Silicone – (METH)acrylate copolymer formulation and processes for preparation and use thereof

Abstract

A composition includes a silicone – (meth)acrylate copolymer, a manganese ion source, and a phenolic compound. Methods for preparation and use of the composition are provided. The composition may be emulsified, and the resulting aqueous emulsion formulation may be used for treating a textile to impart water repellency.

Description

SILICONE - (METH) ACRYLATE COPOLYMER FORMULATION AND PROCESSES FOR PREPARATION AND USE THEREOFCROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of U.S. Provisional Patent Application Serial No. 63 / 588046 filed on 5 October 2023 under 35 U.S.C. §119 (e). U.S. Provisional Patent Application Serial No. 63 / 588046 is hereby incorporated by reference.TECHNICAL FIELD

[0002] A composition including a silicone - (meth)acrylate copolymer, a manganese ion source, and a phenolic compound, and methods for its preparation and use are provided. The composition is useful for treating textiles to impart durable water repellency thereto.INTRODUCTION

[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 an industry need for non- fluorocarbon-based textile treatments. Previously disclosed fluorocarbon-free textile treatments suffer the drawback of providing poor durability, where water repellency of textiles treated therewith decreases significantly after multiple washings.SUMMARY

[0004] A composition comprises a silicone - (meth)acrylate copolymer (copolymer), a manganese ion source, and a phenolic compound. Methods for preparation and use of the composition, are disclosed. An emulsion formulation comprising the copolymer, the manganese ion source, the phenolic compound, a surfactant, and water is suitable for treating a textile.DETAILED DESCRIPTION

[0005] The silicone - (meth)acrylate copolymer (copolymer) introduced above comprises unit formula:where each R1is an independently selected alkyl group of 16 to 24 carbon atoms; each R2is independently selected from the group consisting of H and methyl; each D2is a divalent hydrocarbon group of 2 to 12 carbon atoms; each R3is a group of formula OSi(R4)a; where each R4is independently selected from the group consisting of R and DSi(R5)3, where each R is an independently selected monovalent hydrocarbon group of 1 to 12 carbon atoms, and 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; each R5is independently selected from the group consisting of R and DSi(R6)3; where each R6is independently selected from the group consisting of R and DSiR ,; with the proviso that R4, R5, and R6are selected such that the silicone - (meth)acrylate macromonomer unit with subscript x has at least 6 silicon atoms; each R7is independently selected from the group consisting of an oxygen atom and NH; D3is a divalent hydrocarbon group of 1 to 12 carbon atoms; D4is an alkylene group of 2 to 4 carbon atoms or a divalent alkylarylene group; subscript v represents the number of units of formula (OD4) in the unit with subscript y, and subscript v has a value of 0 to 12; each R8is a crosslinkable group; each R9is a monovalent hydrocarbon group of 1 to 14 carbon atoms; each R10is independently selected from the group consisting of a halogen (e.g., chloride), an acetate group, or a monovalent hydrocarbon group of 1 to 14 carbon atoms; subscripts w, x, y, zl, and z2 represent relative weights of each unit in the copolymer, 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 zl has a value of 0 to 18.75; and subscript z2 has a value of 0 to 18.75, and a quantity (w + x + y + zl + z2) = 100. The copolymer further comprises a terminal moiety.

[0006] In the unit formula above, R1has 16 to 24 carbon atoms. Alternatively, R1, may have 16 to 22 carbon atoms, alternatively 18 to 24 carbon atoms, and alternatively 18 to 22 carbon atoms. R1may be selected from the group consisting of stearyl, eicosyl, and behenyl. Alternatively, R1may be stearyl.

[0007] In the unit formula above, each R3is a group of formula OSi(R4)a; where each R4is independently selected from the group consisting of R and DSi(R5)3, where each R is an independently selected monovalent hydrocarbon group of 1 to 12 carbon atoms, and 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; each R5is independently selected from the group consisting of R and DSi(R6)3; where each R6is independently selected from the group consisting of R and DSiR ,; with the proviso that R4, R5, and R6are selected such that the silicone - (meth)acrylate macromonomer unit with subscript x has at least 6 silicon atoms. Alternatively, R4, R5, and R6are selected such that the unit has at least 6 silicon atoms, alternatively 6 to 20 silicon atoms, alternatively 7 to 19 silicon atoms, alternatively 8 to 18 silicon atoms, alternatively 9 to 17 silicon atoms, and alternatively 10 to 16 silicon atoms, per unit.

[0008] In the silicone - (meth) acrylate macromonomer unit, each R is a monovalent hydrocarbon group of 1 to 12 carbon atoms. The monovalent hydrocarbon group for R may be an alkyl group, such as an alkyl group of 1 to 6 carbon atoms. Alternatively, the alkyl groups may have 1 to 3 carbon atoms, alternatively 1 to 2 carbon atoms. Alternatively, each R group may be methyl.

[0009] 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. Each D2is a divalent hydrocarbon group of 2 to 12 carbon atoms. Alternatively, D2may have 2 to 10, alternatively 3 to 5, and alternatively 3 carbon atoms. Each D3is a divalent hydrocarbon group of 1 to 12 carbon atoms. Alternatively, each D3may be an alkylene group; alternatively ethylene. D4is an alkylene group of 2 to 4 carbon atoms or a divalent alkylarylene group.

[0010] The divalent hydrocarbon group for D4may be exemplified by an alkylene group such as ethylene, propylene, or butylene; an arylene group such as phenylene, or an alkylarylene group such as;each subscript u is independently 1 to 6, alternatively 1 to 2. Alternatively, the divalent hydrocarbon group may be alkylene, and alternatively the divalent hydrocarbon group may be ethylene. The divalent hydrocarbon group for D2and D3may be as described above, and alternatively may be methylene. The divalent hydrocarbon group for D may be alkylene, such as ethylene, propylene, or butylene. Alternatively, each D may be ethylene.

[0011] The (poly)alkylene oxide group for D may have 2 to 4 carbon atoms per unit, e.g., have formula D5(OD6)V-OR, where D5is an alkylene group of 2 to 4 carbon atoms, D6is an alkylene group of 2 to 4 carbon atoms, R is as described above, and subscript v’ is 0 to 12. Alternatively subscript v’ may be 0 or 1 . Alternatively, subscript v’ may be 0. Examples of (poly)alkylene oxide groups include ethyleneoxide-propyleneoxide.

[0012] Alternatively, each D may be selected from an oxygen atom and a divalent hydrocarbon group. Alternatively, each divalent hydrocarbon group for D may be an alkylene group such as ethylene. Alternatively, each D may be oxygen. Alternatively, some instances of D may be oxygen and other instances of D may be alkylene in the same unit.

[0013] In the unit formula above each R7is independently selected from the group consisting of an oxygen atom and NH. Alternatively, each R7may be oxygen.

[0014] In the unit formula above, each R8is a crosslinkable group. Each R8may be independently selected from the group consisting of hydroxy, amino, epoxy, ureido, and acetoxy. Alternatively, each R8may be independently selected from the group consisting of hydroxy and ureido, and alternatively each R8may be hydroxy.

[0015] In the unit formula above, each R9is a monovalent hydrocarbon group, which is free of aliphatic unsaturation and which may be linear, branched, or cyclic (i.e., monocyclic or polycyclic), or combinations thereof. R9may be an alkyl group or an aryl group, which may be monocyclic or polycyclic, and which may optionally have linear or branched groups. Examples of suitable alkyl groups for R9may include methyl, t-amyl, butyl (including t-butyl), cyclohexyl, iso-decyl, isobornyl, and 2-ethylhexyl. Examples of suitable aryl groups include phenyl,naphthyl, anthracyl, and benzyl.

[0016] In the unit formula above, R10may be a halide, an acetate, or a monovalent hydrocarbon group, as described above for R9. The halide may be bromide (Br), chloride (Cl), fluoride (F) or iodide (I); alternatively Br, Cl or F; alternatively Br or Cl; and alternatively Cl.

[0017] In the unit formula above, subscripts w, x, y, and z are relative weights of each unit, and a quantity (w + x + y + z) may total 100. Subscript w has a value of 80 to 98.75.Alternatively, subscript w may be at least 80, alternatively at least 81, alternatively at least 82, alternatively at least 83, alternatively at least 84, and alternatively at least 85. At the same time, 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, and alternatively up to 90. Alternatively, subscript w may be 80 to 98, alternatively 81 to 97, alternatively 82 to 96, alternatively 82 to 95, and alternatively 85 to 90.

[0018] Subscript x has a value of 0.25 to 15. Alternatively, 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, subscript x may be up to 15, alternatively up to 14, alternatively up to 13, alternatively up to 12, alternatively up to 11, and alternatively up to 10. Alternatively, 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; and alternatively 10.

[0019] Subscript y has a value of 1 to 5. Alternatively, subscript y may be at least 1, alternatively at least 1.25, alternatively at least 1.5, alternatively at least 2, and alternatively at least 1.75. At the same time, 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, and alternatively up to 2.25. Alternatively, subscript y may be 1 to 3, alternatively 1 to 2, alternatively 1.5 to 2.5, alternatively 1.75 to 2.25, and alternatively 2.

[0020] Subscript zl may be 0. Alternatively, subscript zl may be at least 0.5, alternatively at least 1, and alternatively at least 2; while at the same time, subscript zl may be up to 18.75, alternatively up to 15, alternatively up to 10, alternatively up to 8, and alternatively up to 5.Alternatively, subscript zl may be 0 to 18.75, alternatively > 0 to 18.75, alternatively 0.5 to 7, alternatively 1 to 6, and alternatively 2 to 5.

[0021] Subscript z2 may be 0. Alternatively, subscript z2 may be at least 0.5, alternatively at least 1, and alternatively at least 2; while at the same time, subscript z2 may be up to 8, alternatively up to 7, alternatively up to 6, alternatively up to 5, and alternatively up to 4. Alternatively, subscript z2 may be 0 to 8, alternatively > 0 to 8, alternatively 0.5 to 7, alternatively 1 to 6, and alternatively 2 to 5.

[0022] The total number of units per molecule of copolymer is not specifically restricted. The units shown above may be in any order, e.g., the copolymer may be a random copolymer or a block copolymer.

[0023] One skilled in the ait would recognize that the copolymer may be prepared by radical polymerization, via a process as described below, and that this process would form the terminal moiety for the copolymer. The copolymer further comprises a terminal moiety which 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.

[0024] The copolymer may be prepared by any convenient means such as that disclosed in PCT Patent Application Publication WO2022 / 197350 to Jeletic et al. by using the manganese ion source and the phenolic compound described herein as inhibitors, instead of the inhibitor described therein. Alternatively, the copolymer may be prepared as described in U.S. Patent 10,047,199 to limura et al. by varying appropriate starting materials and their amounts. PCT Patent Application Publication WO2022 / 197350 and U.S. Patent 10,047,199 are hereby incorporated by reference.

[0025] For example, a composition according to this invention may be prepared via a process comprising:1) copolymerizing starting materials comprising80 weight % to 98.75 weight % of (A) a crystallizable monomer of formula, where R1 is an alkyl group of 16 to 24 carbon atoms as described above, and R^ is selected from the group consisting of H and methyl, as described above;0.25 weight % to 15 weight % of (B) a silicone - (meth)acrylate macromonomer of formulaeach R3is a group of formula OSi(R4)a; each R4is independently selected from the group consisting of R and DSi(R5)3, where each R is an independently selected monovalent hydrocarbon group 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 group of 2 to 4 carbon atoms; each R5is independently selected from the group consisting of R and Dsi(R6)a; where each R6is independently selected from the group consisting of R and DsiR?; with the proviso that R4, R5, and R6are selected such that the macromonomer has at least 6 silicon atoms per molecule, as described above; and1 weight % to 5 weight % of C) a crosslinkable (meth)acrylate monomer of formulaindependently selected from oxygen and NH,D3is a divalent hydrocarbon group of 1 to 12 carbons, D4is a divalent group of 2 to 4 carbon atoms, subscript v is 0 to 12, and R8is a crosslinkable group, each as described above; where the amounts of starting materials (A), (B), and (C) shown above total 100 weight% based on combined amounts of starting materials (A), (B), and (C). The starting materials used in step 1) of the process to prepare the composition further comprise:(I) an initiator;(K) a manganese ion source, and(L) a phenolic compound. The starting materials used in the process to prepare the composition may optionally further comprise (H) a chain transfer agent; (J) an additional non- crystallizable monomer that is distinct from each of (A), (B) and (C); and a combination of both (H) and (J).

[0026] Copolymerizing, as introduced above, may comprise preparing the copolymer described above by a method comprising dissolving one or more of starting materials (A), (B), (C), and when present (H) and / or (J), with (K) the manganese ion source and (L) the phenolic compound in a solvent (e.g., an organic solvent such as a monohydric alcohol). Without wishing to be bound by theory, it is thought that during processing to combine (A), (B), (C), (H), and (J), starting materials (K) and (L) may inhibit formation of acrylic radicals that can impact the formation of the copolymer during copolymerization in step 1). In step 1) copolymerizing starting materials (A), (B), (C), (I), and when present (H) and / or (J), in the presence of (K) the manganese ion source and (L) the phenolic compound, may be performed in a process such as that disclosed in U.S. Patent 10,047,199 to limura et al. by varying appropriate stalling materials and their amounts. The resulting reaction product, which comprises the copolymer, the manganese ion source, and the phenolic compound, may be solvent borne. When solvent is present, all or a portion of the solvent may be removed by any convenient means, such as by stripping or distillation with optionally with heat and / or optionally reduced pressure. The resulting composition comprises (F) the copolymer, (K) the manganese ion source, and (L) the phenolic compound. An aqueous emulsion may be prepared by a process comprising emulsifying said composition by mixing, under shear, the composition described above and additional starting materials comprising (D) a surfactant and (E) water. The resulting aqueous emulsion comprises (F) the silicone - (meth)acrylate copolymer, (K) the manganese ion source, (L) the phenolic compound, (D) the surfactant, and (E) the water.

[0027] Alternatively, the process for preparing the composition may comprise an emulsion polymerization, e.g., the copolymer may be prepared via an emulsion polymerization process comprising:1) copolymerizing starting materials comprising80 weight % to 98.75 weight % of (A) the crystallizable monomer of formula, where R1is an alkyl group of 16 to 24 carbon atoms as described above, and R2is selected from the group consisting of H and methyl, as described above;0.25 weight % to 15 weight % of (B) the silicone - (meth)acrylate macromonomer of formulaeach R3is a group of formula OSi(R4)3; each R4is independently selected from the group consisting of R and DSi(R5)3, where each R is an independently selected monovalent hydrocarbon group 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 group of 2 to 4 carbon atoms; each R5is independently selected from the group consisting of R and DSi(R6)3; where each R6is independently selected from the group consisting of R and DSiR3; with the proviso that R4, R5, and R6are selected such that the macromonomer has at least 6 silicon atoms per molecule, as described above; and1 weight % to 5 weight % of (C) the crosslinkable (meth)acrylate monomer of formulaindependently selected from oxygen and NH,D3is a divalent hydrocarbon group of 1 to 12 carbons, D4is a divalent group of 2 to 4 carbon atoms, subscript v is 0 to 12, and R8is a crosslinkable group, each as described above;where amounts of starting materials (A), (B), and (C) total 100 weight% based on combined amounts of starting materials (A), (B), and (C); and starting materials (A), (B), and (C) arc copolymerized in an emulsion further comprising(D) a surfactant;(E) water;(H) the chain transfer agent;(I) the initiator; optionally (J) the additional non-crystallizable monomer that is distinct from each of (A), (B) and (C); and(K) the manganese ion source, and(L) the phenolic compound; thereby forming an aqueous emulsion comprising (F) the silicone - (meth) acrylate copolymer, (D) the surfactant, (E) the water, (K) the manganese ion source, and (L) the phenolic compound.

[0028] The emulsion polymerization process described above may comprise forming an emulsion comprising starting materials (A), (B), (C), (D), (E), (H), (K), and (L) (and optionally(J)), and thereafter adding (I) the initiator and copolymerizing. Without wishing to be bound by theory, it is thought that during processing to combine and emulsify (A), (B), (C), (D), (E), (H), and (J), starting materials (K) and (L) may inhibit formation of acrylic radicals that can impact the formation of the copolymer during copolymerization in step 1).

[0029] If starting material (A) is a solid at RT, the starting materials may be heated to a temperature and for a time sufficient to melt starting material (A), e.g., 30 °C to 50 °C for 5 minutes to 15 minutes. The resulting starting materials may be mixed under shear to form the aqueous emulsion. Mixing under shear may be performed by any convenient means for forming an aqueous emulsion, such as sonication and with subsequent microfluidization. Equipment for mixing under shear, such as sonicators, homogenizers, microfluidizers, and speedmixers are known in the art and are commercially available. Without wishing to be bound by theory, it is thought that mixing under shear may be used to obtain a submicron particle size in the emulsion. In step 1), starting materials comprising (A), (B), (C), and (I) (and when present (H) and (J)) copolymerize to form (F) the silicone - (meth)acrylate copolymer in the presence of starting materials (K) and (L).

[0030] Before step 1) the starting materials comprising (A), (B), (C), (H), (K), (L), and when present (J) may be combined under aerobic or anaerobic conditions, optionally with heating for extended times. For example, the starting materials comprising (A), (B), (C), (H) (K), (L), and when present (J) may be emulsified with (D) and (E) before adding initiator and copolymerizing in step 1). In step 1), copolymerizing (either in solvent or via emulsion polymerization) in the process described above may be performed on a commercial scale under aerobic or anaerobic conditions optionally at elevated temperature, e.g., up to 100 °C, alternatively 40 °C to 80 °C, and alternatively 45 °C to 50 °C. Copolymerizing may be performed in a batch process with a residence time of 15 minutes to 24 hours, alternatively 30 minutes to 12 hours, alternatively 40 minutes to 8 hours, and alternatively 40 minutes to 2 hours. For purposes of this application, aerobic or anaerobic conditions means that oxygen is not required to be present in the gas in the headspace of the reactor or dissolved in the liquid where copolymerizing takes place. The balance of the gas in the headspace could be an inert gas such as nitrogen or argon.

[0031] The product produced in step 1), e.g., either via emulsion polymerization or by emulsifying the solvent borne composition (after solvent removal) is an aqueous emulsion comprising (F) the silicone - (meth)acrylate copolymer, (K) the manganese ion source, (E) the phenolic compound, (D) the surfactant, and (E) the water. This aqueous emulsion can be used to prepare an emulsion formulation useful for treating a textile. A process for preparing the emulsion formulation suitable for treating the textile may comprise practicing step 1) of the process described above, thereby preparing the aqueous emulsion, and 2) combining the aqueous emulsion prepared in step 1) and an additional starting material comprising (G) a water dispersible crosslinker. Step 2) may optionally further comprise adding a further additional starting material, which may be selected from the group consisting of (M) a wax, (N) a biocide, (O) additional water (which may be the same as starting material (E)), (P) a flame retardant, (Q) a wrinkle reducing agent, (R) an antistatic agent, (S) a penetrating agent and a combination of two or more of starting materials (M), (N), (O), (P),(Q), (R) and (S). Step 2) of this process may optionally further comprise adding additional (D) surfactant.

[0032] Step 2) of the process described above may be performed by any convenient means, such as mixing using in a jacketed vessel equipped with an agitator. Step 1) and step 2), and any optional and / or additional steps as described above may be performed sequentially in the same vessel. Alternatively, step 1) and step 2) may be performed in different equipment. Step 2) maybe performed at RT or elevated temperature, e.g., up to 100°C, alternatively 40°C to 80°C. Alternatively, heating may be performed in step 1), and step 2) may be performed at RT. Alternatively, step 2) may be performed at lower temperatures and elevated pressures, such as up to 5 atmospheres. The starting materials used in the processes described above are further described below.(A) Crystallizable Monomer

[0033] Starting material (A) is a crystallizable monomer of formula (A-l):, where R1and R2are as described above. Examples of crystallizable monomers for starting material (A) include stearyl (meth)acrylate, eicosyl (meth)acrylate, behenyl (meth)acrylate, and combinations thereof. Alternatively, when R2is hydrogen, starting material (A) may be an acrylate selected from stearyl acrylate, eicosyl acrylate, behenyl acrylate, and combinations thereof. Crystallizable monomers suitable for starting material (A) are commercially available, e.g., from Millipore Sigma of St. Louis, Missouri, USA and from BASF SE of Ludwigshafen, Germany. Crystallizable means that the monomer has a melting point) > 25 °C ± 5 °C.

[0034] Starling material (A) is used in an amount of 80% to 98.75%, based on combined weights of starting materials (A), (B), and (C), and when 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%, and 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 98.5%, alternatively 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%, and alternatively up to 89%, on the same basis. Alternatively, the amount of starting material (A) may be 80% to 98%, alternatively 81% to 97%, alternatively 82% to 96%, alternatively 82% to 95%, alternatively 85% to 90%; on the same basis.

[0035] Starting material (B) is a silicone - (meth)acrylate macromonomer of formula (B- 1 ):are as described above.

[0036] Alternatively, starting material (B) may comprise formula (B-2):are as described above.

[0037] Alternatively, starting material (B) may comprise a macromonomer selected from the group consisting of:3-(5-((l,l,l,3,5,5,5-heptamethyltrisiloxan-3-yl)oxy)-l,l,l,3,7,9,9,9-octamethyl-3,7- bis((trimethylsilyl)oxy)pentasiloxan-5-yl)propyl methacrylate of formula3-( 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, which has formulaand a combination thereof. Stalling material (B) may be prepared by known methods, such as those disclosed in PCT Publication WO2020 / 142388 and U.S. Patent 6,420,504.

[0038] Starting material (B) is used in an amount of 0.25% to 15%, based on combined weights of starting materials (A), (B), and (C), and when present (J). 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, stalling material (B) may be present in an amount up to 15%, alternatively up to 14%, alternatively up to 13%, alternatively up to 12%, alternatively up to 11%, and 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%; and alternatively 10%, on the same basis described above.Starting Material (C) Crosslinkable (Meth)acrylate Monomer

[0039] Starting material (C) is a crosslinkablc (mcth)acrylatc monomer. The crosslinkablc(meth)acrylate monomer may have formula (where R2, R7, D3, R8, and subscript v are as described above. Examples of suitable crosslinkable (meth)acrylates for starting material (C) include (2-acetoacetoxy)ethyl methacrylate,hydroxybutyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxyethylcaprolactone (mcth)acrylatc, hydroxypropyl (mcth)acrylatc, urcido (mcth)acrylatc, glycidyl (mcth)acrylatc (GMA), poly(ethylene glycol) (meth)acrylate (PEGMA), and combinations thereof. The ureido (meth)acrylate monomer may have formula (C-2):oxygen atom or an NH moiety. Examples of ureido monomers are known in the art and are disclosed, for example, in U.S. Patent 9,212,292 to Pressley, et al. Other crosslinkable (meth)acrylate monomers are known in the ail and are commercially available, e.g., from BASF SE. Other crosslinkable (meth)acrylates are commercially available as Sipomer WAM1 and 2.

[0040] Alternatively, starting material (C), the crosslinkable (meth) acrylate monomer may be (C-3) (meth)acrylic acid. Acrylic acid and methacrylic acid are commercially available from Sigma-Aldrich, Inc. of St. Louis, Missouri, USA.

[0041] Starting material (C) is used in an amount 1% to 5%, based on combined weights of starting materials (A), (B), and (C), and when 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%, and 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%, and 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%, and alternatively 2%; on the same basis.Starting Material (D) Surfactant

[0042] Stalling material (D) is a surfactant. The surfactant may be selected from the group consisting of (D-l) a cationic surfactant, (D-2) a nonionic surfactant, and (D-3) a combination of both the cationic surfactant and the nonionic surfactant. Cationic surfactants useful herein include compounds containing quaternary ammonium hydrophilic moieties in the molecule which are positively charged, such as quaternary ammonium salts, which may be represented by formula (D-l-1): R12R13R14R15N+X’" where R12to R15are alkyl groups containing 1-30 carbonatoms, or alkyl groups derived from tallow, coconut oil, or soy; and X’ is a halogen, e.g., chlorine or bromine. Alternatively, the quaternary ammonium compounds may be alkyl trimethylammonium and dialkyldimethylammonium halides, or acetates, having at least 8 carbon atoms in each alkyl substituent. Dialkyl dimethyl ammonium salts can be used and are represented by formula (D-l-2): R16R17N+(CH3)2X’_where R16and R17are alkyl groups containing 12-30 carbon atoms or alkyl groups derived from tallow, coconut oil, or soy; and X’ is halogen. Monoalkyl trimethyl ammonium salts can be used and are represented by formula (D- 1-3): R18N+(CH3)3X”- where R18is an alkyl group containing 12-30 carbon atoms or an alkyl group derived from tallow, coconut oil, or soy; and X” is halogen or acetate.

[0043] Representative quaternary ammonium halide salts are dodecyltrimethyl ammonium chloride / lauryltrimethyl ammonium chloride (LTAC), cetyltrimethyl ammonium chloride (CTAC), hexadeclyltrimethyl ammonium chloride, didodecyldimethyl ammonium bromide, dihexadecyldimethyl ammonium chloride, dihexadecyldimethyl ammonium bromide, dioctadecyldimethyl ammonium chloride, dieicosyldimethyl ammonium chloride, and didocosyldimethyl ammonium chloride. These quaternary ammonium salts are commercially available under trademarks such as ADOGEN™, ARQUAD™, TOMAH™, and VARIQUAT™.

[0044] Other suitable cationic surfactants which can be used include fatty acid amines and amides and their salts and derivatives, such as aliphatic fatty amines and their derivatives. Such cationic surfactants that are commercially available include compositions sold under the names ARQUAD™ T27 W, ARQUAD™ 16-29, by Akzo Nobel Chemicals Inc., Chicago, Illinois; and Ammonyx Cetac-30 by the Stepan Company, Northfield, Illinois, USA.

[0045] The amount of (D-l) the cationic surfactant may be 0.1% to 5%, based on weight of starting material (F) the 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 at the same time 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%, and alternatively 0.5% to 2%; on the same basis.

[0046] Starting material (D-2) is a nonionic surfactant. Some suitable nonionic surfactants which can be used include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers,alkylglucosides, polyoxyethylene fatty acid esters, sorbitan fatty acid esters, and polyoxyethylene sorbitan fatty acid esters. Nonionic surfactants which arc commercially available include compositions such as (i) 2,6,8-trimethyl-4-nonyl polyoxyethylene ether sold under the names TERGITOL™ TMN-6 and TERGITOL™ TMN-10; (ii) the Cl 1-15 secondary alkyl polyoxyethylene ethers sold under the names TERGITOL™ 15-S-7, TERGITOL™ 15-S-9, TERGITOL™ 15-S-15, TERGITOL™ 15-S-30, and TERGITOL™ 15-S-40, by the Dow Chemical Company, of Midland, Michigan, USA; octylphenyl polyoxyethylene (40) ether sold under the name TRITON™ X405 by the Dow Chemical Company; (iii) nonylphenyl polyoxyethylene (10) ether sold under the name MAKON™ 10 by the Stepan Company; (iv) ethoxylated alcohols sold under the name Trycol 5953 by Henkel Corp. / Emery Group, of Cincinnati, Ohio, USA; (v) ethoxylated alcohols sold under the name BRIJ™ L23 and BRU™ L4 by Croda Inc. of Edison, New lersey, USA, (vi) alkyl-oxo alcohol polyglycol ethers such as GENAPOL™ UD 050, and GENAPOL™ UDI 10, (vii) alkyl polyethylene glycol ether based on ClO-Guerbet alcohol and ethylene oxide such as LUTENSOL™ XP 79.

[0047] Suitable nonionic surfactants also include poly(oxyethylene)-poly(oxypropylene)- poly (oxy ethylene) tri-block copolymers. Poly(oxyethylene)-poly(oxypropylene)- poly(oxyethylene) tri-block copolymers are also commonly known as Poloxamers. They are nonionic triblock copolymers composed 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) tri-block copolymers are commercially available from BASF of Florham Park, New Jersey, USA, and are sold under the tradename PLURONIC™, such as PLURONIC™ L61, L62, L64, L81, P84.

[0048] Other suitable nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenol ethers, polyoxyethylene lauryl ethers, polyoxyethylene sorbitan monooleates, polyoxyethylene alkyl esters, polyoxyethylene sorbitan alkyl esters, polyethylene glycol (such as polyethylene glycol having 23 ethylene-oxide units), polypropylene glycol, diethylene glycol, ethoxylated trimethylnonanols, and polyoxyalkylene glycol modified polysiloxane surfactants. Commercially available nonionic surfactants which can be used include compositions such as 2,6,8-trimethyl-4-nonyloxy polyethylene oxyethanols (6EO) and (10EO) sold under the trademarks TERGITOL™ TMN-6 and TERGITOL™ TMN-10; alkyleneoxy polyethylene oxyethanol (C| _ 5 secondary alcohol ethoxylates 7EO, 9EO, and15E0) sold under the trademarks TERGITOL™ 15-S-7, TERGITOL™ 15-S-9, TERGITOL™ 15-S-15; other C | ]_ 15 secondary alcohol ethoxylates sold under the trademarks TERGITOL™ 15-S-12, 15-S-20, 15-S-30, 15-S-40; octylphenoxy polyethoxy ethanol (40EO) sold under the trademark TRITON™ X-405; and alcohol ethoxylates with tradename ECOSURF™ EH, such as ECOSURF™ EH-40. All of these surfactants are sold by the Dow Chemical Company.

[0049] Other useful commercial nonionic surfactants are nonylphenoxy polyethoxy ethanol (10EO) sold under the trademark MAKON™ 10 by Stepan Company; polyoxyethylene 23 lauryl ether (Laureth-23) sold commercially under the trademark BRIJ™ 35L by ICI Surfactants, of Wilmington, Delaware, USA; and RENEX™ 30, a polyoxyethylene ether alcohol also sold by ICI Surfactants.

[0050] The nonionic surfactant may also be a silicone polyether (SPE). The silicone polyether as an emulsifier may have a rake type structure wherein the polyoxyethylene or polyoxyethylene-polyoxypropylene copolymeric units are grafted onto the siloxane backbone, or the SPE can have an ABA block copolymeric structure wherein A represents the poly ether portion and B the siloxane portion of an ABA structure. Suitable SPE’s include DOWSIL™ OFX-5329 Fluid from Dow Silicones Corporation of 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 may be used to form such aqueous emulsions and are known in the art, and have been described, for example, in U.S. Patent 4,122,029 to Gee et al., U.S. Patent 5,387,417 to Rentsch, and U.S. Patent 5,811,487 to Schulz et al.

[0051] Starting material (D-2) the nonionic surfactant may be delivered in a dilution, and the amount used may be sufficient to provide 0.1% to 10% of the surfactant, based on weight of starting material (F) the 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%, and alternatively 0.5% to 2%; on the same basis. Alternatively, starting materials (D-l) the cationic surfactant and (D-2) the nonionic surfactant may be present incombined amounts < 10%, based on weight of starting material (F) the silicone - (meth) acrylate copolymer in the aqueous emulsion.Starting Material (E) Water

[0052] Starting material (E) is water. The water is not generally limited, for example, the water may be processed or unprocessed. Examples of processes that may be used for purifying the water include distilling, filtering, deionizing, and combinations of two or more thereof, such that the water may be deionized, distilled, and / or filtered. Alternatively, the water may be unprocessed (e.g. may be tap water, i.e., provided by a municipal water system or well water, used without further purification). The amount of water is sufficient to form an aqueous emulsion for emulsion polymerization in step 1) of the process described above. Additional water may be added after step 1). For example, the aqueous emulsion prepared as described above may be diluted with additional water to achieve a desired amount of starting materials before treating a textile with the emulsion formulation. The 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%, and alternatively 60% to 80%; based on combined weights of all starting materials in step 1). Alternatively, the 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 at the same time the amount of water may be up to 97%, alternatively up to 96%, alternatively up to 95%, and alternatively up to 80%, on the same basis.

[0053] Without wishing to be bound by theory, it is thought that starting materials (A), (B), and (C), and when present (J), copolymerize to form (F) the silicone - (meth)acrylate copolymer described below as starting material (F). It is further thought that starting materials (D) surfactant and (E) water do not participate in the copolymerization reaction, however, a copolymer including one or both of starting materials (D) and (E) is not excluded from the scope herein.Starting Material (F) Silicone - (Meth) acrylate Copolymer

[0054] The silicone - (meth)acrylate copolymer is prepared by emulsion copolymerization of starting materials comprising (A), (B), (C), and (I) described above. Alternatively, the silicone - (meth)acrylate copolymer is a reaction product of starting materials consisting essentially of starting materials (A), (B), (C), and (I) (and when present, (H) the chain transfer agent and / or (J) the additional monomer). Alternatively, the silicone - (meth)acrylate copolymer is a reactionproduct of starting materials consisting of starting materials (A), (B), (C), and (I) (and, when present, (H) and / or (J)). Without wishing to be bound by theory, it is thought that none of starting materials (D) and (E) copolymerize with starting materials (A), (B), and (C), but merely serve as a vehicle for copolymerization. However, nothing herein shall exclude the possibility that a portion of one or more of starting materials (D) and / or (E), or any other starting material added during the method, may participate in the copolymerization reaction of starting materials comprising (A), (B), (C), and (I).Stalling Material (G) Water Dispersible Crosslinker

[0055] Starting material (G) is a water dispersible crosslinker (crosslinker) that may be added to the emulsion formulation for treating textiles. Suitable crosslinkers include blocked isocyanates and diols. The term “blocked isocyanates” encompasses mono-, di- and polyisocyanates in which an isocyanate group has been reacted with a blocking agent, which upon heating, release the isocyanate and the blocking agent. Suitable blocking agents are known in the ail such as amines, amides, compounds having an active hydrogen atom, alcohols, or oximes. Blocked isocyanates are commercially available, such as ARKOPHOB™ DAN and ARKOPHOB™ SR from Archroma of Reinach, Switzerland; RUCO-GUARD™ WEB from Rudolf GmbH of Geretsreid, Bayern, Germany, and PHOBOL™ UXN extender and PHOBOL™ XAN extender from Archroma. Diols include, for example, 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-l,3-propanediol; 2,2- diethyl-l,3-propanediol. Examples of suitable crosslinkers are known in the art and are disclosed, for example, in U.S. Patent Application 2017 / 0204558 to Knaup; U.S. Patent 9,777,105 to Hamajima et al., beginning at col. 11, line 54, which are hereby incorporated by reference for the purpose of describing suitable crosslinkers. The exact amount of crosslinker (G) depends on various factors including the type and amount of (F) silicone - (meth) acrylate copolymer formed in step 1) and the textile to be treated, however, the weight of the crosslinker (G) may 0.25% to 3.75% on fabric weight, alternatively 0.25% to 1%, and alternatively 0.25% to 0.5%, on the same basis.Starting Material (H) Chain Transfer Agent

[0056] An additional starting material that may be added in step 1) of the process described above comprises (H) a chain transfer agent. Suitable chain transfer agents include mercaptans such as alkyl mercaptans, e.g., n-octyl mercaptan, n-dodecyl mercaptan, dodecyl mercaptan (dodecane thiol), 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 have been 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 © 2012 John Wiley & Sons, Ltd.

[0057] Starting material (H) is optional and may be added in an amount of 0 to 1%, based on combined weights of starting materials (A), (B), and (C) (and when present (J). Alternatively,(H) the chain transfer agent may be used in an amount of 0.5% to 0.6% on the same basis.Starting Material (I) Initiator

[0058] Stalling material (I), an initiator, is also added in step 1) described 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 and 1-t-butylazo-cy anocyclohexane, 2,2’-azo- bis-(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 ail and are commercially available, e.g., under the tradename VAZO™ WSP from The Chemours Company of Wilmington, Delaware, USA. The peroxide compound may be a peroxide or a hydroperoxide, such as t-butylperoctoate, 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. Additionally, 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-butyl peroxycarbo)cyclohexane, 1 ,2-di(t-butyl peroxy)cyclohexane, and 2,5-di(t-butyl peroxy)-3-hexyne. Suitable peroxide compounds are known in the art and are commercially available from various sources, such as Sigma- Aldrich, Inc. Alternatively, the initiator may comprise isoascorbic acid.

[0059] An initiator may be used alone as starting material (I). Alternatively, stalling material(I) may be a redox pair, which comprises an initiator as the oxidizing component and a reducingcomponent. Alternatively, a redox pair including isoascorbic acid and a hydrophobic organic hydroperoxide such as t-amyl hydroperoxide or t-butyl hydroperoxide may be used as starting material (I). Examples of suitable initiators and / or redox pairs for stalling material (I) are disclosed in U.S. Patent 6,576,051 to Bardman et al., beginning at col. 11, 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 pair is used). Typically, when a thermal initiator is used, all the initiator is added at once at the beginning of step 1). Alternatively, when a redox pair is used, it may be metered in over time.

[0060] Alternatively, the initiator may optionally further comprise Iron(II) sulfate heptahydrate, Potassium persulfate, or a combination thereof. The initiator (I) may be used in an amount sufficient to provide 0.01% to 3%, alternatively 0.1% to 1.5%, based on weight of the silicone - (meth)acrylate copolymer.Starting Material (J) Additional Monomer

[0061] Stalling material (J) is an optional additional monomer that may be added in step 1). Starting material (J) is a non-crystallizable monomer that is distinct from starting materials (A), (B), and (C), described above. The additional monomer, when present, may be used in an amount of > 0 to 18.75 weight % based on weight of (F) the 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, e.g., from Polysciences, Inc. Alternatively, the additional monomer (J) may be selected from the group consisting of isobomyl methacrylate (IBMA), isobomyl acrylate (IB A), and a combination thereof. The additional monomer is optional and may be present in an amount of 0 to 18.75%, based on combined weights of starting materials (A), (B), and (C), and when present, (J). Alternatively, (J) the additional monomer may be present in an amount of at least 0.5%, alternatively at least 1%, and alternatively at least 2%; while at the same time the additional monomer may be present in an amount up to 18.75%, alternatively up to 15%, alternatively up to 10%, alternatively up to 8%, and alternatively up to 5%, on the same basis. Alternatively, the amount of (I) the additional monomer may be > 0 to18.75%, alternatively 0.5% to 7%, alternatively 1 % to 6%, and alternatively 2% to 5%, on the same basis.Starting Material (K) Manganese Ion Source

[0062] Starting material (K) is a manganese ion source, which may be a manganese (II) compound. Suitable manganese compounds include manganese (II) acetate, manganese (II) nitrite, manganese (II) propionate, manganese (II) oxide, manganese (II) hydroxide, manganese (II) chloride, manganese (II) phosphate, manganese (II) perchlorate, hydrates thereof (e.g., manganese (II) tetrahydrate) and combinations thereof. Alternatively, the manganese ion source may comprise manganese (II) acetate or manganese (II) tetrahydrate, or a combination thereof. Suitable manganese ion sources are commercially available from Millipore Sigma of St. Louis, Missouri, USA, Fisher Scientific of Waltham, Massachusetts, USA, and City Chemical LLC of Connecticut, USA. The amount of manganese ion source depends on various factors including the selections and amounts of other starting materials used, however the amount may be 0.1 ppm to 5,000 ppm based on combined weights of stalling materials (A), (B), and (C). Alternatively, the amount of the manganese ion source may be > 0 ppm, alternatively at least 0.5 ppm, alternatively at least 1 ppm, alternatively at least 1.5; while at the same time, the amount of manganese ion source may be up to 10 ppm, alternatively up to 5 ppm, alternatively up to 4 ppm, and alternatively up to 3 ppm, and alternatively up to 2 ppm, based on combined weights of all starting materials in the emulsion formulation for treating the textile.(L) Phenolic Compound

[0063] Starting material (L) is a phenolic compound. Suitable phenolic compounds include hydroquinone (HQ), dihydroxybenzene (catechol), resorcinol, dihydroxyxylene, methoxyphenols such as guaiacol, p-methoxyphenol (also called methyl ether of hydroquinone or MeHQ), tertbutyl hydroquinone (tBuHQ), pyrogallol, methylpyrogallol, cresol, phenol, xylenols, and combinations thereof. Alternatively, the phenolic compound may be selected from the group consisting of HQ, MeHQ, tBuHQ, and a combination of two or more thereof. Suitable phenolic compounds are commercially available, e.g., from Millipore Sigma of St. Louis, Missouri, USA. The amount of phenolic compound source depends on various factors including the selections and amounts of other starting materials used, however the amount may be 5 ppm to 5,000 ppm based on combined weights of starting materials (A), (B), and (C). Alternatively, the amount of the phenolic compound may be at least 5 ppm, alternatively at least 50 ppm, alternatively at least100 ppm, alternatively at least 150 ppm; while at the same time, the amount of phenolic compound may be up to 500 ppm, alternatively up to 400 ppm, alternatively up to 350 ppm, and alternatively up to 320 ppm, based on combined weights of all stalling materials in the emulsion formulation for treating the textile.Starting Material (M) Wax

[0064] Stalling material (M) is a wax, which may optionally be added to provide improved water repellency or softness to the textile to which the emulsion formulation will be applied. The amount of wax will vary depending on factors including the type of wax selected, the benefit desired, and the fabric to be treated with the emulsion formulation. However, the amount of wax may be 0 to 75%, alternatively 0 to 50%, alternatively 25% to 50% based on weight of (F) the silicone - (meth)acrylate copolymer. Alternatively, when used, the amount of wax may be > 0%, alternatively at least 10%, and alternatively at least 25%, while at the same time 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. ., n-paraffins, iso-paraffins, and / or cycloparaffins), silicone waxes such as silicone wax with long chain alkyl groups (e.g., alkyl methyl silicone wax) and / or amino-silicone wax, and a combination of two or more thereof. Suitable waxes are disclosed, for example, in U.S. Patent Application 2017 / 0204558 to Knaup and U.S. Patent 10,844,151 to Probst, et al. Waxes may be delivered as water-based dispersions, for example Michelman wax 743 and others from Michelman of Cincinnati, Ohio, U.S.A. Other waxes are also commercially available, for example, from Sasol Wax of Hamburg, Germany, and silicone waxes, such as DOWSIL™ AMS-C30, are available from Dow Silicones Corporation of Midland, Michigan, U.S.A.Starting Material (N) Biocide

[0065] Starting material (N) is an optional biocide. The amount of biocide will vary depending on factors including the type of biocide selected and the benefit desired. However, when used, the amount of biocide may be > 0% to 5% based on the combined weights of all starting materials in the emulsion formulation. Starting material (N) is exemplified by (M-l) a fungicide, (M-2) an herbicide, (M-3) a pesticide, (M-4) an antimicrobial agent, or a combination thereof. Suitable biocides are disclosed, for example, in U.S. Patent 9,480,977.Starting Material (S) Penetrating Agent

[0066] Starting material (S) is a penetrating agent. Suitable penetrating agents are exemplifiedby glycol ethers, which are commercially available from The Dow Chemical Company and include DOWANOL™ DPM, TPM, PPh, EPh, Methyl CARBITOL™, and Butyl CARBITOL™.

[0067] When selecting starting materials to add to the aqueous emulsion prepared as described above in step 1) and the emulsion formulation formed in step 2) described above, there may be overlap between types of starting materials because certain starting materials described herein may have more than one function. The starting materials used in aqueous emulsion and / or the emulsion formulation, may be distinct from one another.

[0068] The emulsion formulation suitable for treating a textile comprises: (F) the silicone - (meth)acrylate copolymer, (D) the surfactant, (E) the water, (K) the manganese ion source, (L) the phenolic compound and (G) the water dispersible crosslinker, as described above. The emulsion formulation may optionally further comprise an additional starting material selected from the group consisting of (M) the wax, (N) the biocide, (O) additional water, (P) the flame retardant, (Q) the wrinkle reducing agent, (R) the antistatic agent, (S) the penetrating agent, and a combination of two or more of starting materials (M), (N), (O), (P), (Q), (R) and (S). These additional starting materials and their amounts are as described above. Furthermore, the emulsion formulation described herein may be formulated with starting materials that are fluorocarbon-free. For example, the emulsion formulation may be free of any starting material that contains a fluorine atom covalently bonded to a carbon atom.

[0069] An additional starting material may optionally be used in the process described above. For example, a chelating agent may be used when making the copolymer.Process for Treating Textiles

[0070] The emulsion formulation prepared as described above may be used for treating a textile. For example, a method for treating a textile comprises: I) coating the textile with the emulsion formulation described above, and II) heating the textile. Step I) may be performed by any convenient method, such as padding, dipping, or spraying the textile with the emulsion formulation. However, the method should be sufficient to deliver a sufficient amount of (F) the silicone - (meth)acrylate copolymer and (G) the water dispersible crosslinker sufficient to impart durable water resistance properties to the textile, according to the methods described below. The method may be sufficient to deliver on fabric weight of 0.25 weight % to 10 weight % of (F), the silicone - (meth)acrylate copolymer, and on fabric weight of 0.1 weight % to 3.75 weight %,alternatively 0.25% to 1 %, of (G), the water dispersible crosslinker, both based on weight of the textile.

[0071] Step II) may be performed by any convenient method, such as placing the textile in an oven. Heating the textile may be performed to remove all or a portion of the water and / or cure the emulsion formulation. The exact temperature depends on various factors including the temperature sensitivity of the type of textile selected and the desired drying time. However, heating may be performed at a temperature > 100 °C to remove water. Alternatively, the temperature may be > 100 °C to 200 °C for a time sufficient to remove all or a portion of the water, de-block the blocked isocyanate crosslinker, and / or cure (F) the silicone - (meth)acrylate copolymer.

[0072] The textile to be treated is not specifically restricted. Suitable textiles include naturally derived textiles such as fabrics of cotton, silk, linen, and / or wool; textiles derived from synthetic sources such as rayon, acetate, polyesters, polyamides (such as Nylons), polyacrylonitriles, and polyolefins such as polyethylenes and / or polypropylenes, and combinations of two or more thereof e.g., blends such as polyester / cotton blend). The form of the textile is also not specifically restricted. The emulsion formulation described herein is suitable for use on textiles in any form, e.g., woven fabrics, knitted fabrics, or nonwoven textiles.EXAMPLES

[0073] The following examples are provided to illustrate the invention to one skilled in the art and are not to be interpreted as limiting the invention set forth in the claims. Starting materials used herein were as follows. A textile to be treated was Nylon (style # 01194), which was purchased from Burlington and contained 98.61 % of Nylon and 1.39 % of Spandex. The weight was 6.84 Oz / Lin Yd and plain weave. Another textile to be treated was polyester or PES Woven (crepe), also from Burlington, style 4774075, basis weight 220 g / m2. The textiles to be treated were washed and dried before coating.

[0074] The starting materials used to prepare emulsion formulations for treating textiles are summarized below in Table 1.

[0075] A Fisherbrand™ Model 705 sonic dismembrator was used for sonication. The microfluidizer was a Microfluidics Microfluidizer Model HOY homogenizer. DT-resin-ALMA was a polymethylsilsesquioxane resin comprising difunctional and trifunctional siloxane units, wherein said resin further comprised methacryloxypropyl groups. MQ-resin-ALMA was a polymethylsilsesquioxane resin with methacryloxypropyl groups.

[0076] In this Reference Example 1, samples were prepared as follows.Water was added first and then all starting materials were added on top according to Table 2 for each example. Stearyl acrylate was melted and delivered as a liquid. The entire mix was kept at 45 °C to 50 °C during the emulsion processing step. The starting materials were mixed with aLightin Labmaster at 200 rpm for 10 min and then poured into the hopper of a Niro Soavi spa model NS2002H to homogenize the starting materials at 350 bar, stirring was maintained while in the hopper. 4 L of 50 °C water was poured through the homogenizer to warm the lines before pouring the emulsion. After this first pass the sample was placed into a forced air oven set to 50 °C for 2.5 h . This cycle was repeated 2 more times to make the monomer emulsion mix 1.Note: Example Bl did not have any 50 °C holds between passes, and the total residence time was 12 min to complete 3 passes through the homogenizer for this example only.Table 2: amounts (g) of starting materials in monomer emulsion mix 1Table 3: inhibitor ppm in the monomer emulsion (based on entire emulsion wt)

[0077] In this Reference Example 2, textile treatment emulsions were prepared as follows: 3 separate solutions were prepared (A) 1.053g 70%tBHP in 40 g of DI water (B) 1.44 g Isoascorbic acid in 40 g of water (C) 47 mg of Iron(II) sulfate heptahydrate in 15 g of water.

[0078] 940 g of a monomer emulsion mix 1 from Table 2 above, was added to a 4 neck flask.1 neck had an overhead stirrer set to 200 rpm (IKA KW20 Digital), 1 had a condenser, 1 had a temperature probe and the final had 2 feed lines connected to a dual syringe pump (KD scientific model 200). The 2 syringes were loaded with solutions A and B and then the reaction mixture was heated to 45 °C. After reaching temperature, 5 g of solution C was injected into the flaskand then the initiator feeds started (1 mL / min). Once the feeds were finished the reaction was cooled to room temperature and then a 5 g solution of sodium benzoate (1.5g in 13.5 g of water) was added to make textile treatment emulsion formulation.Textile Treatment Emulsion Formulations:

[0079] The amount of water pickup for each fabric was measured and then textile treatment emulsion formulations were made based on that pick-up weight. See sections below for contents of each formulation. The formulation was then poured into Mathis HVF padder (roll speed of 2m / min at 60psi) for coating. The fabric was passed through the coater until not more dry spots were observed (generally twice) then placed through a forced air Mathis LTF oven at 160°C for 3min. The fabric was weighed both before coating and after coating to get the actual weight coated. 8 replicates were made per sample for each wash cycle (0,1,10,20), and the average value was reported.

[0080] The targeted weight was ~2wt% on fabric. To achieve this a textile treatment emulsion formulation containing of 35.56 g of an emulsion from Table 2, above, 7.41 g of Phobol Extender Xan, and 757.04 g water were mixed. The final weights delivered to the fabric were 1.8 to 2 wt%.Washing / Drying:

[0081] The sheets were laundered using a 90 °F wash followed by a cold rinse cycle (~70 °F) in a Whirlpool model WTW4855HW1 washing machine (settings: normal cycle, hot wash temperature, deep water wash, auto sensing rinse). Dye and perfume free Tide™ was used as the detergent using 39g for 6 pound loads. For smaller loads, the detergent amount was modified proportionally. The hot water for washing the samples went through a building wide water softening system. The cold water was also softened and went through a PDIMX-60 water softener system from Franklin Electric using the standard settings (default 20 setting for hardness). A Whirlpool model WED4850HW0 dryer was used to dry the samples (auto dry cycle on high- 140°F).Durable water repellent testing:

[0082] The Bundesmann test was carried out using the ISO 9865 method. An SDL Atlas M230 Bundesmann test apparatus was used to collect face rating data after 0, 1, 10, and 20 washes. The instrument was calibrated so that each cup collected between 190 and 210mL after 150s. Face Ratings were assigned based on the images in the ISO 9865 method using halfincrements as intermediate assignments. Ratings are averages values from the 8 replicants and arc shown below in Tabic 4. A passing value was > 4.5 to 5.Table 4 Averaged Bundesmann Face Rating for at least 4 samples. Passing requires at least 4.5 at every wash cycle.

[0083] Sample II (working example according to this invention) contained manganese (II) acetate, HQ, and MEHQ and had the best face rating at each time tested. Sample B 1 contained MEHQ and 4-hydroxyTEMPO as inhibitors, but initially failed the face rating test even with only 4 minutes processing time at high temperature. Sample Cl contained the same inhibitors as sample Bl, but was exposed to high temperature for extended time. Sample Cl failed the face rating test after 20 washes. Sample C2 contained MEHQ as inhibitor (but without Mn(II)), and sample C2 failed the face rating test after 1, 10, and 20 washes. Sample C3 contained MEHQ and 4-hydroxyTEMPO as inhibitors and Sample C3 failed the face rating test after 10 and 20 washes.PROBLEMS TO BE ADDRESSED

[0084] There is an industry need for non-fluorocarbon-based textile treatments that impart durable water repellency to various fabrics. Furthermore, there is an industry need for fluorocarbon-free solutions with high durability as measured by the Bundesmann test, described above. There is a further need to produce commercial scale quantities of non-fluorocarbon-based textile treatments and to stabilize the monomer emulsion at higher temperatures for long processing times while maintaining excellent performance properties.INDUSTRIAL APPLICABILITY

[0085] The above examples show that the emulsion formulation and process described herein can produce a fabric having durable water repellency as measured by the Bundesmann test described herein. More specifically, the fabric can have Bundesmann face rating > 4.5 after initial treatment and can maintain the face rating > 4.5 after 1, 5, 10, and 20 washes. Theinventors surprisingly found that using the manganese ion source and the phenolic compound provided the unexpected benefits, c.g., the manganese ion source and the phenolic compound led to better monomer emulsion stability and imparted improved post polymerization emulsion formulation water repellency to fabric (as compared to monomer emulsions that did not contain one or both of the manganese ion source and the phenolic compound).DEFINITIONS AND USAGE OF TERMS

[0086] All amounts, ratios, and percentages herein are by weight, unless otherwise indicated. The SUMMARY and ABSTRACT are hereby incorporated by reference. The articles, “a”, “an”, and “the” each refer to one or more, unless otherwise indicated by the context of the specification. The transitional phrases “comprising”, “consisting essentially of’, and “consisting of’ are used as described in the Manual of Patent Examining Procedure Ninth Edition, Revision 08.2017, Last Revised January 2018 at section §2111.03 I., IL, and III. The use of “for example,” “e.g.,” “such as,” and “including” to list illustrative examples does not limit to only the listed examples. Thus, “for example” or “such as” means “for example, but not limited to” or “such as, but not limited to” and encompasses other similar or equivalent examples. The abbreviations used herein have the definitions in Table 5.Table 5 - Abbreviations

[0087] The invention has been described in an illustrative manner, and it is to be understood that the terminology which has been used is intended to be in the nature of words of description rather than of limitation. With respect to any Markush groups relied upon herein for describing particular features or aspects, different, special, and / or unexpected results may be obtained from each member of the respective Markush group independent from all other Markush members. Each member of a Markush group may be relied upon individually and or in combination and provides adequate support for specific embodiments within the scope of the appended claims.

[0088] Furthermore, any ranges and subranges relied upon in describing the present invention independently and collectively fall within the scope of the appended claims and are understood to describe and contemplate all ranges including whole and / or fractional values therein, even if such values are not expressly written herein. One of skill in the art readily recognizes that the enumerated ranges and subranges sufficiently describe and enable various embodiments of the present invention, and such ranges and subranges may be further delineated into relevant halves, thirds, quarters, fifths, and any other subrange subsumed within the range. As just one example, a range of “16 to 24” may be further delineated into a lower third, i.e.. 16 to 18, a middle third, i.e.. 19 to 21, and an upper third, i.e., from 22 to 24, and alternatively, the range “16 to 24” includes the subrange “18 to 22”, each which individually and collectively are within the scope of the appended claims, and may be relied upon individually and / or collectively and provide adequate support for specific embodiments within the scope of the appended claims. In addition, with respect to the language which defines or modifies a range, such as “at least,” “greater than,” “less than,” “no more than,” and the like, it is to be understood that such language includes subranges and / or an upper or lower limit.

Claims

Claims:

1. A composition comprising: a silicone - (meth)acrylate copolymer comprising unit formula:where each R1is an independently selected alkyl group of 16 to 24 carbon atoms; each R2is independently selected from the group consisting of H and methyl; each D2is a divalent hydrocarbon group of 2 to 12 carbon atoms; each R3is independently a group of formula OSi(R4)3; where each R4is independently selected from the group consisting of R and DSi(R5)a, where each R is an independently selected monovalent hydrocarbon group of 1 to 12 carbon atoms, and 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; each R5is independently selected from the group consisting of R and DSi(R6)a; where each R6is independently selected from the group consisting of R and DSiRa; with the proviso that R4, R5, and R6are selected such that the silicone - (meth) acrylate macromonomer unit with subscript x has at least 6 silicon atoms; each R7is independently selected from the group consisting of an oxygen atom and NH; D3is a divalent hydrocarbon group of 1 to 12 carbon atoms; D4is an alkylene group of 2 to 4 carbon atoms or a divalent alkylarylene group; subscript v represents number of units of formula (OD4), and subscript v has a value of 0 to 12; each R8is a crosslinkable group; each R9is a monovalent hydrocarbon group of 1 to 14 carbon atoms; each R10is independently selected from the group consisting of a halogen, an acetate group, or a monovalent hydrocarbon group of 1 to 14 carbon atoms; subscripts w, x, y, zl, and z2 represent relative weights of each unit in the copolymer, 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 zl has a value of 0 to 18.75; and subscript z2 has a value of 0 to 18.75, and a quantity (w + x + y + zl + z2) = 100; and with the proviso that the copolymer further comprises a terminal moiety; a manganese ion source, anda phenolic compound.A process for preparing the composition of claim 1, the process comprising:1) copolymerizing starting materials comprising80 weight % to 98.75 weight % of (A) a crystallizable monomer of formula, where each R1is an independently selected alkyl group of 16 to 24 carbon atoms; and each R2is independently selected from the group consisting of H and methyl;0.25 weight % to 15 weight % of (B) a silicone - (meth)acrylate macromonomer of (B) a silicone - (meth)acrylate macromonomer of formulahydrocarbon group of 2 to 12 carbon atoms, and each R3is a group of formula OSi(R4)3; where each R4is independently selected from the group consisting of R and DSi(R5)3, where each R is an independently selected monovalent hydrocarbon group of 1 to 12 carbon atoms, and 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; each R5is independently selected from the group consisting of R and DSi(R6)3; where each R6is independently selected from the group consisting of R and DSiR ;; with the proviso that R4, R5, and R6are selected such that the silicone - (meth)acrylate macromonomer unit with subscript x has at least 6 silicon atoms; each R7is independently selected from the group consisting of an oxygen atom and NH;1 weight % to 5 weight % of (C) a crosslinkable (meth) acrylate monomer of formula, where each_R7is independently selected from the group consisting of an oxygen atom and NH, D3is a divalent hydrocarbon group of 1 to 12 carbon atoms, D4is an alkylene group of 2 to 4 carbon atoms, subscript v has a value of 0 to 12, and each R8is a crosslinkable group; where amounts of starting materials (A), (B), and (C) total 100 weight% based on combined amounts of starting materials (A), (B), and (C); and starting materials (A), (B), and (C) are copolymerized in the presence of additional starting materials, wherein the additional starting materials comprise a chain transfer agent; an initiator; optionally an additional monomer distinct from starting materials (A), (B), and (C); and a manganese ion source, and a phenolic compound; thereby forming the composition comprising the silicone - (meth)acrylate copolymer, the manganese ion source, and the phenolic compound.

3. The process of claim 2, further comprising adding a solvent before or during step 1).

4. The process of claim 3, further comprising: removing the solvent after forming the copolymer, and forming an aqueous emulsion comprising the silicone - (meth)acrylate copolymer, the manganese ion source, the phenolic compound, a surfactant, and water.

5. The process of claim 2, wherein step 1 ) comprises an emulsion polymerization reaction; the additional starting materials further comprise a surfactant and water; and the product of step 1 )comprises an aqueous emulsion comprising the silicone - (meth)acrylate copolymer, the manganese ion source, the phenolic compound, the surfactant, and water.

6. The process of claim 4 or claim 5, where starting material (A) is selected from the group consisting of stearyl acrylate, stearyl methacrylate, behenyl methacrylate and behenyl acrylate.

7. The process of any one of claims 4 to 6, where starting material (B) is selected from the group consisting of 3-(5-((l,l,l,3,5,5,5-heptamethyltrisiloxan-3-yl)oxy)-l,l,l,3,7,9,9,9-octamethyl-3,7- bis((trimethylsilyl)oxy)pentasiloxan-5-yl)propyl methacrylate of formula(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)-l,l,5,5- tetramethyltrisiloxan-3-yl)propyl methacrylate of formulacombination thereof.

8. The process of claim 7, where starting material (B) is3-(l,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.

9. The process of any one of claims 4 to 8, where in starting material (C), where each R8is independently selected from the group consisting of hydroxy, amino, epoxy, ureido, and acetoxy.

10. The process of any one of claims 4 to 9, where starting material (C) is 2- hydroxy ethylmethacrylate.

11. The process of any one of claims 4 to 10, where the surfactant is selected from the group consisting of a cationic surfactant, a nonionic surfactant, and a combination thereof.

12. The process of claim 11, where the cationic surfactant comprises a quaternary ammonium compound; or the nonionic surfactant comprises a polyethylene glycol, an alcohol ethoxylate, or a combination thereof.

13. The process of any one of claims 4 to 12, where the chain transfer agent is present, and the chain transfer agent comprises dodecane thiol.

14. The process of any one of claims 4 to 13, where the manganese ion source comprises manganese (II) acetate, manganese (II) acetate tetrahydrate, or a combination thereof.

15. The process of any one of claims 4 to 14, where the phenolic compound is selected from the group consisting of hydroquinone, monomethyl ether of hydroquinone, tert-butylhydroquinone, and a combination of two or more thereof.

16. A process for preparing an emulsion formulation suitable for treating a textile, wherein the process comprises:1 ) practicing the process of any one of claims 4 to 15, thereby preparing the aqueous emulsion; and2) combining the aqueous emulsion and a water dispersible crosslinker comprising a blocked isocyanate.

17. The process of claim 16, further comprising an additional starting material selected from the group consisting of a wax, a biocide, additional water, a flame retardant, a wrinkle reducing agent, an antistatic agent, a penetrating agent or a combination of two or more thereof.

18. An emulsion formulation suitable for treating a textile, where the emulsion formulation comprises: a silicone - (meth)acrylate copolymer comprising unit formula:where each R1is an independently selected alkyl group of 16 to 24 carbon atoms; each R2is independently selected from the group consisting of H and methyl; each D2is a divalent hydrocarbon group of 2 to 12 carbon atoms; each R3is independently a group of formula OSi(R4) ; where each R4is independently selected from the group consisting of R and DSi(R5)3, where each R is an independently selected monovalent hydrocarbon group of 1 to 12 carbon atoms, and 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; each R5is independently selected from the group consisting of R and DSi(R6)3; where each R6is independently selected from the group consisting of R and DSiRa; with the proviso that R4, R5, and R6are selected such that the silicone - (meth)acrylate macromonomer unit with subscript x has at least 6 silicon atoms; each R7is independently selected from the group consisting of an oxygen atom and NH; D3is a divalent hydrocarbon group of 1 to 12 carbon atoms; D4is an alkylene group of 2 to 4 carbon atoms or a divalent alkylarylene group; subscriptv represents number of units of formula (OD4), and subscript v has a value of 0 to 12; each R8is a crosslinkablc group; each R9is a monovalent hydrocarbon group of 1 to 14 carbon atoms; each R10is independently selected from the group consisting of a halogen, an acetate group, or a monovalent hydrocarbon group of 1 to 14 carbon atoms; subscripts w, x, y, zl, and z2 represent relative weights of each unit in the copolymer, 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 zl has a value of 0 to 18.75; and subscript z2 has a value of 0 to 18.75, and a quantity (w + x + y + zl + z2) = 100; and with the proviso that the copolymer further comprises a terminal moiety; a manganese ion source; a quinone compound; a surfactant, water, a water dispersible crosslinker, optionally a wax, optionally a biocide, optionally a flame retardant, optionally a wrinkle reducing agent, optionally an antistatic agent, and optionally a penetrating agent.

19. A process for treating a textile, the process comprising:I) coating the textile with the emulsion formulation of claim 18; andII) heating the textile.

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