Emulsion formulations for treating textiles containing silicone-(meth)acrylate copolymers and silicone additives

Abstract

The emulsion formulation includes a silicone-(meth)acrylate copolymer and a silicone additive, and can be coated onto a textile and dried to impart both durable water repellency and softness to the textile.

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 / 277671, filed November 10, 2021. U.S. Provisional Patent Application No. 63 / 277671 is incorporated herein by reference.

[0002] FIELD OF THEINVENTION Silicone-(meth)acrylate copolymers (copolymers) and methods for preparing same via emulsion polymerization are provided. An aqueous emulsion of the copolymer can be combined with an aqueous emulsion of a silicone additive to form an emulsion formulation suitable for treating textiles to impart durable water repellency and softness to the textiles. [Background technology]

[0003] Introduction 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 have contributed 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] A suitable emulsion formulation for treating textiles includes (I) a silicone-(meth)acrylate copolymer, (II) an additive, (III) a water-dispersible crosslinker, (IV) a surfactant, and (V) water. The textiles can be treated by coating the textile with the emulsion formulation and heating the textile. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0005] A process for forming an emulsion formulation suitable for treating textiles includes combining (I) a first aqueous emulsion containing a silicone-(meth)acrylate copolymer with a second aqueous emulsion containing (II) an additive, (III) a water-dispersible crosslinker, and optionally one or more additional starting materials described below. Alternatively, the process for preparing the above emulsion formulation includes: 1) The starting material (I), a silicone-(meth)acrylate copolymer, (A) 80% by weight to 98.75% by weight of the formula

[0006] [ka] A crystalline monomer of formula (wherein R 1 and R 2 (as above), and (B) 0.25% by weight to 15% by weight of the formula

[0007] [ka] Silicone-(meth)acrylate macromonomers of the formula 2 , D 2 , and R 3 (as above), and (C) 1% by weight to 5% by weight of the formula

[0008] [ka] A crosslinkable (meth)acrylate monomer of the formula 7 , D 3 , D 4 , subscript v, and R 8 (as above), and (D) a surfactant; (E) water; (F) an initiator; and thereby forming (I) a first aqueous emulsion comprising a silicone-(meth)acrylate copolymer; 2) (II) providing a second aqueous emulsion comprising an additive, (D'), a surfactant, and (E') water; 3) mixing ingredients including the first aqueous emulsion prepared in step 1), the second aqueous emulsion from step 2), (III) a water-dispersible crosslinker, and optionally one or more additional starting ingredients selected from the group consisting of additional surfactants, waxes, biocides, additional water, flame retardants, wrinkle reducing agents, antistatic agents, and penetrating agents.

[0009] (I) Silicone-(meth)acrylate copolymer The silicone-(meth)acrylate copolymer (copolymer) comprises the following unit formula:

[0010] [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; 2 is a divalent hydrocarbon radical of 2 to 12 carbon atoms, and each R 3 is expressed by the formula OSi(R 4 ) 3 where each R 4 are independently R and DSi(R 5 ) 3 each R is an independently selected monovalent hydrocarbon radical of 1 to 12 carbon atoms; each D is independently selected from the group consisting of an oxygen atom, a (poly)alkylene oxide group of 1 to 12 units, and a divalent hydrocarbon radical of 2 to 4 carbon atoms; and each R 5 are independently R and DSi(R 6 ) 3 Each R is selected from the group consisting of 6 are independently R and DSiR 3 where R is selected from the group consisting of4 , R 5 , and R 6 is selected such that the silicone-(meth)acrylate macromonomer unit having subscript w has at least 6 silicon atoms, and each R 7 is independently selected from the group consisting of an oxygen atom and NH; D 3 is a divalent hydrocarbon radical of 1 to 12 carbon atoms, D 4 is an alkylene group or a divalent alkylarylene group of 2 to 4 carbon atoms, and the subscript v represents the formula (OD 4 ) units, the subscript v has a value from 0 to 12, and each R 8 is a crosslinkable group, and each R 9 is a monovalent hydrocarbon radical of 1 to 14 carbon atoms, and each R 10 are 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, z1, and z2 represent the relative weights of each unit in the copolymer, where subscript x has a value of 0.25 to 15, subscript w has a value of 80 to 98.75, subscript y has a value of 1 to 5, subscript z1 has a value of 0 to 18.75, and subscript z2 has a value of 0 to 18.75, such that the amount (w+x+y+z1+z2)=100. The copolymer further comprises a terminal moiety.

[0011] In the above formula, R 1 has 16 to 24 carbon atoms. 1 R may have 16 to 22 carbon atoms, alternatively 18 to 24 carbon atoms, alternatively 18 to 22 carbon atoms. 1 may be selected from the group consisting of stearyl, eicosyl, and behenyl. 1 can be stearyl.

[0012] In the above formula, each R 3 is expressed by the formula OSi(R 4 ) 3 where each R 4 are independently R and DSi(R5 ) 3 each R is an independently selected monovalent hydrocarbon radical of 1 to 12 carbon atoms; each D is independently selected from the group consisting of an oxygen atom, a (poly)alkylene oxide group of 1 to 12 units, and a divalent hydrocarbon radical of 2 to 4 carbon atoms; and each R 5 are independently R and DSi(R 6 ) 3 Each R is selected from the group consisting of 6 are independently R and DSiR 3 where R is selected from the group consisting of 4 , R 5 , and R 6 is selected such that the silicone-(meth)acrylate macromonomer unit having the subscript w has at least 6 silicon atoms. 4 , R 5 , and R 6 is selected such that the units have at least 6 silicon atoms per unit, alternatively 6-20 silicon atoms, alternatively 7-19 silicon atoms, alternatively 8-18 silicon atoms, alternatively 9-17 silicon atoms, alternatively 10-16 silicon atoms.

[0013] In the silicone-(meth)acrylate macromonomer units, each R is a monovalent hydrocarbon group of 1 to 12 carbon atoms. The monovalent hydrocarbon group of R can be an alkyl group, such as an alkyl group of 1 to 6 carbon atoms. Alternatively, the alkyl group can have 1 to 3 carbon atoms, or alternatively 1 to 2 carbon atoms. Alternatively, each R group can be methyl.

[0014] Each D is independently selected from the group consisting of an oxygen atom, a (poly)alkylene oxide group of 1 to 12 units, and a divalent hydrocarbon group of 2 to 4 carbon atoms. 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 is a divalent hydrocarbon radical of 1 to 12 carbon atoms. Alternatively, each D 3may be an alkylene group or ethylene. 4 is an alkylene group of 2 to 4 carbon atoms or a divalent alkylarylene group.

[0015] D 4 The divalent hydrocarbon group is an alkylene group such as ethylene, propylene, or butylene, an arylene group such as phenylene, or

[0016] [ka] where each subscript u is independently 1 to 6, alternatively 1 to 2. Alternatively, the divalent hydrocarbon group may be an alkylene, or the divalent hydrocarbon group may be ethylene. D 2 and D. 3 The divalent hydrocarbon group of may be the same as those described above, or may be methylene. The divalent hydrocarbon group of D may be an alkylene, such as ethylene, propylene, butylene, etc. Alternatively, each D may be ethylene.

[0017] The (poly)alkylene oxide group for D may have 2 to 4 carbon atoms per unit, for example, the formula D 5 (OD 6 ) v’ -OR, wherein D 5 is an alkylene group of 2 to 4 carbon atoms, D 6 is an alkylene group of 2 to 4 carbon atoms, R is as defined above, and subscript v' is 0 to 12. Alternatively, subscript v' can be 0 or 1. Alternatively, subscript v' can be 0. Examples of (poly)alkylene oxide groups include ethylene oxide-propylene oxide.

[0018] Alternatively, each D may be selected from an oxygen atom and a divalent hydrocarbon group. Alternatively, each divalent hydrocarbon group of D may be an alkylene group, such as ethylene. Alternatively, each D may be oxygen. Alternatively, in the same unit, some instances of D may be oxygen and other instances of D may be alkylene.

[0019] In the above formula, each R 7 is independently selected from the group consisting of an oxygen atom and NH. 7 may be oxygen.

[0020] 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.

[0021] 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 combinations thereof. 9 R may be an alkyl or aryl group, may be monocyclic or polycyclic, and may optionally have linear or branched groups. 9 Examples of suitable alkyl groups include methyl, t-amyl, butyl (including t-butyl), cyclohexyl, isodecyl, isobornyl, and 2-ethylhexyl. Examples of suitable aryl groups include phenyl, naphthyl, anthracyl, and benzyl.

[0022] In the above formula, R 10 is R 9As 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 it may be Br, Cl or F, or it may be Cl or Br, or it may be Cl.

[0023] In the above unit formula, the subscripts w, x, y, and z are the relative weights of each unit, and the amount (w+x+y+z) may sum to 100. The subscript w has a value between 80 and 98.75. 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. At the same time, the subscript w may be up to 98.75, alternatively up to 98, alternatively up to 97, alternatively up to 96, 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, the subscript w may be 80 to 98, alternatively 81 to 97, alternatively 82 to 96, alternatively 82 to 95, alternatively 85 to 90.

[0024] The subscript x has a value of 0.25 to 15. Alternatively, the subscript x is at least 0.25, alternatively at least 0.5, alternatively at least 0.75, alternatively at least 1, alternatively at least 2, alternatively at least 3, alternatively at least 4, alternatively at least 5. At the same time, 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 5 to 15, alternatively 10.

[0025] 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 2, alternatively at least 1.75. At the same time, the subscript y may be up to 5, alternatively up to 4, alternatively up to 3, alternatively up to 2.75, alternatively up to 2.5, alternatively up to 2.25. Alternatively, the subscript y may be 1 to 3, alternatively 1 to 2, alternatively 1.5 to 2.5, alternatively 1.75 to 2.25, alternatively 2.

[0026] 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 18.75, alternatively up to 15, alternatively up to 10, alternatively up to 8, alternatively up to 5. Alternatively, the subscript z1 may be 0 to 18.75, alternatively greater than 0 to 18.75, alternatively 0.5 to 7, alternatively 1 to 6, alternatively 2 to 5.

[0027] 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 up to 7, alternatively up to 6, alternatively up to 5, alternatively up to 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.

[0028] 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, preferably 200,000 g / mol to 3,000,000 g / mol. The units shown above may be in any order, for example, the copolymer may be a random copolymer or a block copolymer.

[0029] Those skilled in the art will recognize that the copolymers may be prepared by radical polymerization via a process such as that described below, and that this process forms end moieties for the copolymers. The copolymers further include end moieties that may be derived from an initiator, a 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.

[0030] The copolymer is 1) (A) 80% by weight to 98.75% by weight of the formula

[0031] [ka] A crystallizable monomer of the formula R 1 is an alkyl group of 16 to 24 carbon atoms as described above, and R 2 is selected from the group consisting of H and methyl, as defined above; (B) 0.25% by weight to 15% by weight of the formula

[0032] [ka] Silicone-(meth)acrylate macromonomers of the formula 3 is expressed by the formula OSi(R 4 ) 3 Each R 4 are independently R and DSi(R 5 ) 3 wherein each R is an independently selected monovalent hydrocarbon radical of 1 to 12 carbon atoms, each D is independently selected from the group consisting of an oxygen atom, a (poly)alkylene oxide group of 1 to 12 units, and a divalent hydrocarbon radical of 2 to 4 carbon atoms, and each R 5 are independently R and DSi(R 6 ) 3Each R is selected from the group consisting of 6 are independently R and DSiR 3 where R is selected from the group consisting of 4 , R 5 and R 6 is selected as above such that the macromonomer has at least 6 silicon atoms per molecule; (C) 1% by weight to 5% by weight of the formula

[0033] [ka] A crosslinkable (meth)acrylate monomer of the formula 7 is independently selected from oxygen and NH; D 3 is a divalent hydrocarbon group of 1 to 12 carbons, D 4 is a divalent radical of 2 to 4 carbon atoms, the subscript v is 0 to 12, R 8 are crosslinkable groups, each as defined above, (D) a surfactant; (E) water; (F) copolymerizing the starting materials, Thereby, it may be prepared via a process that includes forming an aqueous emulsion that includes (I) a silicone-(meth)acrylate copolymer, (D) a surfactant, and (E) water.

[0034] A process for preparing an emulsion formulation suitable for preparing a textile fabric may include carrying out step 1) above, thereby forming a first aqueous emulsion; and 2) combining the first aqueous emulsion prepared in step 1) with a second aqueous emulsion comprising (II) an additive (as introduced above and described in detail below), (III) a water-dispersible crosslinker (as introduced above and described in detail below), and optionally one or more additional starting materials.

[0035] Alternatively, one or more additional starting materials may be added in step 1) to produce a copolymer. For example, starting materials selected from the group consisting of (H) a chain transfer agent, (J) an additional non-crystallizable monomer different from each of (A), (B) and (C), (K) an initiator, and combinations of two or more of (H), (J) and (K) may be added in step 1).

[0036] Step (1) of the above process may include forming an emulsion including starting materials (A), (B), (C), (D), (E), and (F) (and optionally (H), (J), and / or (K)). If starting material (A) is a solid at room temperature, it may be heated at 30° C. to 50° C. for a sufficient temperature and time 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, such as ultrasonicators, homogenizers, microfluidizers, and speed mixers, are 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, (H) and (J)) are copolymerized to form (I) a silicone-(meth)acrylate copolymer, together with starting materials (D) and (E) (and, if present, (K)) in an aqueous emulsion.

[0037] Step 2) of the above process for producing an emulsion formulation may be carried out by any convenient means, such as mixing in a jacketed vessel equipped with an agitator. Steps 1) and 2) may be carried out sequentially in the same vessel. Alternatively, steps 1) and 2) may be carried out in different equipment. Steps 1) and / or 2) may be carried out at room temperature or at elevated temperatures, for example up to 100°C, or from 40°C to 80°C. Alternatively, heating may be carried out in step 1) and step 2) may be carried out at room temperature. Alternatively, one or both of steps 1) and 2) may be carried out at lower temperatures and elevated pressures, such as up to 5 atmospheres.

[0038] Alternatively, the copolymers may be prepared by a method that includes dissolving one or more of the starting materials in an organic solvent (e.g., a monohydric alcohol) and copolymerizing starting materials (A), (B), (C), (F), and, if present, (H) and / or (J) by varying the appropriate starting materials and their amounts in a process such as that disclosed in U.S. Pat. No. 10,047,199 to Iimura et al. The resulting copolymer may be solvent-based. All or a portion of the solvent may be removed by any convenient means, such as stripping or distillation using heat and, optionally, reduced pressure. The copolymer may be emulsified using (D) a surfactant and (E) water. The starting materials for producing the copolymers and emulsion formulations containing the copolymers are further described below.

[0039] The starting material (A) is represented by the formula (A-1):

[0040] [ka] A crystallizable monomer of the formula R 1 and R 2(wherein R is 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. Suitable crystallizable 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.±5° C.

[0041] Starting material (A) is used in an amount of 80% to 98.75%, based on the combined weight of starting materials (A), (B), and (C), and, if present, (J). 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%, on the same basis. At the same time, the amount of starting material (A) may be up to 98.75%, alternatively up to 98%, alternatively up to 97%, alternatively up to 96%, 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%, on the same basis. Alternatively, the amount of starting material (A), on the same basis, may be from 80% to 98%, alternatively from 81% to 97%, alternatively from 82% to 96%, alternatively from 82% to 95%, alternatively from 85% to 90%.

[0042] The starting material (B) is represented by the formula (B-1):

[0043] [ka] Silicone-(meth)acrylate macromonomers of the formula 2, D 2 , and R 3 is as above).

[0044] Alternatively, the starting material (B) is represented by the formula (B-2):

[0045] [ka] (In the formula, R 2 , R 4 , and R 5 is as defined above).

[0046] Alternatively, the starting material (B) has the formula (Si10):

[0047] [ka] 3-(5-((1,1,1,3,5,5,5-heptamethyltrisiloxan-3-yl)oxy)-1,1,1,3,7,9,9,9-octamethyl-3,7-bis((trimethylsilyl)oxy)pentasiloxan-5-yl)propyl methacrylate, of formula (Si16):

[0048] [ka] and combinations thereof. The starting material (B) may comprise a macromonomer selected from the group consisting of 3-(1,5-bis(2-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)ethyl)-3-(((2-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)ethyl)dimethylsilyl)oxy)-1,1,5,5-tetramethyltrisiloxan-3-yl)propyl methacrylate having the formula:

[0049] Starting material (B) is used in an amount of 0.25% to 15%, based on the combined weight of starting materials (A), (B), and (C), and (J), if present. Alternatively, starting material (B) may be used in an amount of at least 0.25%, alternatively at least 0.5%, alternatively at least 0.75%, alternatively at least 1%, alternatively at least 2%, alternatively at least 3%, alternatively at least 4%, alternatively at least 5%, on the same basis. At the same time, starting material (B) may be present in an amount of up to 15%, alternatively up to 14%, alternatively up to 13%, alternatively up to 12%, alternatively up to 11%, alternatively up to 10%, on the same basis. Alternatively, the amount of starting material (B) may be 1% to 14%, alternatively 2% to 13%, alternatively 3% to 12%, alternatively 4% to 11%, alternatively 5% to 10%, alternatively 5% to 15%, alternatively 10%, on the same basis as above.

[0050] Starting material (C) Crosslinkable (meth)acrylate monomer The starting material (C) has the formula (C-1):

[0051] [ka] (In the formula, R 2 , R 7 , D 3 , R 8 and subscript v are as 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:

[0052] [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.

[0053] 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, (J). The amount of starting material (C) may be at least 1%, alternatively at least 1.25%, alternatively at least 1.5%, alternatively at least 2%, alternatively at least 1.75%, on the same basis. At the same time, the amount of starting material (C) may be up to 5%, alternatively up to 4%, alternatively up to 3%, alternatively up to 2.75%, alternatively up to 2.5%, alternatively up to 2.25%, on the same basis. Alternatively, the amount of starting material (C) may be 1% to 3%, alternatively 1% to 2%, alternatively 1.5% to 2.5%, alternatively 1.75% to 2.25%, alternatively 2%, on the same basis.

[0054] Starting material (D) Surfactant The starting material (D) is a surfactant. The surfactant may be selected from the group consisting of (D-1) cationic surfactants, (D-2) nonionic surfactants, and (D-3) a combination of both cationic and nonionic surfactants. Cationic surfactants useful herein include compounds containing a quaternary ammonium hydrophilic moiety in the molecule that is positively charged, such as those represented by the formula (D-1-1): 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 compounds may be alkyltrimethylammonium and dialkyldimethylammonium halides or acetates, each having at least 8 carbon atoms in the alkyl substituent. Dialkyldimethylammonium salts can be used and are represented by the formula (D-1-2): R 16 R 17 N + (CH 3 ) 2 X' - (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 be used, represented by the formula (D-1-3): R 18 N + (CH 3 ) 3 X” - (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, acetate.

[0055] 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™.

[0056] Other suitable cationic surfactants that can be used include fatty acid amines and amides, and their salts and derivatives, such as fatty fatty amines and their derivatives.Commercially available such cationic surfactants include the composition sold under the trade name ARQUAD T27 W, ARQUAD 16-29 by Akzo Nobel Chemicals Inc. (Chicago, Illinois), and the composition sold under the trade name Ammonyx Cetac-30 by Stepan Company (Northfield, Illinois, USA).

[0057] The amount of (D-1) cationic surfactant may be 0.1% to 5% based on the weight of the starting material (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%, alternatively at least 0.5%, while the amount of cationic surfactant may be up to 5%, alternatively up to 4%, alternatively up to 3%, alternatively up to 2%, alternatively up to 1%, on the same basis. Alternatively, the amount of cationic surfactant may be 0.2% to 4%, alternatively 0.3% to 3%, alternatively 0.4% to 2.5%, alternatively 0.5% to 2%, on the same basis.

[0058] The starting material (D-2) is a non-ionic surfactant. Some suitable non-ionic surfactants that can be used include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, alkyl glucosides, polyoxyethylene fatty acid esters, sorbitan fatty acid esters, and polyoxyethylene sorbitan fatty acid esters. 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; (ii) C11-15 secondary alkyl polyoxyethylene ethers sold under the trade names TERGITOL™ 15-S-7, TERGITOL™ 15-S-9, TERGITOL™ 15-S-15, TERGITOL™ 15-S-30, and TERGITOL™ 15-S-40 by Dow Chemical Company, Midland, Michigan, USA; octylphenyl polyoxyethylene (40) ether sold under the trade name TRITON™ X405 by Dow Chemical Company; (iii) nonylphenyl polyoxyethylene (10) ether sold under the name MAKON™ 10 by Stepan Company; (iv) phenylphenyl polyoxyethylene (10) ether sold under the name MAKON™ 10 by Henkel Chemical Company; (v) ethoxylated alcohols sold under the trade names BRIJ™ L23 and BRIJ™ L4 by Croda Inc., Edison, New Jersey, USA; (vi) alkyl oxoalcohol polyglycol ethers (e.g., GENAPOL™ UD050, and GENAPOL™ UD110); (vii) alkyl polyethylene glycol ethers based on C10 Guerbet alcohols and ethylene oxide (e.g., LUTENSOL™ XP79).

[0059] Suitable nonionic surfactants also include poly(oxyethylene)-poly(oxypropylene)-poly(oxyethylene) tri-block copolymers. Poly(oxyethylene)-poly(oxypropylene)-poly(oxyethylene) tri-block copolymers are also commonly known as poloxamers. They are nonionic triblock copolymers consisting of a central hydrophobic chain, which is polyoxypropylene (poly(propylene oxide)), flanked by two hydrophilic chains, which are polyoxyethylene (poly(ethylene oxide)). Poly(oxyethylene)-poly(oxypropylene)-poly(oxyethylene) tri-block copolymers are commercially available from BASF (Florham Park, New Jersey, USA) and are sold under the trade name PLURONIC™, such as PLURONIC™ L61, L62, L64, L81, P84.

[0060] Other suitable nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenol ethers, polyoxyethylene lauryl ethers, 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, and polyoxyalkylene glycol modified polysiloxane surfactants. Commercially available nonionic surfactants that can be used include 2,6,8-trimethyl-4-nonyloxypolyethyleneoxyethanol (6EO) and (10EO), sold under the trademarks TERGITOL™ TMN-6 and TERGITOL™ TMN-10; alkyleneoxypolyethyleneoxyethanol (C EO), sold under the trademarks TERGITOL™ 15-S-7, TERGITOL™ 15-S-9, TERGITOL™ 15-S-15; 11~15secondary alcohol ethoxylates 7EO, 9EO, and 15EO; other C sold under the trademarks TERGITOL® 15-S-12, 15-S-20, 15-S-30, 15-S-40 11~15 Secondary alcohol ethoxylates, including compositions such as octylphenoxypolyethoxyethanol (40EO) sold under the trademark TRITON™ X-405, and alcohol ethoxylates branded ECOSURF™ EH, such as ECOSURF™ EH-40. All of these surfactants are sold by Dow Chemical Company.

[0061] Other useful commercial nonionic surfactants are nonylphenoxypolyethoxyethanol (10EO), sold under the trademark MAKON® 10 by Stepan Company, polyoxyethylene 23 lauryl ether (Laureth-23), sold under the trademark BRIJ® 35L by ICI Surfactants (Wilmington, Delaware, USA), and RENEX® 30, a polyoxyethylene ether alcohol also sold by ICI Surfactants.

[0062] Nonionic surfactants can also be silicone polyethers (SPEs). Silicone polyethers as emulsifiers can have a pitchfork structure, in which polyoxyethylene or polyoxyethylene-polyoxypropylene copolymer units are grafted to a siloxane backbone, or SPEs can have an ABA block copolymer structure, in which A represents the polyether portion and B represents the siloxane portion of the ABA structure. Suitable SPEs include DOWSIL OFX-5329 Fluid, manufactured by Dow Silicones Corporation (Midland, Michigan, USA). Alternatively, nonionic surfactants can 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.

[0063] The starting material (D-2) nonionic surfactant may be provided in dilution and the amount used may be sufficient to provide 0.1% to 6% surfactant based on the weight of the starting material (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%, while at the same time, the amount of nonionic surfactant may be up to 5%, alternatively up to 4%, alternatively up to 3%, alternatively up to 2%, alternatively up to 1%, on the same basis. Alternatively, the amount of nonionic surfactant may be 0.2% to 4%, alternatively 0.3% to 3%, alternatively 0.4 to 2.5%, alternatively 0.5% to 2%, on the same basis. Alternatively, the starting materials (D-1) cationic surfactant and (D-2) nonionic surfactant may be present in a combined amount of 10% or less, based on the weight of the starting material (I) silicone-(meth)acrylate copolymer in the aqueous emulsion.

[0064] 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 provided by a municipal water system or well water used without further purification). The amount of water is sufficient to form an aqueous emulsion for emulsion polymerization in step 1) of the above process. Additional water may be added after step 1). For example, the first aqueous emulsion and / or the second aqueous emulsion prepared as above may be diluted with additional water to achieve the desired amount of starting material before treating the textile with the emulsion formulation. In step 1), 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 combined 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%, alternatively up to 80%, based on the same basis.

[0065] Without wishing to be bound by theory, it is believed that starting materials (A), (B), and (C), and, if present, (J), copolymerize to form (I) a silicone-(meth)acrylate copolymer, described herein as starting material (I). Additionally, starting materials (D) surfactant and (E) water are believed not to participate in the copolymerization reaction, although copolymers including one or both of starting materials (D) and (E) are not excluded from the scope of this specification.

[0066] Starting material (I) Silicone-(meth)acrylate copolymer The silicone-(meth)acrylate copolymer may be prepared by emulsion copolymerization of starting materials including (A), (B), (C) and (F) above. Alternatively, the silicone-(meth)acrylate copolymer may be the reaction product of starting materials consisting essentially of starting materials (A), (B), (C) and (F) (and, if present, (H) a chain transfer agent and / or (J) additional monomer). Alternatively, the silicone-(meth)acrylate copolymer may be the reaction product of starting materials consisting of starting materials (A), (B), (C) and (F) (and, if present, (H) and / or (J)). Without wishing to be bound by theory, it is believed that neither starting material (D) nor (E) copolymerizes with starting materials (A), (B) and (C) but merely serves as a vehicle for the copolymerization. However, nothing herein excludes the possibility that a portion of one or more of starting materials (D) and / or (E), or any other starting materials added during the course of the process, may participate in a copolymerization reaction of starting materials including (A), (B), (C) and (F).

[0067] In emulsion formulations suitable for treating textiles, the (I) silicone-(meth)acrylate copolymer may be present in an amount of 57.2% to 88.5%, based on the combined weight of all starting materials in the emulsion formulation, excluding water. Alternatively, the amount of the (I) silicone-(meth)acrylate copolymer may vary depending on factors such as the type of fabric being treated. For example, the amount of the (I) silicone-(meth)acrylate copolymer may be 58.2% to 88.5%, on the same basis, when the textile being treated is polyester. Alternatively, the amount of the (I) silicone-(meth)acrylate copolymer may be 57.2% to 79.3%, on the same basis, when the textile being treated is a polyamide, such as nylon.

[0068] Starting material (III) Water-dispersible crosslinker The starting material (III) is a water-dispersible crosslinking agent (crosslinker) that can be added to the emulsion formulation for treating textiles, for example, to accelerate the curing of the (I) silicone-(meth)acrylate copolymer and (II) additive. The starting material (III) may be combined with the first aqueous emulsion prepared in step 1). Alternatively, the starting material (III) may be combined with the second aqueous emulsion in step 2) of the process for preparing an emulsion formulation suitable for treating textiles. Alternatively, the first aqueous emulsion and the second aqueous emulsion may be combined to form a third aqueous emulsion, to which the (III) water-dispersible crosslinking agent is then added. Suitable water-dispersible crosslinking agents include blocked isocyanates and diols. The term "blocked isocyanates" encompasses mono-, di-, and polyisocyanates in which the isocyanate groups have reacted with a blocking agent, releasing the isocyanate and the 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, such as 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 crosslinking 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 crosslinking agents. The exact amount of crosslinking agent (III) will depend on a variety of factors, including the type and amount of (I) silicone-(meth)acrylate copolymer formed in step 1) and the textile to be treated, but the weight of crosslinking agent (III) may be sufficient to provide, on the same basis, 0.25% to 3.75% of the textile weight, alternatively 0.25% to 1%, alternatively 0.25% to 0.5%. Alternatively, the amount of crosslinking agent may be 9.1% to 30%, based on the combined weight of all starting materials in the emulsion formulation suitable for treating textiles, excluding water. Alternatively, the amount of (III) crosslinking agent may vary depending on factors such as the type of fabric being treated. For example, the amount of (III) crosslinking agent may be 9.2% to 20.1% when the fabric being treated is polyester. Alternatively, the amount of (III) crosslinking agent may be 9.1% to 30.7% when the fabric being treated is a polyamide such as nylon.

[0069] Starting material (H) Chain transfer agent Additional starting materials that may be added in step 1) of the above process include (H) 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.

[0070] Starting material (H) chain transfer agent is optional and may be added in an amount of 0 to 1%, based on the combined weight of starting materials (A), (B), and (C) (and (J), if present). Alternatively, (H) chain transfer agent may be used in an amount of 0.5% to 0.6% on the same basis.

[0071] Starting material (F) Initiator The initiator starting material (F) is also added in step 1) above. 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, 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, under the trade name VAZO™ WSP from The Chemours Company (Wilmington, Delaware, USA). 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, and combinations of two or more thereof. In addition, di-peroxide initiators may be used alone or in combination with other initiators. Such di-peroxide 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 are commercially available from various suppliers, such as Sigma-Aldrich, Inc. Alternatively, the initiator may include isoascorbic acid.

[0072] 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 Bardman et al., U.S. Pat. No. 6,576,051 (column 11, beginning at 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 a redox couple is used). Typically, if a thermal initiator is used, all the initiator is added at once at the beginning of step 1). Alternatively, if a redox couple is used, it may 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 silicone-(meth)acrylate copolymer.

[0073] Starting material (J) additional monomer Starting material (J) is any additional monomer that may be added in step 1). Starting material (J) is a non-crystallizable monomer different from starting materials (A), (B) and (C) above. The additional monomer, if present, may be used in an amount of more than 0 to 18.75% by weight, based on the weight of (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 (J) are known in the art and are commercially available, for example, from Polysciences, Inc. Alternatively, the additional monomer (J) 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 0-18.75%, based on the combined weight of starting materials (A), (B), and (C), and, if present, (J). Alternatively, the (J) additional monomer may be present in an amount of at least 0.5%, alternatively at least 1%, alternatively at least 2%. At the same time, the additional monomer may be present in an amount of up to 18.75%, alternatively up to 15%, alternatively up to 10%, alternatively up to 8%, alternatively up to 5%, based on the same basis. Alternatively, the amount of (J) additional monomer may be, on the same basis, from greater than 0 to 18.75%, alternatively from 0.5% to 7%, alternatively from 1% to 6%, alternatively from 2% to 5%.

[0074] Starting material (K) Inhibitor Starting material (K) is an inhibitor that may be optionally added in step 1) of the above process. When present, starting material (K), the inhibitor may be used in an amount of from greater than 0 to less than 0.01% based on the weight of the (I) silicone-(meth)acrylate copolymer, alternatively from greater than 0 to less than 2,000 ppm on the same basis, alternatively from 1 ppm to 1818 ppm, alternatively from 10 ppm to 500 ppm. Suitable inhibitors for the starting material (K) 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).

[0075] Additional starting materials may be optionally added after step 1) and / or after step 2) to prepare an emulsion formulation suitable for treating textiles. The starting materials may be selected from the group consisting of (VI) additional surfactants (as described above for starting material (D)), (VII) waxes, (VIII) biocides, (IX) additional water (as described above for starting material (E)), (X) flame retardants, (XI) wrinkle reducing agents, (XII) antistatic agents, (XIII) penetrating agents, or combinations of two or more of the additional starting materials.

[0076] Starting material (VII) wax Starting material (VII) is a wax, which may be optionally added to provide improved water repellency or softness to the textile 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%, alternatively 25%-50%, based on the weight of (I) silicone-(meth)acrylate copolymer. Alternatively, when 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., alkylmethyl silicone 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, for example, Michelman wax 743 and others from Michelman (Cincinnati, Ohio, USA) may be supplied as water-based 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).

[0077] Starting material (VIII) Biocides Starting material (VIII) is a biocide. The amount of biocide varies depending on factors such as the type of biocide selected and the effect desired. 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 (VIII) is exemplified by (M-1) a fungicide, (M-2) a herbicide, (M-3) an insecticide, (M-4) an antimicrobial agent, or a combination thereof. Suitable biocides are disclosed, for example, in U.S. Pat. No. 9,480,977.

[0078] Starting material (XIII) Penetrant Starting material (XIII) is a penetrating agent. Suitable penetrating agents are exemplified by glycol ethers available from The Dow Chemical Company, including DOWANOL DPM, TPM, PPh, EPh, Methyl CARBITOL, and Butyl CARBITOL.

[0079] (II) Additives Suitable emulsion formulations for treating textiles include a compound of formula (II-1) in an amount sufficient to impart softness to the textile without significantly reducing water repellency.

[0080] [ka] (wherein each R 19are independently selected monovalent saturated hydrocarbon radicals having 1 to 18 carbon atoms, the subscript a having an average value of 20 to 300), or (II-2) 60 to 70 weight % of the combination of (II-1) alkyl polysiloxane, based on the combined weight of all the starting materials in (II-2), 29 to 39 weight % of the combination of (II-2-1) silicone resin having a hardness of 20 or more as measured by a Type A durometer according to JIS K6249:2003, based on the combined weight of all the starting materials in (II-2), and 0 to 2 weight % of the combination of (II-2) amino-functional polyorganosiloxane having a functional group equivalent, meaning the molecular weight of the amino-functional polyorganosiloxane per mole of nitrogen atom, of 100 to 20,000 g / mol and a kinematic viscosity at 25°C measured by the method of JIS K2283:2000 of 10 to 100,000 mm 2 / sec. (II-2-2) amino-functional polyorganosiloxane. Alternatively, (II-2-2) amino-functional polyorganosiloxane may be present in an amount of 1% to 2% on the same basis.

[0081] (II-1) Alkylpolysiloxane has the formula

[0082] [ka] wherein each R 19 is an independently selected monovalent saturated hydrocarbon radical having 1 to 18 carbon atoms, and the subscript a has an average value of 20 to 300. 19 The monovalent saturated hydrocarbon group may be an alkyl group, alternatively an alkyl group of 1 to 6 carbon atoms. Alternatively, the alkyl group may have 1 to 3 carbon atoms, alternatively 1 to 2 carbon atoms. Alternatively, each R 19 may be methyl. Suitable alkylpolysiloxanes, such as bis-trimethylsiloxy terminated polydimethylsiloxane, are known in the art and are commercially available, for example, from DSC as XIAMETER™ 200 fluid.

[0083] Alternatively, the additive (II) is (II-2) (II-2) based on the combined weight of all the starting materials in (II-2), 60 to 70% by weight of the above alkyl polysiloxane (II-1), based on the combined weight of all the starting materials in (II-2), 29 to 39% by weight of the combination of (II-2-1) silicone resin having a hardness of 20 or more as measured by a type A durometer according to JIS K6249:2003 based on the combined weight of all the starting materials in (II-2), and 1 to 2% by weight of the combination of an amino-functional polyorganosiloxane having a functional group equivalent, meaning the molecular weight of the amino-functional polyorganosiloxane per mole of nitrogen atom, of 100 to 20,000 g / mol and a kinetic viscosity at 25 °C measured by the method of JIS K2283:2000 of 10 to 100,000 mm 2 / sec. (II-2-2) may contain a combination of amino-functional polyorganosiloxanes.

[0084] The starting material (II) additive may be delivered in a second aqueous emulsion comprising the (II) additive, (D') a surfactant (which may be as described above for starting material (D)), and (E') water (which may be as described above for starting material (E)). The second aqueous emulsion may be prepared by known methods, such as those described in U.S. Patent Application Publication No. 2020 / 0332148, by varying the types and amounts of the starting materials described herein.

[0085] In emulsion formulations suitable for treating textiles, the (II) additive may be present in an amount of 0.4% to 29.3%, based on the combined weight of all starting materials in the emulsion formulation, excluding water. Alternatively, the amount of the (II) additive may vary depending on the type of additive selected and / or the type of textile being treated. For example, when the additive is (II-1) an alkyl polysiloxane, the alkyl polysiloxane may be present in an amount of 0.7% to 28.5%. Alternatively, when the textile being treated is a polyester, the alkyl polysiloxane may be present in an amount of 0.7% to 28.5%. Alternatively, when the textile being treated is a polyamide, such as nylon, the alkyl polysiloxane may be present in an amount of 1% to 28.5%. Alternatively, when the additive is (II-2) a combination of the above, the additive may be present in an amount of 0.4% to 29.3%, based on the combined weight of all starting materials in the emulsion formulation, excluding water. Alternatively, if the treated fabric is a polyester, the combination may be present in an amount of 0.4% to 29.3%. Alternatively, if the treated fabric is a polyamide, such as nylon, the combination may be present in an amount of 0.8% to 28.5%.

[0086] When selecting starting materials to be added to the above first and second aqueous emulsions, as well as suitable emulsion formulations for treating textiles, there may be overlap between the types of starting materials, as certain starting materials described herein may have more than one function. The starting materials used in the first aqueous emulsion, the second aqueous emulsion, and / or the emulsion formulations may be different from each other.

[0087] The emulsion formulation suitable for treating textiles comprises (I) silicone-(meth)acrylate copolymer, (II) additive, (III) water-dispersible crosslinker, (IV) surfactant (described above as starting material (D)), and (V) water (described above as starting material (E)). The emulsion formulation may optionally further comprise additional starting materials selected from the group consisting of (VII) wax, (VIII) biocide, (IX) additional water, (X) flame retardant, (XI) wrinkle reducing agent, (XII) antistatic agent, (XIII) penetrant, and combinations of two or more of starting materials (VII), (VIII), (IX), (X), (XI), (XII) and (XIII), which may be added during the preparation of the first aqueous emulsion comprising (I) silicone-(meth)acrylate copolymer or thereafter in the process for preparing the emulsion formulation. These additional starting materials and their amounts are as described above. Additionally, the emulsion formulations described herein may be formulated using starting materials that do not contain fluorocarbons, for example, the emulsion formulations may be free of any starting materials that contain fluorine atoms covalently bonded to carbon atoms.

[0088] Textile processing The emulsion formulation prepared as 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 textile with the emulsion formulation. However, the method must be sufficient to deliver 0.25% to 7.5% by weight of the textile of (I) silicone-(meth)acrylate copolymer, 0.01% to 0.5% by weight of the textile of (II) additive, and 0.05% to 0.5% by weight of the textile of (III) water-dispersible crosslinking agent, all based on the weight of the textile. When the (II) additive is a combination of (II-2), the amount of (I) silicone-(meth)acrylate copolymer and the amount of the combination of (II-2) are sufficient to provide a weight ratio of (I):(II-2) of 2:1 to less than 200:1.

[0089] Step II) may be carried out by any convenient method, such as 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 depends 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 from 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 and (II) additive.

[0090] The textile to be treated is not particularly limited. Suitable textiles include textiles of natural origin, such as cotton, silk, linen, and / or wool fabrics, textiles of synthetic origin, 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 textile is also not particularly limited. The emulsion formulations described herein are suitable for use on any form of textile, such as woven fabric, knitted fabric, carpet, or nonwoven fabric. EXAMPLES

[0091] The following examples are provided to illustrate the invention to one of ordinary skill in the art and should not be construed as limiting the invention as claimed. The starting materials used herein were as follows: The fabric 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 treated was style 4774 075, also from Burlington, with a basis weight of 220 g / m 2The crosslinking monomers were polyester or PES woven fabrics (crepe). The water-dispersible crosslinking agent (H-1) was PHOBOL™ XAN extender (oxime-blocked isocyanate emulsion) purchased from Huntsman and used as received. The crystallizable monomers (A-1) were stearyl acrylate and / or lauryl methacrylate, and the crosslinking (meth)acrylate monomers (C-1) were 2-hydroxyethyl methacrylate (HEMA), the nonionic surfactant BRIJ™ L23-69 (69% active), the cationic surfactant ARQUAD™ 16-29 (hexadecyltrimethylammonium chloride, 29% active), and 2,2'-azobis(2-methylpropionitrile) (AIBN), Ec The emulsion (Emulsion 1) was prepared according to U.S. Patent Application Publication No. 2020 / 0332148 and included oSurf™ EH-14 nonionic surfactant (90% active), EcoSurf™ EH-40 nonionic surfactant (75% active), Synperonic™ 13 / 6 co-emulsifier and wetting agent, Synperonic™ 13 / 12 co-emulsifier and wetting agent, alkyl polysiloxane, silicone resin, and amino functional polyorganosiloxane. Nicca BG2 penetrant, t-butyl hydroperoxide, isoascorbic acid, dodecanethiol, dipropylene glycol, XIAMETER™ PMX-200 silicone fluid (100 cSt bis-trimethylsiloxy terminated polydimethylsiloxane), and XIAMETER™ OHX-0750 polymer (bis-silanol terminated polydimethylsiloxane with a DP of about 200) were commercially available and obtained from commercial sources. A terminated aminosiloxane (TAS, a bis-amino-alkyl terminated polydimethylsiloxane with a DP of about 16) was prepared as described in PCT Publication No. 2021108068.The starting material (B-1) was 3-(1,5-bis(2-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)ethyl)-3-(((2-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)ethyl)dimethylsilyl)oxy)-1,1,5,5-tetramethyltrisiloxan-3-yl)propyl methacrylate (abbreviated as Sil6), prepared as described in U.S. Pat. No. 6,420,504. A Fisherbrand™ Model 705 sonic dismembrator was used for sonication. The microfluidizer was a Microfluidics Microfluidizer Model 110Y homogenizer. DT-Resin-ALMA is a polymethylsilsesquioxane resin containing di- and trifunctional siloxane units, which further contained methacryloxypropyl groups.

[0092] In this Reference Example A, a silicone-(meth)acrylate copolymer emulsion was prepared as follows: Initiator solution A was prepared as follows: 0.702g of 70% t-butyl hydroperoxide was diluted with 45mL of DI water to form a stock solution. The final solution was made by taking 5g of this stock solution and mixing with 5g of DI water.

[0093] Initiator solution B was prepared as follows: 0.96 g of isoascorbic acid was added to 45 mL of DI water to form a stock solution. The final solution was made by taking 5 g of this stock solution and mixing with 5 g of DI water.

[0094] Stearyl acrylate (47.5 g), Si16 (1.5 g), HEMA (1 g), dodecanethiol (0.05 g), Ecosurf™ EH-40 nonionic surfactant (1.67 g), and deionized water (200 g) were placed in a 400 mL jar. The mixture was heated in a 40° C. water bath for 10 minutes to melt the stearyl acrylate. The ingredients were sonicated for 2 minutes using a sonicator at 50 Joules amplitude to create a crude emulsion. The crude 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 4-neck flask equipped with a reflux condenser, nitrogen inlet, overhead stirrer (IKA RW20), and thermocouple probe. The emulsion was stirred at 200 RPM with a Teflon blade and heated to 60° C. After reaching temperature, the redox initiator was fed to the solution at 0.25 mL / min (Initiator Solution A and Initiator Solution B in separate feeds) and after 1 hour at 60° C., the resulting emulsion formulation was then cooled to below 35° C. with slow stirring before being poured off. Silicone-(meth)acrylate copolymers of Samples 1-16 and 23-34 were prepared according to this Reference Example A by varying the amounts of the appropriate starting materials.

[0095] In this Reference Example 1, acrylate emulsion samples 17, 18, 35, and 36 were prepared as follows: stearyl acrylate (37.5 g), lauryl methacrylate (11.5 g), HEMA (1 g), dipropylene glycol (20 g), Brij L23-69 (5 g), Arquad16-29 (hexadecyltrimethylammonium chloride, 3 g), and deionized water (180 g) were placed in a 400 mL jar. The mixture was heated in a 40° C. water bath for 10 minutes to melt the stearyl acrylate. The ingredients were sonicated with a sonicator at an amplitude of 50 J for 2 minutes to create an emulsion. The resulting emulsion was then transferred to a 1000 mL 4-neck flask equipped with a reflux condenser, nitrogen inlet, overhead stirrer (IKA RW20), and thermocouple probe. The emulsion was stirred at 200 RPM with a Teflon blade, 0.3 g of 2-2'-azobis(2-methylpropionamidine) dihydrochloride initiator was added, and the mixture was heated to 60° C. The reaction mixture was held at 60° C. for 6 hours. The ingredients were then cooled to 30-40° C. with stirring, and then poured off.

[0096] In this Reference Example 2, acrylate emulsion samples 19, 20, 37 and 38 were prepared as described in US Patent Application Publication No. 2020 / 0332148. Stearyl acrylate (49 g), HEMA (1 g), Brij L23-69 (5 g), Arquad16-29 (hexadecyltrimethylammonium chloride, 3 g), and deionized water (200 g) were placed in a 400 mL jar. The mixture was heated in a 40° C. water bath for 10 minutes to melt the stearyl acrylate. The raw materials were sonicated with a sonicator at an amplitude of 50 J for 2 minutes to create an emulsion. The resulting emulsion was then transferred to a 1000 mL 4-neck flask equipped with a reflux condenser, nitrogen inlet, overhead stirrer (IKA RW20), and thermocouple probe. The emulsion was stirred at 200 RPM with a Teflon blade, 0.3 g of 2-2'-azobis(2-methylpropionamidine) dihydrochloride initiator was added, and the mixture was heated to 60° C. The reaction mixture was held at 60° C. for 6 hours. The ingredients were then cooled to 30-40° C. with stirring, and then poured off.

[0097] In this Example 3, 35 g of PMX-200 fluid and 1.5 g of EcoSurf™ EH-14 were placed in a plastic beaker and mixed at 10,000 RPM using an IKA Ultra Turrax T25 equipped with an 18 mm dispersion tool. Deionized water (15.5 g) was added dropwise to the mixture to create an emulsion.

[0098] In this Example 4, 10 g of the comparative polymer (either OHX-0750 polymer or amino-terminated siloxane), 0.5 g of Synperonic 13 / 6, 0.5 g of Synperonic 13 / 12, and 0.75 g of deionized water were placed in a SpeedMixer cup and mixed at 3500 RPM for 30 seconds twice. The resulting emulsion was diluted by adding 1.25 g and 3.67 g aliquots of deionized water and mixing at 3500 RPM after the addition of each aliquot.

[0099] In this Example 5, an emulsion formulation suitable for treating textiles was prepared by combining water, penetrant, emulsifying additive (PMX-200 silicone fluid, OHX-0750 polymer, or TAS, or Emulsion 1), silicone-(meth)acrylate copolymer emulsion, and water-dispersible crosslinker (PHOBOL™ XAN Extender) in a plastic bottle and mixing by hand shaking. The resulting formulation is set forth in Table X below.

[0100] [Table 1-1]

[0101] [Table 1-2]

[0102] In Table X, in the column listing starting materials, the first value represents the grams of starting material and the second value (in parentheses) represents the weight of fabric in the emulsion formulation. Copolymer refers to silicone-(meth)acrylate copolymer.

[0103] In this Example 6, the evaluation procedure for water repellency and wash durability was as follows: Nylon / polyester sheets were treated with the emulsion formulation prepared according to Example 5, and then the sheets were washed using a 90°F wash / cold rinse cycle and dried at about 150°F. This process was repeated up to 20 times. For every 6 lbs of sheets, 37 g of Tide detergent (unscented) was used. AATCC-22 spray testing was performed after the first treatment (0 washes), after 10 washes, and after 20 washes. A value of less than 90 in the spray test was considered a failure. The results are shown in Table Y.

[0104] In this Reference Example 7, the softness evaluation procedure was as follows: The nylon / polyester sheets were dried at about 150°F and then evaluated for both stiffness and hand. For stiffness, the sheets were folded in half and the stiffness / drape was ranked on a scale of 1 to 5, with 5 being best. For hand, the hand of the fabric was ranked on a scale of 1 to 5, with 5 being best. Anything less than 4 was considered a failure. The results are shown in Table Y.

[0105] [Table 2]

[0106] In Table Y, a "*" indicates that the sample did not pass the spray test after the first treatment, and therefore a clean-up spray test was not performed. A "-" indicates that it was not tested.

[0107] Samples 1-6 showed that treating PES fabric with emulsion formulations providing 1-2% silicone-(meth)acrylate copolymer and 0.01-0.5% emulsion 1 provided durable water repellency (as indicated by passing the spray test after 10 and 20 washes) and good softness (as indicated by drape and feel test values ​​of 4 or greater). Example 7 showed that treating PES fabric with emulsion formulations providing 1-2% silicone-(meth)acrylate copolymer and 0.01% trimethylsiloxy terminated polydimethylsiloxane provided durable water repellency (as indicated by passing the spray test after 10 and 20 washes) and good softness (as indicated by drape and feel test values ​​of ≧4). Examples 10 and 11 showed that treating PES fabric with emulsion formulations providing 1-2% silicone-(meth)acrylate copolymer but not an additive corresponding to starting material (II) described herein did not provide sufficient softness. Examples 13, 14, 15 and 16 show that under the conditions tested, insufficient water repellency is achieved when additives outside the scope of the present invention are used instead of starting material (II) as defined herein. Examples 17, 18, 19 and 20 show that under the conditions tested, insufficient water repellency is achieved when copolymers outside the scope of the present invention are used instead of starting material (I) as defined herein. Examples 21 and 22 show that under the conditions tested, insufficient water repellency is achieved in the absence of starting material (I) as defined herein.

[0108] Issues to be resolved Silicone-(meth)acrylate hybrid copolymers can impart excellent and long-lasting water resistance to various textiles, but they can have the drawback of imparting negative aesthetics such as stiffness and poor hand. Known compositions for treating textiles, such as those disclosed in U.S. Patent Application Publication No. 2020 / 0332148, can impart sufficient aesthetics, but in some applications, the durable water repellency is insufficient.

[0109] solution The present invention provides emulsion formulations which, when used to treat textile fabrics, impart both good durable water repellency as measured by a score of at least 90 in the spray test after 10-20 washes, and desirable aesthetics as measured by a score of at least 4 in the stiffness and hand test described in Reference Example 7 above.

[0110] 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 otherwise specified by the context of the specification, 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," "eg," "such as," and "including" to list examples does not limit 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 Z.

[0111] [Table 3]

[0112] The present invention has been described in an illustrative manner, and it is to 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 a description of a particular feature or aspect is relied upon herein, different, unusual, and / or unexpected results may result from each element of the respective Markush group, independent of all other elements of the Markush group. Each element of the Markush group may be relied upon individually and / or in combination to provide sufficient support for specific embodiments within the scope of the appended claims.

[0113] Moreover, any ranges and subranges relied upon in describing the invention are understood to be independently and inclusively within the scope of the appended claims and to describe and contemplate the entire range encompassing all and / or partial values ​​therein, even if all and / or partial values ​​therein are 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 may be further delineated into relevant halves, thirds, quarters, fifths, and any other subranges contained within the ranges. As merely one example, 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 sub-range "18-22," which are individually and collectively within the scope of the appended claims, and which may be relied upon and provide appropriate justification for, individually and / or collectively, for particular embodiments within the scope of the appended claims. In addition, with respect to words defining or modifying ranges, such as "at least," "greater than," "less than," "less than," etc., such words should be understood to include subranges and / or upper or lower limits.

Claims

1. 1. An emulsion formulation suitable for treating textile fabrics, said emulsion formulation comprising: A unit formula sufficient to impart water repellency to the fabric. 【Chemistry 1】 (In the formula, each R １ is an independently selected alkyl group of 16 to 24 carbon atoms, and each R ２ is independently selected from the group consisting of H and methyl; ２ is a divalent hydrocarbon radical of 2 to 12 carbon atoms, and each R ３ is represented by the formula OSi(R ４ ) ３ where each R ４ are independently R and DSi(R ５ ) ３ each R is an independently selected monovalent hydrocarbon radical of 1 to 12 carbon atoms; each D is independently selected from the group consisting of an oxygen atom, a (poly)alkylene oxide group of 1 to 12 units, and a divalent hydrocarbon radical of 2 to 4 carbon atoms; and each R ５ are independently R and DSi(R ６ ) ３ and each R ６ are independently R and DSiR ３ where R is selected from the group consisting of ４ , R ５ , and R ６ is selected such that the silicone-(meth)acrylate macromonomer unit having subscript w has at least 6 silicon atoms, and each R ７ is independently selected from the group consisting of an oxygen atom and NH; D ３ is a divalent hydrocarbon radical of 1 to 12 carbon atoms; D ４ is an alkylene group or a divalent alkylarylene group of 2 to 4 carbon atoms, and the subscript v is a group of the formula (OD ４ ) units, the subscript v has a value from 0 to 12, and each R ８ is a crosslinkable group, and each R ９ is a monovalent hydrocarbon radical of 1 to 14 carbon atoms, and each R １０ are independently selected from the group consisting of halogens, acetate groups, or monovalent hydrocarbon groups of 1 to 14 carbon atoms; and the subscripts w, x, y, z1, and z2 represent the relative weight of each unit in the copolymer, where subscript x has a value of 0.25 to 15, subscript w has a value of 80 to 98.75, subscript y has a value of 1 to 5, subscript z1 has a value of 0 to 18.75, and subscript z2 has a value of 0 to 18.75, and the amount (w+x+y+z1+z2)=100, with the proviso that the copolymer further comprises a terminal moiety; A sufficient amount to impart softness to the fabric without significantly reducing water repellency. formula 【Chemistry 2】 (II-1) Alkylpolysiloxane (wherein each R １９ is an independently selected monovalent saturated hydrocarbon radical having 1 to 18 carbon atoms, and the subscript a has an average value of 20 to 300; or (II-2) A combination, (II-1) said alkylpolysiloxane in an amount of 60 to 70% by weight based on the combined weight of all starting materials in (II-2); (II-2-1) a silicone resin having a hardness of 20 or more as measured with a type A durometer according to JIS K6249:2003, in an amount of 29 to 39% by weight based on the combined weight of all starting materials in (II-2); Based on the combined weight of all the starting materials in (II-2), 0 to 2% by weight of the combination has a functional group equivalent, which means the molecular weight of the amino-functional polyorganosiloxane per mole of nitrogen atom, of 100 to 20,000 g / mol, and a kinematic viscosity at 25 ° C. measured by the method of JIS K2283:2000 of 10 to 100,000 mm ２ (II-2) an additive selected from the group consisting of combinations of (II-2-2) the amino-functional polyorganosiloxane, (III) a water-dispersible crosslinking agent in an amount sufficient to crosslink the starting materials (I) and (II); (IV) a surfactant; and (V) water.

2. R １ is a stearyl group, subscript w=95, D ２ Ha-(CH ２ ) ３ -, and each R ３ is -OSi(CH ３ ) ２ (CH ２ ) ２ Si(OSi(CH ３ ) ３ ), where subscript x=3, and R ７ is O, subscript v=0, and R ８ 2. The emulsion formulation of claim 1, wherein: is OH; subscript y=2; subscript z1=0; and subscript z2=0.

3. 3. The emulsion formulation of claim 1 or claim 2, further comprising one or more additional starting materials selected from the group consisting of (VI) additional surfactants, (VII) waxes, (VIII) biocides, (IX) flame retardants, (X) wrinkle reducing agents, (XI) antistatic agents, and (XII) penetrating agents.

4. The emulsion formulation of claim 3, wherein (II) the additive is (II-2), and the emulsion formulation further comprises (XII) the penetrating agent.

5. (III) The emulsion formulation of any one of claims 1 to 4, wherein the water-dispersible crosslinker comprises a blocked isocyanate.

6. 6. The emulsion formulation of any one of claims 1 to 5, wherein (I) the silicone-(meth)acrylate copolymer is present in an amount sufficient to provide 0.25 to 7.5 wt. % on the fabric, (II) the additive is present in an amount sufficient to provide 0.01 to 0.5 wt. % on the fabric, and (III) the water-dispersible crosslinker is present in an amount sufficient to provide 0.05 to 0.5 wt. % on the fabric, with the proviso that when the additive is (II-2) the combination, the amount of (I) the silicone-(meth)acrylate copolymer and the amount of (II-2) the combination are sufficient for the weight ratio of (I):(II-2) to be from 2:1 to less than 200:

1.

7. A process for preparing an emulsion formulation according to any one of claims 1 to 6, said process comprising the steps of: 1) The silicone-(meth)acrylate copolymer, which is the starting material (I), (A) 80% to 98.75% by weight of a compound of the formula 【Chemistry 3】 A crystalline monomer of formula R １ and R ２ is as above), and (B) 0.25% to 15% by weight of a compound of the formula 【Chemistry 4】 Silicone-(meth)acrylate macromonomer of the formula ２ , D ２ , and R ３ is as above), and (C) 1% to 5% by weight of a compound of formula 【Chemistry 5】 A crosslinkable (meth)acrylate monomer of the formula ７ , D ３ , D ４ , subscript v, and R ８ is as above), and (D) a surfactant; and (E) water; (F) an initiator, thereby forming (I) a first aqueous emulsion comprising said silicone-(meth)acrylate copolymer; 2) (II) providing a second aqueous emulsion comprising the additives (D') a surfactant and (E') water; and 3) mixing ingredients including the first aqueous emulsion prepared in step 1), the second aqueous emulsion from step 2), (III) the water-dispersible crosslinker, and optionally one or more additional starting ingredients selected from the group consisting of additional surfactants, waxes, biocides, additional water, flame retardants, wrinkle reducing agents, antistatic agents, and penetrating agents.

8. 8. The process of claim 7, wherein the starting material (A) is selected from the group consisting of stearyl acrylate, stearyl methacrylate, behenyl methacrylate and behenyl acrylate.

9. The starting material (B) is represented by the formula 【Chemistry 6】 9. The process of claim 7 or claim 8, comprising:

10. The starting material (B) is 3-(5-((1,1,1,3,5,5,5-heptamethyltrisiloxan-3-yl)oxy)-1,1,1,3,7,9,9,9-octamethyl-3,7-bis((trimethylsilyl)oxy)pentasiloxan-5-yl)propyl methacrylate, 10. The process of any one of claims 7 to 9, wherein the aryl group may be selected from the group consisting of 3-(1,5-bis(2-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)ethyl)-3-(((2-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)ethyl)dimethylsilyl)oxy)-1,1,5,5-tetramethyltrisiloxan-3-yl)propyl methacrylate, and combinations thereof.

11. In the starting material (C), each R ８ is independently selected from the group consisting of hydroxy, amino, epoxy, ureido, and acetoxy.

12. The process of claim 11, wherein the starting material (C) is 2-hydroxyethyl methacrylate.

13. The process of any one of claims 7 to 12, wherein starting material (D) and starting material (D') are each independently selected from the group consisting of cationic surfactants, nonionic surfactants, and combinations thereof.

14. 14. The process of claim 13, wherein the cationic surfactant comprises a quaternary ammonium compound or the non-ionic surfactant comprises a polyethylene glycol, an alcohol ethoxylate, or a combination thereof.

15. 15. The process of any one of claims 7 to 14, further comprising adding in step 1) an additional starting material selected from the group consisting of: (H) a chain transfer agent, (J) an additional monomer, (K) an inhibitor, or a combination of two or more of (H), (J), and (K).

16. 1. A process for treating a textile fabric, the process comprising: I) coating the textile with an emulsion formulation according to any one of claims 1 to 6 or with the emulsion formulation prepared by the process according to any one of claims 7 to 15; II) heating the fabric.

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