, a pH adjuster, a solvent, a dispersant, a catalytic material, a fabric softener, a processing aid, and a combination of two or more thereof.

6. The process of claim 5, where the acid compound is present.

7. The process of claim 5 or claim 6, where the amino-functional polydiorganosiloxane is present.

8. The process of any one of claims 1 to 7, where the textile is selected from the group consisting of a fiber and a fabric.

9. The process of any one of claims 1 to 8, where the textile comprises cotton.

10. The process of any one of claims 1 to 9, where the emulsion is applied to the textile by a method selected from the group consisting of padding, dipping, spraying or exhausting.

11. The process of any one of claims 1 to 10, where the emulsion is applied to the textile in an amount sufficient to provide 0.1 % to 0.5 weight % of the aminosiloxane ester copolymer on the textile, based on dry weight of the textile.

12. The process of any one of claims 1 to 11, where drying in step ii) comprises heating.

13. A textile treatment emulsion, wherein the emulsion comprises:

(A) an aminosiloxane ester copolymer;

(B) a surfactant; (C) water;

(D) an amino-functional polydiorganosiloxane; and

(E) an acid compound.

14. The textile treatment emulsion of claim 13, further comprising an additional starting material selected from the group consisting of: a co-solvent, an acid anhydride, a thickener, a stabilizer, a preservative, a brightener, a perfume, a perfume delivery system, a pH adjuster, a solvent, a dispersant, a catalytic material, a fabric softener, a processing aid, and a combination of two or more thereof.

15. The textile treatment emulsion of claim 13 or claim 14, wherein any one or more of conditions (i) to (v) is met, wherein condition (i) is that (A) the aminosiloxane ester copolymer comprises formula:

wherein each R¹ is an independently selected monovalent hydrocarbon group of 1 to 12 carbon atoms, each R^E is independently selected from the group consisting of hydroxyl and an amino-functional group of formula H N-R -, each R^A is an independently divalent hydrocarbon group of 1 to 12 carbon atoms, each R² is independently selected from the group consisting of hydrogen and methyl, each R^D is an independently selected divalent hydrocarbon group of 2 to 20 carbon atoms, each subscript a independently has a value such that 0 < a < 150; subscript has a value such that 1 < b < 100; and wherein the copolymer has a molar ratio of amino/acrylate groups in its backbone of 1.05/1 to 1.5/1; condition (ii) is that (B) the surfactant comprises a nonionic surfactant; condition (iii) is that the amino-functional polydiorganosiloxane is present; condition (iv) is that the co-solvent is present; and condition (v) is that the acid compound is present.