Silicone-(meth)acrylate copolymer emulsion formulations for treating textiles

Abstract

An emulsion formulation suitable for treating textiles includes a siloxane-(meth)acrylate copolymer, a non-ionic surfactant, water, and a water-dispersible crosslinker. Methods for preparing the emulsion formulation and the copolymer are provided.

Description

[Technical Field]

[0001] (CROSS-REFERENCE TO RELATED APPLICATIONS) This application claims the benefit under 35 U.S.C. §119(e) of U.S. Provisional Patent Application No. 63 / 231,280, filed August 10, 2021. U.S. Provisional Patent Application No. 63 / 231,280 is incorporated herein by reference.

[0002] FIELD OF THE INVENTION Emulsion formulations containing silicone-(meth)acrylate copolymers and methods for preparing the emulsion formulations are provided, which are useful for treating textiles to impart durable water repellency to the textiles. [Background technology]

[0003] In water-repellent textile treatment applications, fluorocarbon materials have dominated the market due to their ability to provide excellent durable water repellency. However, regulatory and customer pressures are contributing to the industry need for non-fluorocarbon textile treatments. Previously disclosed fluorocarbon-free textile treatments have the disadvantage of providing poor durability, with the water repellency of treated textiles decreasing significantly after multiple washes. Summary of the Invention

[0004] Disclosed is an emulsion formulation and a process for preparing the same. The emulsion formulation includes (I) a silicone-(meth)acrylate copolymer, (II) a nonionic surfactant, (III) water, and (IV) a water-dispersible crosslinker. The emulsion formulation is suitable for treating textiles. DETAILED DESCRIPTION OF THE INVENTION

[0005] As introduced above, the starting material (I) in the emulsion formulation is a silicone-(meth)acrylate copolymer (copolymer). The copolymer has the unit formula:

[0006] [ka] (In the formula, each R 1 are independently selected alkyl groups of 16 to 24 carbon atoms, and each R 2 is independently selected from the group consisting of H and methyl, and each D 2 is a divalent hydrocarbon group of 2 to 12 carbon atoms, and each R 3 are independently 4 and the formula -OSi(R 4 )3 groups, and each R 4 are independently selected monovalent hydrocarbon radicals of 1 to 12 carbon atoms, and each R 7 are independently selected from the group consisting of oxygen atoms and NH; D 3 is a divalent hydrocarbon radical of 1 to 12 carbon atoms, and D 4 is an alkylene group or a divalent alkylarylene group of 2 to 4 carbon atoms, and the subscript v indicates the formula (OD 4 ) represents the number of units, the subscript v has a value from 0 to 12, and each R 8 is a crosslinkable group, and each R 5 is independently selected from the group consisting of an oxygen atom and NH; D is a divalent hydrocarbon radical of 1 to 12 carbon atoms; and each D 1 is an alkylene group or a divalent alkylarylene group of 2 to 4 carbon atoms, and the subscript v2 is a group of the formula (OD 1 ) and the subscript v2 has a value between 0 and 20, and each R 6 are independently selected from the group consisting of hydroxyl groups and alkoxy groups (e.g., methoxy), and each R 9 is a monovalent hydrocarbon radical of 1 to 14 carbon atoms, and each R 10are independently selected from the group consisting of a halogen (e.g., chlorine), an acetate group, or a monovalent hydrocarbon group of 1 to 14 carbon atoms, and the subscripts w, x, y, y2, z1, and z2 represent the relative weight of each unit in the copolymer, where subscript w has a value of 80 to 98, subscript x has a value of 1 to 15, subscript y has a value of 1 to 5, subscript y2 has a value of 0 to 5, subscript z1 has a value of 0 to 18, and subscript z2 has a value of 0 to 18, such that the amount (w+x+y+y2+z1+z2)=100. The copolymer further comprises a terminal moiety.

[0007] In the above formula, R 1 has 16 to 24 carbon atoms. 1 may have at least 16, alternatively at least 17, alternatively at least 18 carbon atoms, while R 1 may have up to 24, alternatively up to 23, alternatively up to 22 carbon atoms. 1 R may have 17 to 23 carbon atoms, alternatively 16 to 22 carbon atoms, alternatively 17 to 24 carbon atoms, or alternatively 18 to 22 carbon atoms. 1 may be selected from the group consisting of stearyl, eicosyl, and behenyl. 1 may be stearyl.

[0008] In the above unit formula, the unit with the subscript x is a silicone-(meth)acrylate macromonomer unit. In the silicone-methacrylate macromonomer unit, each R 3 are independently 4 and the formula -OSi(R 4 )3(in the formula, each R 4 is an independently selected monovalent hydrocarbon group of 1 to 12 carbon atoms. 4The monovalent hydrocarbon group in R may be an alkyl group, for example, an alkyl group of 1 to 6 carbon atoms. Alternatively, the alkyl group may have 1 to 3 carbon atoms, or alternatively, 1 to 2 carbon atoms. Alternatively, each R 4 may be methyl.

[0009] In the above unit formula, each D 2 is a divalent hydrocarbon radical of 2 to 12 carbon atoms; or D 2 Each D may have 2 to 10, alternatively 3 to 5, alternatively 3 carbon atoms. 3 and each D is independently a divalent hydrocarbon group of 1 to 12 carbon atoms. Alternatively, each D 3 and each D may be an alkylene group, or alternatively, ethylene. 4 and D 1 are each independently an alkylene group or a divalent alkylarylene group of 2 to 4 carbon atoms.

[0010] D 4 and D 1 The divalent hydrocarbon group may be an alkylene group such as ethylene, propylene, or butylene, an arylene group such as phenylene, or

[0011] [ka] or

[0012] [ka] (wherein each subscript u is independently 1 to 6, or 1 to 2). Alternatively, the divalent hydrocarbon group may be alkylene, or the divalent hydrocarbon group may be ethylene. D, D 2 , and D 3 The divalent hydrocarbon group of may be as described above or may be methylene. 2may be methylene, ethylene, or propylene, or is propylene. 2 may be linear, for example, -(CH2)2- or -(CH2)3-.

[0013] In the above unit formula, each R 7 are independently selected from the group consisting of oxygen atoms and NH. Alternatively, each R 7 may be oxygen.

[0014] In the above formula, each R 8 is a crosslinkable group. 8 may be independently selected from the group consisting of hydroxy, amino, epoxy, ureido, and acetoxy. 8 may be independently selected from the group consisting of hydroxy and ureido, or each R 8 may be hydroxy.

[0015] In the above unit formula, each R 5 is an oxygen atom. 6 is selected from the group consisting of —OH and alkoxy. 6 The alkoxy group may be —OCH3.

[0016] In the above formula, each R 9 R is a monovalent hydrocarbon group, is free of aliphatic unsaturation, and may be linear, branched, or cyclic (i.e., monocyclic or polycyclic), or a combination thereof. 9 R may be an alkyl or aryl group, may be monocyclic or polycyclic, and may optionally have linear or branched groups. 9 Suitable examples of alkyl groups include methyl, t-amyl, butyl (including t-butyl), cyclohexyl, isodecyl, isobornyl, and 2-ethylhexyl. Suitable examples of aryl groups include phenyl, naphthyl, anthracyl, and benzyl.

[0017] In the above formula, R 10 is R 9 As described above for , it may be a halide, acetate, or monovalent hydrocarbon group. The halide may be bromide (Br), chloride (Cl), fluoride (F), or iodide (I), or may be Br, Cl, or F, or may be Cl or Br, or may be Cl.

[0018] In the above unit formula, the subscripts w, x, y, y2, z1, and z2 are the relative weights of each unit, and the amount (w+x+y+y2+z1+z2) may total 100. The subscript w has a value from 80 to 98. Alternatively, the subscript w may be at least 80, alternatively at least 81, alternatively at least 82, alternatively at least 83, alternatively at least 84, alternatively at least 85, alternatively at least 86, alternatively at least 87, alternatively at least 88, while the subscript w may be up to 98, alternatively up to 97, alternatively up to 96, alternatively up to 95, alternatively up to 94, alternatively up to 93, alternatively up to 92, alternatively up to 91, alternatively up to 90, alternatively up to 89, alternatively up to 88. Alternatively, the subscript x may be 84 to 92, alternatively 85 to 91, alternatively 86 to 90, alternatively 87 to 89, or alternatively 88.

[0019] The subscript x has a value of 1 to 15, alternatively 5 to 15. Alternatively, the subscript x may be at least 1, alternatively at least 5, alternatively at least 6, alternatively at least 7, alternatively at least 8, alternatively at least 9, alternatively at least 10, while the subscript x may be up to 15, alternatively up to 14, alternatively up to 13, alternatively up to 12, alternatively up to 11, alternatively up to 10. Alternatively, the subscript x may be 1 to 14, alternatively 2 to 13, alternatively 3 to 12, alternatively 4 to 11, alternatively 5 to 10, alternatively 7 to 13, alternatively 10.

[0020] The subscript y has a value from 1 to 5. Alternatively, the subscript y may be at least 1, alternatively at least 1.25, alternatively at least 1.5, alternatively at least 1.75, alternatively at least 2, while the subscript y may be at most 5, alternatively at most 4, alternatively at most 3, alternatively at most 2.75, alternatively at most 2.5, alternatively at most 2.25. Alternatively, the subscript y may be 1 to 3, alternatively at most 1 to 2, alternatively at most 1.5 to 2.5, alternatively at least 1.75 to 2.25, alternatively at least 2.

[0021] The subscript y2 has a value from 0 to 5. Alternatively, the subscript y2 may be at least 1, alternatively at least 1.25, alternatively at least 1.5, alternatively at least 1.75, alternatively at least 2, while the subscript y2 may be at most 5, alternatively at most 4, alternatively at most 3, alternatively at most 2.75, alternatively at most 2.5, alternatively at most 2.25. Alternatively, the subscript y2 may be at most 0 to 3, alternatively at most 1 to 2, alternatively at most 1.5 to 2.5, alternatively at most 1.75 to 2.25, alternatively at least 2.

[0022] The subscript z1 may be 0. Alternatively, the subscript z1 may be at least 0.5, alternatively at least 1, alternatively at least 2, while the subscript z1 may be up to 18, alternatively at most 15, alternatively at most 10, alternatively at most 8, alternatively at most 5. Alternatively, the subscript z1 may be 0 to 18, alternatively greater than 0 to 18, alternatively 0.5 to 7, alternatively 1 to 6, alternatively 2 to 5.

[0023] Subscript z2 may be 0. Alternatively, subscript z2 may be at least 0.5, alternatively at least 1, alternatively at least 2, while subscript z2 may be up to 8, alternatively at most 7, alternatively at most 6, alternatively at most 5, alternatively at most 4. Alternatively, subscript z2 may be 0 to 8, alternatively greater than 0 to 8, alternatively 0.5 to 7, alternatively 1 to 6, alternatively 2 to 5.

[0024] The total number of units per molecule of the copolymer is not particularly limited. However, the copolymer may have a number average molecular weight of 100,000 g / mol to 4,000,000 g / mol, alternatively 200,000 g / mol to 3,000,000 g / mol, alternatively 100,000 g / mol to 1,000,000 g / mol, depending on the conventional method and the selection of the respective monomers and chain transfer agents. The units shown above may be in any order; for example, the copolymer may be a random copolymer or a block copolymer.

[0025] Those skilled in the art will recognize that copolymers can be prepared by radical polymerization via a process such as that described below, which process forms end moieties for the copolymer. The copolymer further comprises end moieties that can be derived from the initiator, the chain transfer agent, or both, as described, for example, in Odian, George (2004). Principles of Polymerization (4th ed.). New York: Wiley-Interscience. ISBN 978-0-471-27400-1.

[0026] The copolymer is (1) 80% by weight to 98% by weight of (A) formula:

[0027] [ka] (In the formula, R 1 and R 2 is as defined above), and 1% by weight to 15% by weight of (B) formula:

[0028] [ka] (In the formula, R 2 , R 3 , and R 4 wherein R is as defined above), and 1% by weight to 5% by weight of (C) formula:

[0029] [ka] (In the formula, R 2 , R 7 , D 3 , D 4 , R 8 and subscript v is as defined above), 1. A process comprising copolymerizing a starting material comprising: The amounts of the starting materials (A), (B) and (C) total 100% by weight based on the total amount of the starting materials (A), (B) and (C), and the starting materials (A), (B) and (C) are (D) a surfactant; (E) water, (F) an initiator; copolymerized in an emulsion further comprising The process can be prepared by forming an aqueous emulsion containing (I) a silicone-(meth)acrylate copolymer, (D) a surfactant, and (E) water. The process may optionally further include adding an additional starting material in step (1), wherein the additional starting material is selected from the group consisting of (G) a chain transfer agent, (H) an additional monomer different from the starting materials (A), (B), and (C), (J) an inhibitor, (K) a reactive surfactant, and a combination of two or more of (G), (H), (J), and (K).

[0030] Step (1) of the above process may include forming an emulsion containing starting materials (A), (B), (C), (D), (E), and (F) (and optionally (G), (H), (J), and / or (K)). If starting material (A) is a solid at room temperature, the starting material may be heated to 30°C to 50°C at a temperature and for a time sufficient to melt starting material (A), for example, 5 minutes to 15 minutes. The resulting starting materials may be mixed under shear to form an aqueous emulsion. Mixing under shear may be performed by any convenient means for forming an aqueous emulsion, such as by sonication followed by microfluidization. Equipment for mixing under shear (e.g., ultrasonicators, homogenizers, microfluidizers, and speed mixers) is known in the art and commercially available. Without wishing to be bound by theory, it is believed that mixing under shear can be used to obtain submicron particle sizes in the emulsion. In step (1), starting materials including (A), (B), (C), and (F) (and, if present, (G), (H), and (K)) are copolymerized to form (I) a silicone-(meth)acrylate copolymer in an aqueous emulsion with starting materials (D) and (E) (and, if present, (J) an inhibitor).

[0031] Alternatively, the copolymers may be prepared by a process comprising dissolving one or more of the starting materials in an organic solvent (e.g., a monohydric alcohol) and copolymerizing the starting materials (A), (B), (C), (F), and, if present, (G) a chain transfer agent and / or (H) additional monomers in a process such as that disclosed in U.S. Pat. No. 10,047,199 to Iimura et al. by varying the appropriate starting materials and their amounts. The resulting copolymers may be solvent-based. All or a portion of the solvent can be removed by any convenient means, such as stripping or distillation using heat and, optionally, reduced pressure. The copolymers may be emulsified using (D) a surfactant and (E) water, as well as the other starting materials from step (2) of the above process. The starting materials for producing the copolymers and emulsion formulations containing the copolymers are further described below.

[0032] (A) Crystalline monomer The starting material (A) is represented by the formula (A-1):

[0033] [ka] (In the formula, R 1 and R 2 is a crystalline monomer of the formula (A) as defined above. Examples of crystalline monomers for starting material (A) include stearyl (meth)acrylate, eicosyl (meth)acrylate, behenyl (meth)acrylate, and combinations thereof. Alternatively, R 2 When is hydrogen, starting material (A) may be an acrylate selected from stearyl acrylate, eicosyl acrylate, behenyl acrylate, and combinations thereof. Alternatively, starting material (A) may be stearyl acrylate. Suitable crystalline monomers for starting material (A) are commercially available, for example, from Millipore Sigma (St. Louis, Missouri, USA) and BASF SE (Ludwigshafen, Germany). By crystallizable, it is meant that the starting monomer has a melting point of 25°C or higher (±5°C).

[0034] Starting material (A) is used in an amount of 80% to 98% based on the combined weight of starting materials (A) crystalline monomer, (B) silicone-(meth)acrylate macromonomer, and (C) crosslinkable (meth)acrylate monomer, and, if present, (H) additional monomer and / or (K) reactive surfactant. The amount of starting material (A) may be at least 80%, alternatively at least 81%, alternatively at least 82%, alternatively at least 83%, alternatively at least 84%, alternatively at least 85%, alternatively at least 86%, alternatively at least 87%, or alternatively at least 88% on the same basis. At the same time, the amount of starting material (A) may be up to 93%, alternatively at most 92%, alternatively at most 91%, alternatively at most 90%, alternatively at most 89%, or alternatively at most 88% on the same basis. Alternatively, the amount of starting material (A) may be, on the same basis, 84% to 92%, alternatively 85% to 91%, alternatively 86% to 90%, alternatively 87% to 89%, or alternatively 88%.

[0035] (B) Silicone-(meth)acrylate macromonomer The starting material (B) has the formula:

[0036] [ka] (In the formula, R 2 , R 3 , R 4 , and D 2 is as defined above). Alternatively, starting material (B) is a silicone-(meth)acrylate macromonomer of the formula:

[0037] [ka] (In the formula, R 2 , D 2 , and R 4 wherein

[0038] Alternatively, the starting material (B) is a compound of the formula:

[0039] [ka] (In the formula, R 2 , R 3 and R 4 Alternatively, the starting material (B) may have

[0040] [ka] 3-(1,1,1,3,5,5,5-heptamethyltrisiloxan-3-yl)propyl methacrylate, and

[0041] [ka] 3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl methacrylate.

[0042] The starting material (B) can be prepared by known methods, such as those disclosed in WO 2020 / 142388 and U.S. Pat. No. 6,420,504.

[0043] Starting material (B) is used in an amount of 1% to 15% based on the combined weight of starting materials (A), (B), and (C), and, if present, (H) additional monomer and / or (K) reactive surfactant. Alternatively, starting material (B) may be used in an amount of at least 5%, alternatively at least 6%, alternatively at least 7%, alternatively at least 8%, alternatively at least 9%, or alternatively at least 10% on the same basis. At the same time, starting material (B) may be present in an amount of up to 15%, alternatively at most 14%, alternatively at most 13%, alternatively at most 12%, alternatively at most 11%, or alternatively at most 10% on the same basis. Alternatively, the amount of starting material (B) may be 6% to 14%, alternatively at most 7% to 13%, alternatively at most 8% to 12%, alternatively at most 9% to 11%, or alternatively at most 5% to 10% on the same basis.

[0044] (C) Crosslinkable (meth)acrylate monomer The starting material (C) is represented by the formula (C-1):

[0045] [ka] (In the formula, R 2 , R 7 , D 3 , R 8 and the subscript v is as defined above). Examples of crosslinkable (meth)acrylates suitable for starting material (C) include (2-acetoacetoxy)ethyl methacrylate, hydroxybutyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxyethyl caprolactone (meth)acrylate, hydroxypropyl (meth)acrylate, ureido (meth)acrylate, glycidyl (meth)acrylate (GMA), poly(ethylene glycol) (meth)acrylate (PEGMA), and combinations thereof. Ureido (meth)acrylate monomers are represented by the formula:

[0046] [ka] (In the formula, R 11 may have an oxygen atom or an NH moiety). Examples of ureido monomers are known in the art and are disclosed, for example, in U.S. Patent No. 9,212,292 to Pressley et al. Other crosslinkable (meth)acrylate monomers are known in the art and are commercially available, for example, from BASF SE. Other crosslinkable (meth)acrylates are commercially available as Sipomer WAM1 and 2.

[0047] Starting material (C) is used in an amount of 1% to 5%, based on the combined weight of starting materials (A), (B), and (C), and, if present, (H) and / or (K). The amount of starting material (C) may be at least 1%, alternatively at least 1.25%, alternatively at least 1.5%, alternatively at least 1.75%, or alternatively at least 2%, on the same basis. At the same time, the amount of starting material (C) may be up to 5%, alternatively at most 4%, alternatively at most 3%, alternatively at most 2.75%, alternatively at most 2.5%, or alternatively at most 2.25%, on the same basis. Alternatively, the amount of starting material (C) may be 1% to 3%, alternatively at most 1% to 2%, alternatively at most 1.5% to 2.5%, alternatively at most 1.75% to 2.25%, or alternatively at most 2%, on the same basis.

[0048] Starting material (D) surfactant The starting material (D) is a surfactant. The surfactant used in the copolymerization in step (1) of the process for preparing an aqueous emulsion is not particularly limited and may be selected from the group consisting of anionic surfactants, amphoteric surfactants, cationic surfactants, nonionic surfactants, and combinations of two or more thereof.

[0049] Anionic surfactants include (i) sulfonic acids and their salt derivatives (e.g., alkyl, aralkyl, alkyl naphthalene, alkyl diphenyl ether sulfonic acids) and salts thereof having at least 6 carbon atoms in the alkyl substituent (e.g., dodecylbenzene sulfonic acid and its sodium or amine salts), (ii) alkyl sulfates having at least 6 carbon atoms in the alkyl substituent (e.g., sodium lauryl sulfate), (iii) sulfate esters of polyoxyethylene monoalkyl ethers, and (iv) long-chain carboxylic acid (e.g., lauric acid, stearic acid, oleic acid) surfactants and their alkali metal and amine salts. 。 Some other examples of anionic surfactants are alkali metal sulfosuccinates; sulfonated glyceryl esters of fatty acids (e.g., sulfonated monoglycerides of coconut oil acid); monohydric sulfonated alcohol ester salts (e.g., sodium oleyl isocyanate); amides of aminosulfonic acids (e.g., the sodium salt of oleylmethyl tauride); sulfonation products of fatty acid nitriles (e.g., palmitonitrile sulfonate); sulfonated aromatic hydrocarbons (e.g., sodium α-naphthalene monosulfonate); condensation products of naphthalene sulfonic acid with formaldehyde; sodium octahydroanthracene sulfonate; alkali metal alkyl sulfates; ether sulfates having alkyl groups of 8 or more carbon atoms (e.g., sodium lauryl ether sulfate); and alkylaryl sulfonates having one or more alkyl groups of 8 or more carbon atoms (e.g., hexadecylbenzene sulfonic acid and C 20 It is a neutral salt of alkylbenzenesulfonic acid.

[0050] Commercially available anionic surfactants that can be used include the sodium salt of dodecylbenzenesulfonic acid sold under the trade name SIPONATE™ DS-10 by Alcolac Inc. (Baltimore, Maryland); the sodium salt of alkyl alkoxylate sulfate sold under the trade name DOWFAX™ AS-801 by The Dow Chemical Company (Midland, Michigan, USA); sodium n-hexadecyldiphenyloxide disulfonate sold under the trade name DOWFAX™ 8390 by The Dow Chemical Company (Midland, Michigan); the sodium salt of secondary alkanesulfonate sold under the trade name HOSTAPUR™ SAS 60 by Clariant Corporation (Charlotte, North Carolina); N-acyltaurates such as sodium N-lauroylmethyl taurate sold under the trade name NIKKOL LMT (registered trademark) by Nikko Chemicals Company, Ltd. (Tokyo, Japan); and Stepan Examples of suitable surfactants include linear alkylbenzene sulfonic acids sold under the trade name BIO-SOFT™ S-100 by The BIO-SOFT Company (Northfield, Illinois). The latter type of composition, such as dodecylbenzene sulfonic acid, is a catalyst as described above, but can also function as an anionic surfactant when neutralized. Other suitable surfactants include sodium alkyl sulfonates such as HOSTAPUR™ SAS-30 and triethanolamine dodecylbenzene sulfonate such as BIO-SOFT™ N 300.

[0051] Suitable amphoteric surfactants include amino acid surfactants, betaines (e.g., lauryl betaine, bis-(2-hydroxyethyl)tallow betaine, cocamidopropyl betaine, N-alkylamido betaine, and derivatives thereof), proteins and their derivatives, glycinates (glycine derivatives such as cocamphoglycinate, cocamphocarboxyglycinate, and cocamphodipropionate), sultaines (e.g., cocamidopropyl hydroxysultaine and lauryl sultaine), alkylaminopropionates, alkylpolyaminocarboxylates, and alkylamphoacetates, lecithin and hydrogenated lecithin, and combinations thereof. These surfactants are commercially available from various sources under various trade names. For example, REWOTERIC™ AM TEG is produced by Evonik (Essen, Germany). AMPHOSOL™ CG is available from Stepan Company (Northfield, Illinois, USA).

[0052] Alternatively, the surfactant (D) used in the copolymerization in step (1) may be selected from the group consisting of (D-1) anionic surfactants as described above, (D-2) cationic surfactants, (D-3) nonionic surfactants, (D-4) amphoteric surfactants as described above, and (D-5) a combination of two or more of (D-1) to (D-4). Cationic surfactants useful herein include compounds containing a positively charged quaternary ammonium hydrophilic moiety in the molecule, such as compounds represented by the formula (D-2-1): R 12 R 13 R 14 R 15 N+X' - (In the formula, R 12 ~R 15X' is an alkyl group containing 1 to 30 carbon atoms, or an alkyl group derived from tallow, coconut oil, or soybean; and X' is a halogen, such as chlorine or bromine. Alternatively, the quaternary ammonium compound may be alkyltrimethylammonium and dialkyldimethylammonium halides or acetates, each having at least 8 carbon atoms in each alkyl substituent. Dialkyldimethylammonium salts can also be used, which have the formula (D-2-2): R 16 R 17 N + (CH3)2X' - (In the formula, R 16 and R 17 is an alkyl group containing 12 to 30 carbon atoms, or an alkyl group derived from tallow, coconut oil, or soybean, and X' is a halogen. Monoalkyltrimethylammonium salts can also be used, which are represented by the formula (D-1-3): R 18 N+(CH3)3X” - (In the formula, R 18 is an alkyl group containing 12 to 30 carbon atoms, or an alkyl group derived from tallow, coconut oil, or soybean, and X″ is a halogen or acetate.

[0053] Exemplary quaternary ammonium halide salts are dodecyltrimethylammonium chloride / lauryltrimethylammonium chloride (LTAC), cetyltrimethylammonium chloride (CTAC), hexadecyltrimethylammonium chloride, didodecyldimethylammonium bromide, dihexadecyldimethylammonium chloride, dihexadecyldimethylammonium bromide, dioctadecyldimethylammonium chloride, dieicosyldimethylammonium chloride, and didocosyldimethylammonium chloride. These quaternary ammonium salts are commercially available under trademarks such as ADOGEN™, ARQUAD™, TOMAH™, and VARIQUAT™.

[0054] Other suitable cationic surfactants that can be used include fatty acid amines and amides, and their salts and derivatives, such as fatty acid amines and their derivatives.Commercially available examples of such cationic surfactants include the composition sold by Akzo Nobel Chemicals Inc. (Chicago, Illinois) under the trade name ARQUAD T27 W, ARQUAD 16-29, and the composition sold by Stepan Company (Northfield, Illinois, USA) under the trade name Ammonyx Cetac-30.

[0055] The amount of (D-2) cationic surfactant may be 0.1% to 5% based on the weight of (I) silicone-(meth)acrylate copolymer in the aqueous emulsion. Alternatively, the amount of cationic surfactant may be at least 0.1%, alternatively at least 0.2%, alternatively at least 0.3%, alternatively at least 0.4%, or alternatively at least 0.5%, while the amount of cationic surfactant may be up to 5%, alternatively at most 4%, alternatively at most 3%, alternatively at most 2%, or alternatively at most 1%, on the same basis. Alternatively, the amount of cationic surfactant may be 0.2% to 4%, alternatively at most 0.3% to 3%, alternatively at most 0.4% to 2.5%, or alternatively at most 0.5% to 2%, on the same basis.

[0056] Alternatively, the surfactant (D) used in the copolymerization in step (1) may be a nonionic surfactant (D-3). Some suitable nonionic surfactants that can be used include polyoxyalkylene copolymers (e.g., polyoxyethylene alkyl ethers, polyoxyethylene alkylphenol ethers, alkyl glycosides (e.g., alkyl glucosides), polyoxyethylene fatty acid esters, polyoxyethylene lauryl ethers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitan monooleate, polyoxyethylene alkyl esters, polyoxyethylene sorbitan alkyl esters, polyethylene glycols (e.g., polyethylene glycols having 23 ethylene oxide units), polypropylene glycols, diethylene glycols, ethoxylated trimethylnonanol, tristyrylphenol ethers (TSPs), distyrylphenol ethers (DSPs), and polyoxyalkylene glycol-modified polysiloxane surfactants). Commercially available nonionic surfactants include (i) 2,6,8-trimethyl-4-nonyl polyoxyethylene ethers sold under the trade names TERGITOL™ TMN-6 and TERGITOL™ TMN-10, and (ii) C surfactants such as those sold under the trade names TERGITOL™ 15-S-7, TERGITOL™ 15-S-9, TERGITOL™ 15-S-12, TERGITOL™ 15-S-15, TERGITOL™ 15-S-20, TERGITOL™ 15-S-30, and TERGITOL™ 15-S-40 by Dow Chemical Company (Midland, Michigan, USA). 11~15Secondary alcohol ethoxylates, octylphenyl polyoxyethylene (40) ether sold under the trade name TRITON® X405 by Dow Chemical Company, (iii) nonylphenyl polyoxyethylene (10) ether sold under the trade name MAKON® 10 by Stepan Company, (iv) ethoxylated alcohol sold under the trade name Trycol 5953 by Henkel Corp. / Emery Group (Cincinnati, Ohio, USA), (v) ethoxylated alcohol sold under the trade name Trycol 5953 by Croda Inc. (Edison, New York, USA), (vi) alkyl oxoalcohol polyglycol ethers (e.g., GENAPOL UD050 and GENAPOL UD110); (vii) C10 Guerbet alcohols and ethylene oxide-based alkyl polyethylene glycol ethers (e.g., LUTENSOL XP79); (viii) other alcohol ethoxylates, such as C10 Guerbet alcohols with the trade name ECOSURF EH manufactured by TDCC; 11~15 Included are compositions such as alkyl alcohol ethoxylates (e.g., ECOSURF™ EH-40).TSPs and DSPs are commercially available from Stepan.

[0057] Suitable nonionic surfactants also include poly(oxyethylene)-poly(oxypropylene)-poly(oxyethylene) triblock copolymers. Poly(oxyethylene)-poly(oxypropylene)-poly(oxyethylene) triblock copolymers are also commonly known as poloxamers. They are nonionic triblock copolymers consisting of a central hydrophobic chain of polyoxypropylene (poly(propylene oxide)) flanked by two hydrophilic chains of polyoxyethylene (poly(ethylene oxide)). Poly(oxyethylene)-poly(oxypropylene)-poly(oxyethylene) triblock copolymers are commercially available from BASF (Florham Park, New Jersey, USA) and sold under the PLURONIC™ trade name, such as PLURONIC™ L61, L62, L64, L81, and P84.

[0058] The nonionic surfactant may also be a silicone polyether (SPE). The silicone polyether emulsifier may have a rake structure in which polyoxyethylene or polyoxyethylene-polyoxypropylene copolymer units are grafted onto a siloxane backbone, or the SPE may have an ABA block copolymer structure in which A represents the polyether moiety and B represents the siloxane moiety of the ABA structure. Suitable SPEs include DOWSIL® OFX-5329 Fluid manufactured by Dow Silicones Corporation (Midland, Michigan, USA). Alternatively, the nonionic surfactant may be selected from polyoxyalkylene-substituted silicones, silicone alkanolamides, silicone esters, and silicone glycosides. Such silicone-based surfactants can be used to form such aqueous emulsions and are known in the art and are described, for example, in U.S. Pat. Nos. 4,122,029 to Gee et al., 5,387,417 to Rentsch, and 5,811,487 to Schulz et al.

[0059] The starting material (D-3) nonionic surfactant may be supplied in a dilution, and the amount used may be sufficient to provide 0.1% to 10% surfactant based on the weight of the (I) silicone-(meth)acrylate copolymer in the aqueous emulsion. Alternatively, the amount of nonionic surfactant may be at least 0.1%, alternatively at least 0.2%, alternatively at least 0.3%, alternatively at least 0.4%, alternatively at least 0.5%, or alternatively at least 1%, while the amount of nonionic surfactant may be up to 10%, alternatively at most 5%, alternatively at most 4%, alternatively at most 3%, alternatively at most 2%, or alternatively at most 1%, on the same basis. Alternatively, the amount of nonionic surfactant may be 0.2% to 4%, alternatively at most 0.3% to 3%, alternatively at most 0.4 to 2.5%, or alternatively at most 1% to 2%, on the same basis. Alternatively, the starting materials (D-1) anionic surfactant, (D-2) cationic surfactant, and (D-3) nonionic surfactant may be present in a combined amount of 10% or less, based on the weight of the (I) silicone-(meth)acrylate copolymer in the aqueous emulsion.

[0060] Starting material (E) water The starting material (E) is water. The water is generally not limited; for example, the water may be treated or untreated. Examples of processes that can be used to purify the water include distillation, filtration, deionization, and combinations of two or more thereof, whereby the water may be deionized, distilled, and / or filtered. Alternatively, the water may be untreated (e.g., tap water, i.e., water from a municipal water system, or well water used without further purification). The amount of water is sufficient to form an aqueous emulsion for copolymerization in step (1) of the above process. The amount of water used in step (1) varies depending on various factors, including the types and amounts of the starting materials (A), (B), and (C), and whether an additional monomer (H) is present. However, water may be added in an amount of 20% to 97%, alternatively 30% to 90%, alternatively 40% to 80%, alternatively 50% to 97%, alternatively 50% to 90%, alternatively 60% to 80%, based on the total weight of all starting materials in step (1). Alternatively, water may be added in an amount of at least 20%, alternatively at least 30%, alternatively at least 40%, alternatively at least 50%, and alternatively at least 60%, while this amount may be up to 97%, alternatively up to 96%, alternatively up to 95%, or alternatively up to 80%, on the same basis.

[0061] Without being bound by theory, it is believed that starting materials (A), (B), and (C), and, if present, (H) and / or (K), copolymerize to form the (I) silicone-(meth)acrylate copolymer described above as starting material (I) in emulsion formulations suitable for treating textiles. Furthermore, it is believed that starting materials (D) surfactant and (E) water do not participate in the copolymerization reaction, although copolymers containing one or both of starting materials (D) and (E) are not excluded from the scope of this specification.

[0062] Additional water may be added after step (1). For example, the aqueous emulsion prepared as described above may be diluted with additional water to obtain the desired amount of starting material before preparing the emulsion formulation and / or before treating textiles with the emulsion formulation. The starting material (III) water in the emulsion formulation suitable for treating textiles may be the same as the above-described (E) water, which may be introduced when the above-described emulsion copolymerization process is used to prepare the aqueous emulsion in step (1).

[0063] (F) Initiator To promote copolymerization in step (1) above, starting material (F) an initiator is also added. Suitable initiators include azo compounds and peroxide compounds. For example, the azo compound may be an aliphatic azo compound such as 1-t-amylazo-l-cyanocyclohexane, azo-bis-isobutyronitrile, and 1-t-butylazo-cyanocyclohexane, 2,2'-azobis-(2-methyl)butyronitrile, 2,2'-azobis(2-methylpropionitrile), 2,2'-azobis(2-methylpropionamidine) dihydrochloride, 2,2'-azobis(cyanovaleric acid), or a combination of two or more thereof. Azo compounds are known in the art and are commercially available, for example, from The Chemours Company (Wilmington, Delaware, USA) under the trade name VAZO™ WSP. The peroxide compound may be a peroxide or hydroperoxide, such as t-butyl peroctoate, t-butyl perbenzoate, dicumyl peroxide, di-t-butyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, di-t-amyl peroxide, or a combination of two or more thereof. Additionally, diperoxide initiators may be used alone or in combination with other initiators. Examples of such diperoxide initiators include, but are not limited to, 1,4-bis-(t-butylperoxycarbo)cyclohexane, 1,2-di(t-butylperoxy)cyclohexane, and 2,5-di(t-butylperoxy)-3-hexyne. Suitable peroxide compounds are known in the art and commercially available from various suppliers, such as Sigma-Aldrich, Inc. Alternatively, the initiator may include isoascorbic acid.

[0064] The initiator may be used alone as starting material (F). Alternatively, starting material (F) may be a redox couple comprising an initiator as an oxidizing component and a reducing component. Alternatively, a redox couple comprising isoascorbic acid and a hydrophobic organic hydroperoxide, such as t-amyl hydroperoxide or t-butyl hydroperoxide, may be used as starting material (F). Examples of suitable initiators and / or redox couples for starting material (F) are disclosed in U.S. Pat. No. 6,576,051 to Bardman et al. (column 11, beginning with line 16). How the initiator is added depends on various factors, including whether the initiator is water-soluble and the type of initiator (e.g., whether a thermal initiator or redox couple is used). Typically, when a thermal initiator is used, all of the initiator is added at once at the beginning of step (1). Alternatively, when a redox couple is used, it can be metered in over time. The initiator (F) may be used in an amount sufficient to provide from 0.01% to 3%, alternatively from 0.1% to 1.5%, based on the weight of the (I) silicone-(meth)acrylate copolymer.

[0065] (G) Chain transfer agent Additional starting materials that can be added to promote copolymerization in step (1) of the above process include (G) chain transfer agents. Suitable chain transfer agents include mercaptans such as alkyl mercaptans, e.g., n-octyl mercaptan, n-dodecyl mercaptan, dodecyl mercaptan (dodecanethiol), and / or 2,2-dimethyldecyl mercaptan. Alternatively, the chain transfer agent may be water-soluble, such as mercaptoacetic acid and / or 2-mercaptoethanol. Suitable chain transfer agents are known in the art and are disclosed, for example, in "Radical Polymerization in Industry" by Peter Nesvadba, Performance Chemical Research, GASF Schweiz AG, Basel, Switzerland, Encyclopedia of Radicals in Chemistry, Biology and Materials, Online (Copyright) 2012 John Wiley & Sons, Ltd.

[0066] Starting material (G), the chain transfer agent, is optional and may be added in an amount of 0 to 10%, based on the total weight of starting materials (A), (B), and (C) (and (H) and / or (K), if present). Alternatively, (G) the chain transfer agent may be used in an amount of 5% to 10% on the same basis.

[0067] (H) Additional Monomers Starting material (H) is an optional additional monomer that can be added for copolymerization in step (1). Starting material (H) may be a non-crystalline monomer different from the above starting materials (A), (B), and (C). When present, the additional monomer can be used in an amount of greater than 0 to 18% by weight, based on the weight of the (I) silicone-(meth)acrylate copolymer. Suitable monomers include (meth)acrylate monomers such as methyl methacrylate, t-amyl methacrylate, butyl (meth)acrylate, such as t-butyl methacrylate, cyclohexyl (meth)acrylate, isodecyl (meth)acrylate, isobornyl (meth)acrylate, 2-naphthyl acrylate, benzyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and combinations of two or more thereof. Alternatively, the additional monomer may be styrene or vinyl chloride. Suitable monomers for starting material (H) are known in the art and are commercially available, for example, from Polysciences, Inc. Alternatively, the additional monomer (H) may be selected from the group consisting of isobornyl methacrylate (IBMA), isobornyl acrylate (IBA), and combinations thereof. The additional monomer is optional and may be present in an amount of 0 to 18%, based on the combined weight of starting materials (A), (B), and (C), and, if present, (H) and (K). Alternatively, the (H) additional monomer may be present in an amount of at least 0.5%, alternatively at least 1%, alternatively at least 2%, while the additional monomer may be present in an amount of up to 18%, alternatively up to 15%, alternatively up to 10%, alternatively up to 8%, alternatively up to 5%, on the same basis. Alternatively, the amount of the (H) additional monomer may be greater than 0 to 18%, alternatively 0.5% to 7%, alternatively 1% to 6%, alternatively 2% to 5%, on the same basis.

[0068] (J) Inhibitor Starting material (J) is an inhibitor that may be optionally added in step (1) of the above process. When present, starting material (J) inhibitor may be used in an amount of from greater than 0 to less than 0.01%, based on the weight of (I) silicone-(meth)acrylate copolymer, or from greater than 0 to less than 2,000 ppm on the same basis, or from 1 ppm to 1818 ppm, or from 10 ppm to 500 ppm. Suitable inhibitors for starting material (J) are commercially available and include, for example, nitrobenzene, butylated hydroxyltoluene, diphenylpicrylhydrazyl (DPPH), p-methoxyphenol, 2,4-di-t-butylcatechol, phenothiazine, N,N-diethylhydroxylamine, salts of N-nitrosophenylhydroxylamine, (2,2,6,6-tetramethylpiperidin-1-yl)oxidanyl (TEMPO), and 4-hydroxy-(2,2,6,6-tetramethylpiperidin-1-yl)oxidanyl (4-hydroxyTEMPO).

[0069] (K) Reactive surfactants Starting material (K) is an optional reactive surfactant that can be used to facilitate emulsion copolymerization and that can react to form part of the copolymer. The reactive surfactant has the formula:

[0070] [ka] (In the formula, R 2 , R 5 , D, D 1 , and R 6 is as above, and the subscript v1 may have a value sufficient to give the reactive surfactant a number average molecular weight of 300 to 950 g / mole, alternatively 350 g / mole to 900 g / mole. For example,

[0071] [ka] Reactive surfactants of the formula (wherein the subscript v1 has a value sufficient to give the reactive surfactant a number average molecular weight of 300 g / mol to 950 g / mol) are commercially available from Sigma-Aldrich, Inc. (St. Louis, Missouri, USA). The reactive surfactant is optional and may be added in an amount of 0 to 5 wt. % based on the total weight of the starting materials (A), (B), and (C), and, if present, (H) and (K). Reactive surfactants are commercially available, for example, from Ethox. Alternatively, the reactive surfactant may be added in an amount of greater than 0 to 2 wt. % on the same basis.

[0072] Method for preparing emulsion formulations suitable for treating textiles The copolymer prepared as described above and / or the aqueous emulsion prepared by the process including step (1) above can be used to prepare an emulsion formulation suitable for treating the above-mentioned textiles. For example, the emulsion formulation can be prepared by a process including shear mixing of starting materials including (I) the copolymer, (II) a nonionic surfactant, (III) water (which may be as described above for the starting material (E)), and (IV) a water-dispersible crosslinking agent (e.g., when the copolymer is formed by the above-mentioned alternative method, for example, by a method including dissolving one or more of the starting materials in an organic solvent, copolymerizing the starting materials (A) a crystalline monomer, (B) a silicone-(meth)acrylate macromonomer, (C) a crosslinking monomer, (F) an initiator, and, if present, (G) a chain transfer agent and / or (H) an additional monomer, followed by removing the solvent). Mixing under shear can be performed by any convenient means for forming an aqueous emulsion formulation (e.g., ultrasonication followed by microfluidization). Devices for mixing under shear (eg, sonicators, homogenizers, microfluidizers, and speed mixers) are known in the art and are commercially available.

[0073] In the emulsion formulation, the (II) nonionic surfactant is represented by the formula (II-1):

[0074] [ka] (In the formula, R 19 is a branched or linear alkyl group having 8 to 15 carbon atoms, the subscript n is at least 23, and each D 5 are independently selected alkylene oxide groups of 2 or more carbon atoms. 19 may be, for example, 2-ethylhexyl, lauryl, or other alkyl groups of 8 to 15 carbon atoms. Alternatively, the subscript n may be 23 to 40, or 23 to 30. Alternatively, each D 5 may be independently selected from the group consisting of ethylene oxide and propylene oxide. 5 may be ethylene oxide. Suitable alcohol ethoxylates of the above formula include C 11~15 secondary alkyl alcohol ethoxylates (e.g., TERGITOL™ 15-S-30 or 15-S-40, as described above); 2-ethylhexyl primary alcohol alkoxylates (e.g., 2-ethylhexyl ethylene oxide / propylene oxide sold under the trade names ECOSURF EH-30 and ECOSURF EH-40, as described above); 12~40 The emulsion formulation may further include an optional additional nonionic co-surfactant, which may be any of the nonionic surfactants described above as starting material (D-3) other than those of formula (II-1) above.

[0075] This process for preparing an emulsion formulation suitable for treating textiles may optionally further comprise adding additional starting materials, which may be selected from the group consisting of (V) wax, (VI) biocide, (VII) additional water (which may be the same as starting material (E)), (VIII) flame retardant, (IX) wrinkle reducing agent, (X) antistatic agent, (XI) penetrating agent, and combinations of two or more of (V)-(XI).

[0076] Alternatively, an emulsion formulation suitable for treating textiles can be prepared using the aqueous emulsion prepared by the process including step (1) above. To prepare the emulsion formulation, the process including step (1) above further includes step (2) of adding starting material (IV) a water-dispersible crosslinking agent to the aqueous emulsion. This process for preparing an emulsion formulation suitable for treating textiles may optionally further include adding an additional starting material after step (1). The additional starting material may be selected from the group consisting of (V) wax, (VI) biocide, (VII) additional water (which may be the same as starting material (D)), (VIII) flame retardant, (IX) wrinkle-reducing agent, (X) antistatic agent, (XI) penetrating agent, and a combination of two or more of (V) to (XI).

[0077] Step (2) of this process can be carried out by any convenient means, such as by mixing in a jacketed vessel equipped with a stirrer. Steps (1) and (2) can be carried out sequentially in the same vessel. Alternatively, steps (1) and (2) can be carried out in different equipment. Steps (1) and / or (2) can be carried out at room temperature or at elevated temperatures, e.g., up to 100°C, or 40°C to 80°C. Alternatively, step (1) can be carried out at heating and step (2) can be carried out at room temperature. Alternatively, one or both of steps (1) and (2) can be carried out at lower temperatures and elevated pressures, e.g., up to 5 atmospheres.

[0078] The process for preparing an emulsion formulation suitable for treating textiles may optionally further include adding an additional surfactant. Alternatively, if the process for preparing the copolymer includes a surfactant that is not nonionic (e.g., the above-mentioned (D-1) anionic surfactant, (D-4) amphoteric surfactant, and / or (D-2) cationic surfactant), the process for preparing the emulsion formulation may further include (3) removing the (D) surfactant (used in the process for making the aqueous emulsion containing the copolymer) and replacing the (D) surfactant with (II) a nonionic surfactant (which may be as described above for D-3). The starting materials (D-1) anionic surfactant, (D-2) cationic surfactant, and (D-4) amphoteric surfactant can be removed by any convenient means, such as adsorption, contact with an ion exchange resin, and / or filtration, such as dialysis and / or ultrafiltration. Alternatively, when the process for preparing the copolymer uses a nonionic surfactant other than the nonionic surfactant of formula (II-1) above as starting material (D-3), the process may further comprise removing all or part of the starting material (D-3) and replacing it with the nonionic surfactant of formula (II-1) by means as described above.

[0079] After the process for preparing the emulsion formulation is completed, the emulsion formulation suitable for treating textiles does not contain cationic surfactants. Alternatively, the emulsion formulation may be free of anionic surfactants, amphoteric surfactants, and cationic surfactants. "Free of anionic surfactants, amphoteric surfactants, and cationic surfactants" means that the surfactants in the emulsion formulation are only nonionic surfactants, or the emulsion formulation contains only an undetectable amount of another surfactant or an amount of another surfactant insufficient to adversely affect the durable water repellency of textiles treated with the emulsion formulation.

[0080] In addition to (I) the copolymer, emulsion formulations suitable for treating textiles include (II) a nonionic surfactant, as described above for starting material (D-3), and (III) water, as described above for starting material (E). Starting materials (IV), a water-dispersible crosslinking agent, and further additional starting materials, which may be selected from the group consisting of (V) a wax, (VI) a biocide, (VII) additional water (which may be the same as starting material (D)), (VIII) a flame retardant, (IX) a wrinkle-reducing agent, (X) an antistatic agent, and (XI) a penetrating agent, are described below.

[0081] Starting material (IV) Water-dispersible crosslinker Starting material (IV) is a water-dispersible crosslinking agent (crosslinker) that can be added to emulsion formulations for treating textiles. Suitable crosslinking agents include blocked isocyanates, polycarbodiimides, polyepoxy compounds, polycarboxy compounds, polyamines, and diols. The term "blocked isocyanates" encompasses mono-, di-, and polyisocyanates in which the isocyanate group has reacted with a blocking agent, releasing the isocyanate and blocking agent upon heating. Suitable blocking agents are known in the art, such as amines, amides, compounds with active hydrogen atoms, alcohols, or oximes. Blocked isocyanates are commercially available, for example, ARKOPHOB™ DAN and ARKOPHOB™ SR from Archroma (Reinach, Switzerland), RUCO-GUARD™ WEB from Rudolf GmbH (Geretsreid, Bayern, Germany), and PHOBOL™ XAN from Huntsman Corporation (Woodlands, Texas, USA). Examples of diols include 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 2-methyl-1,2-propanediol, 1,5-pentanediol, 2-methyl-2,3-butanediol, 1,6-hexanediol, 1,2-hexanediol, 2,5-hexanediol, 2-methyl-2,4-pentanediol, 2,3-dimethyl-2,3-butanediol, 2-ethylhexanediol, 1,2-octanediol, 1,2-decanediol, 2,2,4-trimethylpentanediol, 2-butyl-2-ethyl-1,3-propanediol, and 2,2-dimethyl-1,3-propanediol. Examples of suitable cross-linking agents are known in the art and are disclosed, for example, in U.S. Patent Application Publication No. 2017 / 0204558 to Knaup and U.S. Patent No. 9,777,105 to Hamajima et al. (beginning at column 11, line 54), which are incorporated herein by reference for purposes of describing suitable cross-linking agents.The exact amount of crosslinker (IV) will depend on various factors, including the type and amount of (I) silicone-(meth)acrylate copolymer and textile being treated, but the weight of crosslinker (IV) may be from 0.25% to 3.75%, alternatively from 0.25% to 1%, alternatively from 0.25% to 0.5%, of the fabric weight, on the same basis.

[0082] Starting material (V) wax Starting material (V) is a wax, which may optionally be added to provide improved water repellency or softness to textiles to which the emulsion formulation is applied. The amount of wax varies depending on factors including the type of wax selected, the desired benefit, and the fabric to be treated with the emulsion formulation. However, the amount of wax may be 0-75%, alternatively 0-50%, or alternatively 25-50%, based on the weight of (I) the silicone-(meth)acrylate copolymer. Alternatively, if used, the amount of wax may be greater than 0%, alternatively at least 10%, alternatively at least 25%, while the amount of wax may be up to 75%, alternatively up to 50%, on the same basis. Examples of suitable waxes include paraffin waxes (e.g., n-paraffin, isoparaffin, and / or cycloparaffin), silicone waxes, such as silicone waxes with long-chain alkyl groups (e.g., alkylmethylsilicone waxes) and / or amino-silicone waxes, and combinations of two or more of these. Suitable waxes are disclosed, for example, in U.S. Patent Application Publication No. 2017 / 0204558 to Knaup and U.S. Patent No. 10,844,151 to Probst et al. Waxes such as Michelman wax 743 and others from Michelman (Cincinnati, Ohio, USA) may be supplied as aqueous dispersions. Other waxes are also commercially available, for example, from Sasol Wax (Hamburg, Germany), and silicone waxes such as DOWSIL™ AMS-C30 are available from Dow Silicones Corporation (Midland, Michigan, USA).

[0083] Starting Material (VI) Biocide Starting material (VI) is a biocide. The amount of biocide varies depending on factors such as the type of biocide selected and the desired effect. However, when used, the amount of biocide can be greater than 0% to 5%, based on the total weight of all starting materials in the emulsion formulation. Starting material (VI) is exemplified by (VI-1) a fungicide, (VI-2) a herbicide, (VI-3) an insecticide, (VI-4) an antibacterial agent, or a combination thereof. Suitable biocides are disclosed, for example, in U.S. Pat. No. 9,480,977.

[0084] Starting material (XI) Penetrant Starting material (XI) is a penetrant. Suitable penetrants are exemplified by glycol ethers commercially available from The Dow Chemical Company, including DOWANOL™ DPM, TPM, PPh, EPh, Methyl CARBITOL™, and Butyl CARBITOL™.

[0085] When selecting starting materials to add to the aqueous emulsion described above in step (1) and the emulsion formulation formed as described above, there may be overlap between the types of starting materials, as a particular starting material described herein may have more than one function. The starting materials used in the aqueous emulsion and / or emulsion formulation may be different from each other.

[0086] Emulsion formulations suitable for treating textiles can be formulated using fluorocarbon-free starting materials, for example, the emulsion formulation may be free of any starting materials containing fluorine atoms covalently bonded to carbon atoms.

[0087] Textile treatment process The emulsion formulation prepared as described above can be used to treat textiles. For example, a method for treating textiles includes I) coating the textile with the emulsion formulation described above and II) heating the textile. Step I) may be carried out by any convenient method, such as padding, dipping, or spraying the emulsion formulation onto the textile. However, the method must be sufficient to deliver 0.25% to 10% by weight of (I) silicone-(meth)acrylate copolymer and 0.1% to 3.75%, or alternatively 0.25% to 1% by weight of (IV) water-dispersible crosslinking agent, based on the weight of the textile.

[0088] Step II) may be carried out by any convenient method, such as by placing the fabric in an oven. Heating of the fabric may be carried out to remove all or a portion of the water and / or to cure the emulsion formulation. The exact temperature will depend on various factors, including the temperature sensitivity of the type of fabric selected and the desired drying time. However, heating may be carried out at a temperature above 100°C to remove the water. Alternatively, the temperature may be above 100°C to 200°C for a time sufficient to remove all or a portion of the water, deblock the blocked isocyanate crosslinker, and / or cure the (I) silicone-(meth)acrylate copolymer.

[0089] The textile to be treated is not particularly limited. Suitable textiles include naturally occurring textiles such as cotton, silk, linen, and / or wool fabrics, textiles derived from synthetic sources such as rayon, acetate, polyester, polyamide (such as nylon), polyacrylonitrile, and polyolefins such as polyethylene and / or polypropylene, and combinations of two or more thereof (e.g., blends such as polyester / cotton blends). The form of the textile is also not particularly limited. The emulsion formulations described herein are suitable for use on any form of textile, for example, woven fabric, knitted fabric, or nonwoven fabric. [Example]

[0090] The following examples are provided to illustrate the present invention to one of ordinary skill in the art and should not be construed as limiting the invention as claimed. The starting materials used were as follows: The fabric to be treated was nylon (style #01194), which was purchased from Burlington and contained 98.61% nylon and 1.39% spandex. It weighed 6.84 oz / Lin Yd and was a plain weave. Another fabric to be treated was nylon, style 4774 075, with a basis weight of 220 g / m², also from Burlington. 2The crosslinking agent was a polyester or PES woven fabric (crepe). The water-dispersible crosslinker was PhobolXan™ extender (oxime-blocked isocyanate emulsion) purchased from Huntsman and used as received. The crystalline monomer (A-1) was stearyl acrylate, the crosslinking (meth)acrylate monomer (C-1) was 2-hydroxyethyl methacrylate (HEMA), the nonionic surfactant BRIJ™ L23-69 (69% active), the cationic surfactant ARQUAD™ 16-29 (hexadecyltrimethylammonium chloride, 29% active), the nonionic surfactant ECOSURF™ EH40 (75% active), the nonionic surfactant ECOSURF™ EH9 (100% active), the anionic surfactant DOWFAX 8390 (40% active), nonionic surfactant TERGITOL™ 15-S-40 (70% active), cationic surfactant n-dodecyltrimethylammonium bromide (DTAB, 100% active), chain extender dodecanethiol, initiator isoascorbic acid, initiator t-hydroperoxide (70% active), 3-(1,1,1,3,5,5,5-heptamethyltrisiloxane-3-yl)propyl methacrylate (MDM-ALMA), and 3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxane-3-yl)propyl methacrylate (3MT-ALMA) are commercially available and were purchased from commercial sources. A Fisherbrand™ Model 705 sonic dismembrator was used for sonication. The microfluidizer was a Microfluidics Microfluidizer Model 110Y homogenizer.

[0091] Initiator solution A was prepared as follows: 0.702 g of 70% t-butyl hydroperoxide was diluted with 45 mL of DI water to form a stock solution. 5 g of this stock solution was taken and mixed with 5 g of DI water to make the final solution.

[0092] Initiator solution B was prepared as follows: A stock solution was formed with 0.96 g of isoascorbic acid in 45 mL of DI water. The final solution was made by taking 5 g of this stock solution and mixing it with 5 g of DI water.

[0093] In this Reference Example 1, emulsion formulation samples were prepared as follows: stearyl acrylate (44 g), either MDM-ALMA or 3MT-ALMA (5, 10, or 15 g) (as shown in Table 1 below), HEMA (1 g), one or more surfactants (as shown in Table 1 below), and deionized water (200 g) were placed in a 400 mL jar. In some samples, 0.05 g of dodecanethiol was added (as shown in Table 1 below). The mixture was heated in a 40°C water bath for 10 minutes to melt the stearyl acrylate. The material was sonicated for 2 minutes at an amplitude of 50 using a sonicator to create a coarse emulsion. The coarse emulsion was then passed through a microfluidizer operating at 40°C and 10-15 kPSI. The resulting emulsion was then transferred to a 1000 mL, four-neck flask equipped with a reflux condenser, nitrogen inlet, overhead stirrer (IKA RW20), and thermocouple probe. The emulsion was stirred at 250 RPM with a Teflon blade and heated to 60°C. After reaching temperature, redox initiators were fed to the solution at 0.25 mL / min (Initiator Solution A and Initiator Solution B in separate feeds). After 1 hour at 60°C, the resulting emulsion formulation was then cooled to 30-40°C with slow stirring before being poured off.

[0094] [Table 1]

[0095] In Table 1, * The sample has the formula:

[0096] [ka] (where the subscript v1 indicates that the reactive surfactant also contained 0.5 g of reactive surfactant having a value sufficient to give the reactive surfactant an average Mn (number average molecular weight) of 360 g / mol, purchased from Sigma-Aldrich, Inc. (product 409537).

[0097] In this Reference Example 2, an emulsion formulation for treating the nylon fabric described above was prepared by combining 37 g of the copolymer emulsion prepared above, 6.16 g of PhobolXan™ extender, and 163 g of water in a plastic bottle and shaking by hand to mix so that the weight percentage on the fabric was approximately 2%.

[0098] In this Reference Example 3, an emulsion formulation for treating the PES fabric described above was prepared by combining 22 g of copolymer emulsion, 4.12 g of PhobolXan™ extender, and 174 g of water in a plastic bottle and shaking by hand to mix to a weight percent on the fabric of approximately 2%.

[0099] In this Example 4, textiles were coated with emulsion formulations prepared as described in Examples 2 and 3. A Mathis HVF padder (roll speed of 2 meters / minute at 60 psi) was used to coat the samples. The target weights on nylon (53.5% water absorption) and PES (90% water absorption) were 2% silicone-acrylate copolymer and 0.5% PhobolXan™ extender. Each emulsion formulation was added to the padder for coating and passed through a forced air oven at 160°C for 3 minutes.

[0100] In this Reference Example 5, water repellency and wash durability were evaluated as follows. Coated sheets prepared according to Reference Example 4 were laundered using a 90°F wash / cold rinse cycle and dried at approximately 150°F. This procedure was repeated 20 times. 37 g of Tide detergent (unscented) was used for every 6 pounds of coated sheets. Using ISO-9865 (Bundesmann test), appearance scoring data was collected after 0, 1, 5, 10, and 20 washes. Three values ​​were recorded. Appearance evaluation was subjective and based on the appearance or lack thereof of water droplets during the test. Appearance was considered passing if it was 3 or higher, and failing if it was less than 3. Furthermore, the fabric must absorb no more than 25% of its mass after the 10-minute test. In summary, a durable, water-resistant coating with a water absorption rate (%) of 25% or less and an appearance rating of 3 or higher was desired for all wash cycles tested. The results are shown in Tables 2 and 3 below.

[0101] [Table 2]

[0102] The data in Table 2 show that the examples containing nonionic surfactants had Bundesmann appearance scores of greater than 3 under all wash cycles tested on at least one fabric. In contrast, Examples 17, 18, 19, and 22, each containing a cationic surfactant, all failed the appearance test. Examples 20 and 21, each containing an anionic surfactant, all failed the appearance test.

[0103] [Table 3]

[0104] Issues to be resolved There is an industry need for non-fluorocarbon based fabric treatments that provide durable water repellency. Additionally, there is an industry need for fluorocarbon-free fabric treatments that have high durability as measured by the Bundesmann Test described above.

[0105] Industrial Applicability The above examples demonstrate that the emulsion formulations described herein can be used to treat textiles to impart durable water repellency as measured by the Bundesmann test. More specifically, the textiles can have both a Bundesmann appearance rating of 3 or greater after the initial treatment (0 washes) and after 1 to 10 washes, and a Bundesmann water absorption of 25% or less after the initial treatment and after 1 to 10 washes. This combination of properties can be achieved with at least one type of textile, and for some emulsion formulations, more than one type of textile.

[0106] Definitions and Use of Terms All amounts, ratios, and percentages are by weight unless otherwise specified. The Summary and Abstract are incorporated herein by reference. Unless the context of the specification dictates otherwise, the articles "a," "an," and "the" each refer to one or more. The transitional phrases "comprising," "consisting essentially of," and "consisting of" are used as set forth in sections §2111.03 I, II, and III of the Manual of Patent Examining Procedure, Ninth Edition, Revision 08.2017, Last Revised January 2018. The use of "for example," "e.g.," "such as," and "including" to list examples does not limit the list to only the examples listed. Thus, "for example" or "such as" means "for example, but not limited to" or "such as, but not limited to," and includes other similar or equivalent examples. Abbreviations used herein have the definitions in Table 5.

[0107] [Table 4]

[0108] The present invention has been described in an illustrative manner, and it should be understood that the terminology used is intended to be in the nature of terms of description rather than of limitation. With respect to any Markush group on which the description of an individual feature or aspect herein relies, different, unusual, and / or unexpected results may be obtained from each element of the respective Markush group, independently of all other elements of the Markush group. Each element of a Markush group may be relied upon and provided sufficient support for specific embodiments, individually and / or in combination, within the scope of the appended claims.

[0109] Furthermore, any ranges and subranges relied upon in describing the invention are understood to independently and inclusively fall within the scope of the appended claims and to describe and contemplate the entire range encompassing every and / or portion thereof, even if that whole and / or portion thereof is not expressly set forth herein. Those skilled in the art will readily recognize that the recited ranges and subranges fully describe and enable various embodiments of the invention, and that such ranges and subranges can be further delineated into relevant halves, thirds, quarters, fifths, and any other subranges contained within the ranges. By way of example only, the range "16-24" may be further divided into a lower third (i.e., 16-18), a middle third (i.e., 19-21), and an upper third (i.e., 22-24), or the range "16-24" may include the subrange "18-22," which are individually and collectively within the scope of the appended claims and may individually and / or collectively rely on and provide appropriate justification for specific embodiments within the scope of the appended claims. Additionally, with respect to terms defining or modifying ranges, such as "at least," "greater than," "less than," "less than," etc., such terms should be understood to include subranges and / or upper or lower limits.

[0110] Embodiments of the present invention In a first embodiment, a process for imparting durable water repellency to a textile comprises: I) coating the textile with an emulsion formulation; II) heating the fabric; The emulsion formulation comprises: (I) Unit formula:

[0111] [ka] (In the formula, Each R 1 is an independently selected alkyl group of 16 to 24 carbon atoms; Each R 2 is independently selected from the group consisting of H and methyl; Each D 2 is a divalent hydrocarbon group of 2 to 12 carbon atoms, Each R 3 are independently 4 and the formula -OSi(R 4 )3 groups, Each R 4 is an independently selected monovalent hydrocarbon radical of 1 to 12 carbon atoms; Each R 7 is independently selected from the group consisting of an oxygen atom and NH; D 3 is a divalent hydrocarbon group of 1 to 12 carbon atoms, Each D 4 is an alkylene group or a divalent alkylarylene group of 2 to 4 carbon atoms, The subscript v indicates the formula (OD 4 ) represents the number of units, The subscript v has a value between 0 and 12, Each R 8 is a crosslinkable group, Each R 5 is an oxygen atom, D is a divalent hydrocarbon group of 1 to 12 carbon atoms; Each D 1 is an alkylene group or a divalent alkylarylene group of 2 to 4 carbon atoms, The subscript v2 is the formula (OD 1) represents the number of units, The subscript v2 has a value between 0 and 20, Each R 6 is an alkoxy group or a hydroxy group, Each R 9 is a monovalent hydrocarbon group of 1 to 14 carbon atoms, Each R 10 are independently selected from the group consisting of halogens, acetate groups, or monovalent hydrocarbon groups of 1 to 14 carbon atoms; The subscripts w, x, y, y2, z1, and z2 represent the relative weight of each unit in the copolymer; The quantity (w+x+y+y2+z1+z2)=100, 80≦w<98, 1≦x≦5, 1≦y≦5, 0≦y2≦5, 0≦z1≦18, 0≦z2≦18) a silicone-(meth)acrylate copolymer having the formula: (II) Formula (II-1):

[0112] [ka] (In the formula, R 19 is a branched or linear alkyl group having 8 to 15 carbon atoms, the subscript n is at least 23, and each D 5 are independently selected alkylene oxide groups of 2 or more carbon atoms; and (III) water; (IV) a water-dispersible crosslinker; Including, However, the emulsion formulation does not contain a cationic surfactant.

[0113] In a second embodiment, in the process of the first embodiment, R 1 is a stearyl group, 83≦w≦93, and R 3is selected from the group consisting of -CH3 and -OSi(CH3)3, and R 4 is methyl, and D 2 is -(CH2)2-, 5≦x≦15, and R 7 is O, subscript v=0, R 8 is -OH, subscript y=2, subscript z1=0, and subscript z2=0.

[0114] In a third embodiment, the process of the first or second embodiment further comprises adding an additional starting material selected from the group consisting of a wax, a biocide, a flame retardant, a wrinkle reducing agent, an antistatic agent, a penetrating agent, or a combination of two or more thereof.

[0115] In a fourth embodiment, in the process of any one of the first to third embodiments, (II) the nonionic surfactant is C 11~15 Secondary Alkyl Alcohol Ethoxylate, 2-Ethylhexyl Primary Alcohol Alkoxylate, C 12~40 primary alcohol ethoxylates, primary alcohol ethoxylates, or combinations thereof.

[0116] In a fifth embodiment, in the process of any one of the first to fourth embodiments, the emulsion formulation further comprises a nonionic co-surfactant different from formula (II-1).

[0117] In a sixth embodiment, in the process of any one of the first to fifth embodiments, (IV) the water-dispersible crosslinking agent comprises a blocked isocyanate.

[0118] In a seventh embodiment, the process further comprises, before step I), (1) 80% by weight to 98% by weight of (A) formula:

[0119] [ka] (In the formula, R 1and R 2 is as defined above), and 1% by weight to 15% by weight of (B):

[0120] [ka] (In the formula, R 2 , R 3 , and R 4 wherein R is as defined above), and 1% by weight to 5% by weight of (C) formula:

[0121] [ka] (In the formula, R 2 , R 7 , D 3 , D 4 , R 8 and subscript v is as defined above), copolymerizing a starting material comprising The amounts of the starting materials (A), (B) and (C) total 100% by weight based on the total amount of the starting materials (A), (B) and (C), and the starting materials (A), (B) and (C) are (D) a surfactant; (III) water; (J) an initiator; copolymerized in an emulsion further comprising copolymerizing, thereby forming an aqueous emulsion comprising (I) the silicone-(meth)acrylate copolymer, (D) the surfactant, and (E) water; (2) combining the aqueous emulsion with (IV) additional starting materials, including the water-dispersible crosslinker; The method further comprises preparing the emulsion formulation by a method comprising:

[0122] In an eighth embodiment, in the process of the seventh embodiment, the (D) surfactant is not non-ionic, and the method further comprises (3) removing the (D) surfactant and replacing it with (II) a non-ionic surfactant.

[0123] In a ninth embodiment, in the process of the seventh embodiment or the eighth embodiment, the starting material (A) is selected from the group consisting of stearyl acrylate, stearyl methacrylate, behenyl methacrylate, behenyl acrylate, and combinations of two or more thereof.

[0124] In a tenth embodiment, in the process of any one of the seventh to ninth embodiments, the starting material (B) is selected from the group consisting of 3-(1,1,1,3,5,5,5-heptamethyltrisiloxan-3-yl)propyl methacrylate, 3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl methacrylate, and combinations thereof.

[0125] In an eleventh embodiment, in the process of any one of the seventh to tenth embodiments, the starting material (C) is 2-hydroxyethyl methacrylate.

[0126] In a twelfth embodiment, the process of any one of the seventh to eleventh embodiments further comprises adding an additional starting material in step (1), wherein the additional starting material is selected from the group consisting of (G) a chain transfer agent, (H) an additional monomer different from starting materials (A), (B), and (C), (J) an inhibitor, (K) a reactive surfactant different from starting material (D), and combinations of two or more thereof.

[0127] In a thirteenth embodiment, in the process of the twelfth embodiment, a reactive surfactant is present, the reactive surfactant having the formula:

[0128] [ka] (In the formula, R 2 , R 5 , D, D 1 , and R 6 is as above, with the subscript v1 having a value sufficient to give the reactive surfactant a number average molecular weight of 300 to 950 g / mole.

[0129] In a fourteenth embodiment, in the process of any one of the first to thirteenth embodiments, the woven fabric is selected from the group consisting of polyester and polyamide.

Claims

1. An emulsion formulation suitable for treating fabrics, comprising: (I) Unit formula: 【Chemical 1】 (wherein Each R １ is an alkyl group having 16 to 24 carbon atoms selected independently, Each R ２ is independently selected from the group consisting of H and methyl, Each D ２ is a divalent hydrocarbon group having 2 to 12 carbon atoms, Each R ３ are independently R ４ and the formula -OSi(R ４ ) ３ is selected from the group consisting of the groups Each R ４ is a monovalent hydrocarbon group having 1 to 12 carbon atoms which is independently selected, Each R ７ is independently selected from the group consisting of an oxygen atom and NH, D ３ is a divalent hydrocarbon group having 1 to 12 carbon atoms, Each D ４ is an alkylene group or a divalent alkylarylene group having 2 to 4 carbon atoms, The subscript v represents the number of units of the formula (OD ４ ) in the unit having the subscript y, the subscript v has a value of 0 to 12, Each R ８ is a crosslinkable group, Each R ５ is an oxygen atom, D is a divalent hydrocarbon group having 1 to 12 carbon atoms, Each D １ is an alkylene group having 2 to 4 carbon atoms or a divalent alkylarylene group, The subscript v2 represents the number of units of the formula (OD １ ) in the unit having the subscript y2. the subscript v2 has a value of 0 to 20, Each R ６ is an alkoxy group or a hydroxy group, Each R ９ is a monovalent hydrocarbon group having 1 to 14 carbon atoms, Each R １０ is independently selected from the group consisting of a halogen, an acetate group, or a monovalent hydrocarbon group having 1 to 14 carbon atoms, the subscripts w, x, y, y2, z1, and z2 represent the relative weights of each unit in the copolymer, the amount (w + x + y + y2 + z1 + z2) = 100, 80 ≦ w < 98, 1 ≦ x ≦ 15, 1 ≦ y ≦ 5, 0 ≦ y2 ≦ 5, 0 ≦ z1 ≦ 18, 0 ≦ z2 ≦ 18) a silicone-(meth)acrylate copolymer having, (II) formula: [Chemical Formula 2] (wherein R １９ is a branched or linear alkyl group having 8 to 15 carbon atoms, the subscript n is at least 23, and each D ５ is an alkylene oxide group of 2 or more carbon atoms independently selected), and a nonionic surfactant containing an alcohol alkoxylate (III) water, (IV) a water-dispersible crosslinking agent, provided that the emulsion formulation does not contain a cationic surfactant.

2.

3. R １ is a stearyl group, 83 ≦ w ≦ 93, and R ３ is -CH ３ and -OSi(CH ３ ) ３ selected from the group consisting of, and R ４ is methyl, D ２ is -(CH ２ ) ２ -, 5 ≦ x ≦ 15, and R ７ is O, subscript v = 0, R ８ is -OH, subscript y = 2, subscript z1 = 0, and subscript z2 = 0, the emulsion formulation according to claim 1. The emulsion formulation according to claim 1 or claim 2, further comprising an additional starting material selected from the group consisting of wax, biocide, flame retardant, wrinkle reducing agent, antistatic agent, penetrant, or a combination of two or more thereof.

4. (II) The non-ionic surfactant is

5. C １１～１５ a secondary alkyl alcohol ethoxylate, a 2-ethylhexyl primary alcohol alkoxylate, C １２～４０ a primary alcohol ethoxylate, or a combination thereof, the emulsion formulation according to claim 1 or claim 2. (IV) The water-dispersible crosslinking agent contains a blocked isocyanate, and the emulsion formulation according to claim 1 or claim 2.

6. A method for preparing the emulsion formulation according to claim 1 or claim 2, comprising: copolymerizing starting materials comprising 80% to 98% by weight of (A) formula: （１） 1% to 15% by weight of (B) formula: [Chemical Formula 3] (wherein, R １ and R ２ are as described above), and the crystalline monomer, 1% to 5% by weight of (C) formula: 【Chemical Formula 4】 (wherein, R ２ , R ３ , and R ４ are as described above) and a silicone-(meth)acrylate macromonomer, such that the amounts of starting materials (A), (B), and (C) total 100% by weight based on the total amount of starting materials (A), (B), and (C), and copolymerizing starting materials (A), (B), and (C) 【Chemical Formula 5】 (wherein, R ２ , R ７ , D ３ , D ４ , R ８ , and the subscript v are as described above), and a crosslinkable (meth) acrylate monomer, in an emulsion further comprising (D) a surfactant, (III) water, (J) an initiator, thereby forming an aqueous emulsion comprising (I) the silicone-(meth)acrylate copolymer, (D) the surfactant, and (E) the water, and (2) combining the aqueous emulsion with an additional starting material comprising (IV) the water-dispersible crosslinking agent. A method comprising the above steps.

7. (D) The surfactant is not non-ionic, and the method further comprises (3) removing (D) the surfactant and replacing it with (II) the non-ionic surfactant, and the process according to claim 6.

8. ​ ​ The process according to claim 6, wherein the starting material (A) is selected from the group consisting of stearyl acrylate, stearyl methacrylate, behenyl methacrylate, behenyl acrylate, and combinations of two or more thereof.

9. The process according to claim 6, wherein the starting material (B) is selected from the group consisting of 3-(1,1,1,3,5,5,5-heptamethyltrisiloxan-3-yl)propyl methacrylate, 3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl methacrylate, and combinations thereof.

10. The process according to claim 6, wherein the starting material (C) is 2-hydroxyethyl methacrylate.

11. The process according to claim 6, further comprising adding an additional starting material in step (1), wherein the additional starting material is selected from the group consisting of (G) a chain transfer agent, (H) an additional monomer different from the starting materials (A), (B), and (C), (J) an inhibitor, (K) a reactive surfactant different from the starting material (D), and combinations of two or more thereof.

12. The reactive surfactant is present, and the reactive surfactant has the formula: 【Chemical Formula 6】 (wherein R ２ , R ５ , D, D １ , and R ６ are as defined above, and the subscript v1 has a value sufficient to give the reactive surfactant a number average molecular weight of from 300 to 950 g / mol), the process according to claim 11.

13. The process according to claim 6, further comprising adding a further additional starting material after step (1), wherein the further additional starting material is selected from the group consisting of wax, biocide, flame retardant, anti-wrinkle agent, antistatic agent, penetrant, and combinations of two or more thereof.

14. A process for treating a fabric, comprising: I) coating the fabric with the emulsion formulation according to claim 1; and II) heating the fabric.

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