Textile treatment composition containing a silicone – (METH)acrylate copolymer and methods for the preparation and use thereof

Abstract

A textile treatment composition is in the form of an aqueous emulsion, which includes a silicone – (meth)acrylate copolymer, a blocked isocyanate crosslinker, a surfactant, and water. The textile treatment composition can be coated on a textile and dried, and thereby imparts water repellency to the textile.

Description

TEXTILE TREATMENT COMPOSITION CONTAINING A SILICONE - (METH)ACRYLATECOPOLYMER AND METHODS FOR THE PREPARATION AND USE THEREOFCROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application claims priority under 35 USC § 119(e) to US Provisional Patent Application Number 63 / 557810 filed on 26 February 2024. US Provisional Patent Application Serial Number 63 / 557810 is hereby incorporated by reference.FIELD

[0002] A composition for treating a textile to impart water repellency is provided. More particularly, the composition and methods for its preparation and use, are provided. Treating a textile with the composition can impart initial water repellency and durable water repellency.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.

[0004] Silicone - (meth)acrylate copolymer compositions and emulsion formulations made with them have been proposed to address the need for non-fluorocarbon-based textile treatments. For example, such compositions are disclosed in PCT Publication WO2022197350 corresponding to US Patent Application Serial No. 18 / 258663; PCT Publication W02023010944 corresponding to US Patent Application Serial No. 18 / 558769; PCT Publication WO2023086692 corresponding to US Provisional Patent Application Serial No. 63 / 277671; US Provisional Patent Application Serial No. 63 / 588046; US Provisional Application Serial No. 63 / 588050; and US Provisional Application Serial No. 63 / 588056; each of which is hereby incorporated by reference.PROBLEMS TO BE ADDRESSED

[0005] However, when using the compositions and emulsion formulations referenced above for textile treatment applications, N-heterocycle-blocked isocyanate crosslinkers may be preferred (over oxime -blocked polyisocyanate crosslinkers) for regulatory and other reasons. Unfortunately, the present inventors surprisingly found that initial water repellency performance may be detrimentally impacted when using an N-heterocycle-blocked polyisocyanate as crosslinker with a silicone - (meth Jacrylate copolymer composition referenced above. While incertain instances, the performance could be improved by laundering the textile after treatment, this is costly and undesirable for commercial production of water repellent textiles. There is an industry need for textiles with good initial water repellency, as described hereinbelow.SUMMARY

[0006] A textile treatment composition comprises: (A) a silicone - (meth)acrylate copolymer, (B) a crosslinker, (C) a catalyst, and (D) water. The textile treatment composition may be applied on fabric and dried, thereby imparting water repellency to the textile.DETAILED DESCRIPTION

[0007] The textile treatment composition introduced above comprises: (A) the silicone - (meth) acrylate copolymer, (B) the crosslinker, (C) the catalyst, and (D) water. The textile treatment composition may optionally further comprise one or more additional components, such as (E) a surfactant, (F) a manganese ion source, (G) a phenolic compound, (H) a wax, (I) a biocide, (J) a flame retardant, (K) a wrinkle reducing agent, (L) an antistatic agent, (M) a penetrating agent, and a combination of two or more of components (E), (F), (G), (H), (I), (J), (K), (L), and (M).(A) Silicone - (meth) acrylate copolymer

[0008] In the textile treatment composition introduced above, component (A) is the silicone - (meth) acrylate copolymer (copolymer). The copolymer may comprise unit formula (Al):wherein 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 selected from the group consisting of R and a group of formula OS i ( R4)s ; wherein each R4is independently selected from the group consisting of R and DSi(R5)3, wherein each R is an independently selected monovalent hydrocarbon group of 1 to 12carbon 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; wherein each R6is independently selected from the group consisting of R and DS i Rs ; with the proviso that R4, R5, and R6are selected such that the silicone - (meth)acrylate macromonomer unit with subscript x has at least 4, alternatively 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 R1Sis independently selected from the group consisting of an oxygen atom and NH; each D’ is an independently selected divalent hydrocarbon group of 1 to 12 carbon atoms; each D1is an alkylene group of 2 to 4 carbon atoms or a divalent alkylarylene group; subscript v2 represents the number of units of formula (OD1) in the unit with subscript y2, and subscript v2 has a value of 0 to 20; each R16is independently selected from the group consisting of a hydroxyl group and an alkoxy group (e.g., methoxy); 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, y2, zl, and z2 represent relative weights of each unit in the copolymer of unit formula (Al), subscript w has a value of 80 to 98.75; subscript x has a value of 0.25 to 15; subscript y has a value of 1 to 5; subscript y2 has a value of 0 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 + y2 + zl + z2) = 100. The copolymer further comprises a terminal moiety.

[0009] In the unit formula (Al) above, R1has 16 to 24 carbon atoms. Alternatively, R1may have at least 16, alternatively at least 17, alternatively at least 18 carbon atoms, while at the same time R1may have up to 24, alternatively up to 23, and alternatively up to 22 carbon atoms. Alternatively, R1may have 17 to 23, carbon atoms, alternatively 16 to 22 carbon atoms, alternatively 17 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.

[0010] In the unit formula (Al) above, the unit with subscript x is a silicone - (meth)acrylate macromonomer unit. In the silicone - methacrylate macromonomer unit, each R3is independently selected from the group consisting of R and a group of formula -O8i(R4h; where each R is an independently selected monovalent hydrocarbon group of 1 to 12 carbon atoms. In the silicone - (meth) acrylate macromonomer unit, the monovalent hydrocarbon group for R maybe 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 may be methyl. In the unit formula (Al), each R4is independently selected from the group consisting of R (as defined above) and DSi(R5)s, wherein 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; wherein each R6is independently selected from the group consisting of R and DSiRj; with the proviso that R3, R4, R5, and R6are selected such that the silicone - (meth)acrylate macromonomer unit with subscript w has at least 4, alternatively at least 6 silicon atoms; while at the same time the silicone - (meth) acrylate macromonomer unit with subscript w may have up to 20 silicon atoms, alternatively up to 19 silicon atoms, alternatively up to 18 silicon atoms, alternatively up to 17 silicon atoms, alternatively up to 16 silicon atoms, and alternatively up to 10 silicon atoms. Alternatively, R3, R4, R5, and R5may be selected such that the silicone - (meth)acrylate macromonomer unit has 4 to 16, alternatively 4 to 10, alternatively 6 to 10 silicon atoms, per unit.

[0011] 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. The divalent hydrocarbon group for D may be alkylene, such as ethylene, propylene, or butylene. Alternatively, each D may be ethylene.

[0012] 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.

[0013] 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.

[0014] In the unit formula (Al) above, 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 D3and each D is independently a divalent hydrocarbon group of 1 to 12 carbon atoms. Alternatively, each D3and each D may be an alkylene group; alternatively, ethylene. D4and D1are each independently an alkylene group of 2 to 4 carbon atoms or a divalent alkylarylene group.

[0015] The divalent hydrocarbon group for D4and D1may 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 D, D2and D3may be as described above, and alternatively may be methylene. Alternatively, D2may be methylene, ethylene or propylene; alternatively, propylene. Alternatively, D2may be linear, e.g., -(CH2)2- or -(CH2)3-.

[0016] In the unit formula (Al) above, each R7is independently selected from the group consisting of an oxygen atom and NH. Alternatively, each R7may be oxygen.

[0017] In the unit formula (Al) 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.

[0018] In the unit formula above each R15is an oxygen atom or NH, alternatively oxygen. Each R16is selected from the group consisting of -OH and alkoxy. Alternatively, the alkoxy group for R16may be -OCH3.

[0019] In the unit formula (Al) 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, isobomyl, and 2-ethylhexyl. Examples of suitable aryl groups include phenyl, naphthyl, anthracyl, and benzyl.

[0020] In the unit formula (Al) 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.

[0021] In the unit formula above, subscripts w, x, y, y2, zl, and z2 are relative weights of each unit, and a quantity (w + x + y + y2 + zl + z2) 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 atleast 82, alternatively at least 83, alternatively at least 84, alternatively at least 85, alternatively at least 86, alternatively at least 87, and alternatively at least 88; while at the same time, subscript w is up to 98.75, 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, alternatively up to 89, and alternatively up to 88. Alternatively, subscript w may be 84 to 92, alternatively 85 to 91, alternatively 86 to 90, alternatively 87 to 89, and alternatively 88.

[0022] In the unit formula (Al) above, the unit with subscript x is the silicone - (meth) acrylate macromonomer unit. Subscript x has a value of 1 to 15, alternatively 5 to 15. Alternatively, subscript x may be at least 1, alternatively at least 5, alternatively at least 6, alternatively at least 7, alternatively at least 8, alternatively at least 9, alternatively at least 10; while 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 7 to 13; and alternatively 10.

[0023] In the unit formula (Al) above, 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 1.75, and alternatively at least 2; while 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.

[0024] In the unit formula (Al) above, subscript y2 has a value of 0 to 5. Alternatively, subscript y2 may be at least 1, alternatively at least 1.25, alternatively at least 1.5, alternatively at least 1.75, and alternatively at least 2; while at the same time, subscript y2 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 y2 may be 0 to 3, alternatively 1 to 2, alternatively 1.5 to 2.5, alternatively 1.75 to 2.25, and alternatively 2. Alternatively, subscript y2 may be 0 and the unit may be absent from the copolymer.

[0025] In the unit formula (Al) above, 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, 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, alternatively > 0 to 18, alternatively 0.5 to 7, alternatively 1 to 6, and alternatively 2 to 5.

[0026] In the unit formula (Al) above, subscript z2 may be 0. Alternatively, subscript z2 maybe 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.

[0027] The total number of units per molecule of the copolymer of unit formula (Al) is not specifically restricted. However, the copolymer may have a number average molecular weight of > 100,000 g / mol, alternatively > 1,000,000 g / mol; by conventional methods based on the selection of each monomer and the chain transfer agent. The units shown above may be in any order, e.g., the copolymer may be a random copolymer or a block copolymer.

[0028] One skilled in the art would recognize that the copolymer may be prepared by radical polymerization, via a process as described in the references cited 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. The copolymer may be prepared as described in PCT Publication WO / 2022 / 197350 corresponding to US Patent Application Serial No. 18 / 258663; PCT Publication WO / 2023 / 010944 corresponding to US Patent Application Serial No. 18 / 558769; PCT Publication WO / 2023 / 086692 corresponding to US Provisional Patent Application Serial No. 63 / 277671; US Provisional Patent Application Serial No. 63 / 588046; US Provisional Application Serial No. 63 / 588050; and US Provisional Application Serial No. 63 / 588056; each of which is hereby incorporated by reference.

[0029] Alternatively, (A) the silicone - (meth)acrylate copolymer may comprise unit formula (A2):wherein each R1is the independently selected alkyl group of 16 to 24 carbon atoms; each R2is independently selected from the group consisting of H and methyl; each D2is the divalent hydrocarbon group of 2 to 12 carbon atoms; each R3is the group of formula OSi(R4)s; wherein each R4is independently selected from the group consisting of R and DSi(R5)3, wherein 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 the oxygen atom, the (poly) alkylene oxidegroup of 1 to 12 units, and the divalent hydrocarbon group of 2 to 4 carbon atoms; each R5is independently selected from the group consisting of R and DSi(R6)3; wherein 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 the oxygen atom and NH; D3is the divalent hydrocarbon group of 1 to 12 carbon atoms; D4is the alkylene group of 2 to 4 carbon atoms or the 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 the crosslinkable group; each R9is the monovalent hydrocarbon group of 1 to 14 carbon atoms; each R10is independently selected from the group consisting of the halogen, the acetate group, or the 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 of unit formula (A2), subscript w has a value of 80 to 98.75; subscript x has a value of 0.25 to 15; 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.

[0030] In the unit formula (A2) above, R1, R2, R, D2, D3, D4, R7, R8, R9, and R10, are as described and exemplified above for unit formula (Al).

[0031] In the unit formula (A2) above, each R3is the 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 DS i R3 ; 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 R5are 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. The monovalent hydrocarbon groups for R, and the (poly) alkylene oxide groups and divalent hydrocarbon groups for D are as described and exemplified above for unit formula (Al).

[0032] In the unit formula (A2) above, subscripts w, x, y, zl, and z2 are relative weights of each unit, and a quantity (w + x + y + zl + z2) 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 atleast 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.

[0033] In the unit formula (A2) above, subscript x has a value of 0.25 to 15. Alternatively, subscript w 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.

[0034] In the unit formula (A2) above, 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.

[0035] In the unit formula (A2) above, 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.

[0036] In the unit formula (A2) above, 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.

[0037] The total number of units per molecule of copolymer of unit formula (A2) is not specifically restricted. However, the copolymer may have a number average molecular weight of > 100,000 g / mol, alternatively > 100,000 g / mol to 4,000,000 g / mol; alternatively 200,000 g / mol to 3,000,000 g / mol measured by GPC. The samples for GPC analysis may be prepared in THF eluent at concentration 10 mg / mL copolymer. The solution may be shaken on a flat-bedshaker at ambient temperature for 2 hours. The solution may then be filtered through a 0.45 m PTFE syringe filter prior to injection. Agilent GPC software Cirrus version 3.3 may be used for data collection and for data reduction. A total of 16 PS linear narrow molecular weight standards from Agilent having Mp values from 3750 to 0.58 kg / mol may be used for molecular weight calibration. A 3rdorder polynomial was used for calibration curve fitting. Thus, all molecular weight averages, distributions and references to molecular weight provided in this report are PS equivalent values. The units of the copolymer shown above may be in any order, e.g., the copolymer may be a random copolymer or a block copolymer.

[0038] One skilled in the art would recognize that the copolymer of formula (A2) may be prepared by radical polymerization, via a process in the references cited below, and that this process would form the terminal moiety for the copolymer. This copolymer may be prepared as described in PCT Publication WO2022197350 corresponding to US Patent Application Serial No. 18 / 258663, or US Provisional Patent Application Serial No. 63 / 588046.

[0039] The silicone - (meth)acrylate copolymer (e.g., of unit formula (Al) or unit formula (A2)) described above may be prepared via an emulsion polymerization process, wherein monomers, a surfactant, water, a chain transfer agent, and an initiator, and optionally a manganese ion source and a phenolic compound) may be combined to form an aqueous emulsion. Alternatively, an aqueous emulsion comprising the silicone - (meth)acrylate copolymer, a surfactant, and water (and optionally a manganese ion source and a phenolic compound) may be prepared after formation of the silicone - (meth) acrylate copolymer. The resulting aqueous emulsion may comprise 20% to 97% of water and 0.1% to 10% of the surfactant, each based on weight of (A) the silicone - (meth)acrylate copolymer, with the balance to 100% being the silicone - (meth)acrylate copolymer.(B) Crosslinker

[0040] Component (B) in the textile treatment composition is a crosslinker that is free of oxime blocking agents. The crosslinker may comprise a nitrogen containing heterocycle (N- heterocycle) - blocked isocyanate. The N-heterocycle-blocked isocyanate comprises an isocyanate compound and an N-heterocycle-blocking agent. The isocyanate compound may be monomeric or polymeric. The isocyanate compound may comprise, or maybe, a unit selected from the group consisting of IPDI, H12MDI, TMXDI, TMI, XDI, H6XDI, MDI, TDI, and HDI. Alternatively, the polyisocyanate may be an aliphatic isocyanate where the NCO group is not directly attached to an aromatic ring. Alternatively, the polyisocyanate may be HDI or MDI. The N-heterocycle blocking agent may be caprolactam, 2,6-dimethylpyrazine or a dimethylpyrazole, e.g., 3,5-dimethylpyrazole. The blocking agent is not an oxime. Thecrosslinker for use herein may be free of oxime compounds. Suitable crosslinkers are commercially available and may be delivered in aqueous dispersions, and examples thereof are shown below in Table 1.Table 1 - Commercially Available Crosslinkers

[0041] The exact amount of component (B) depends on various factors including the type and amount of component (A) the silicone - (meth) acrylate copolymer, and the selection of textile to be treated, however, the amount of component (B) in the textile treatment composition may be sufficient to provide 0.1% to 0.75% of solids, on fabric weight, alternatively 0.1% to 0.35%, on the same basis; wherein solids refers to the amount of N-heterocycle blocked isocyanate that may be delivered in an aqueous dispersion with other components, e.g., water and a surfactant.(C) Catalyst

[0042] Component (C) in the textile treatment composition is a catalyst. The catalyst comprises a metal complex, which may be a metal carboxylate (e.g., a metal acetate or a metal acetylacetonate), wherein the metal is selected from the group consisting of manganese (Mn), zinc (Zn), and zirconium (Zr). Alternatively, the metal may be Zn or Zr, and alternatively Zn. Suitable catalysts include manganese (II) acetate (CAS No. 638-38-0), manganese (II) acetatetetrahydrate (CAS No. 6156-78-1), manganese (II) acetylacetonate (CAS No. 14024-58-9), manganese (III) acetylacetonate (CAS No. 14284-89-0), zinc acetate hydrate (CAS No. 16788- 43-5), zinc (II) acetate (CAS No. 557-34-6), zinc (II) acetate dihydrate (CAS No. 5970-45-6), zinc(II) acetylacetonate (CAS No. 14024-63-6), zinc (II) acetylacetonate hydrate (CAS No. 108503-47-5), zirconium acetate (CAS No. 7585-20-8), and zirconium (IV) acetylacetonate (CAS No. 17501-44-9), all of which are commercially available from Sigma Aldrich, Inc. of St. Louis, Missouri, USA. The amount of component (C) depends on various factors including the types and amounts of components (A) and (B), however, the amount of component (C) may be > 0 to 10%, alternatively 0.5% to 7.5%, alternatively > 0.5% to < 7.5%, and alternatively 1% to 5%, based on weight of metal complex to crosslinker (solids). Alternatively, the textile treatment composition may comprise 0.001 weight % to 0.1 weight %, based on combined weights of starting materials (A), (B), (C), and (D), of (C) the catalyst.(D) Water

[0043] The textile treatment composition may be in the form of an aqueous emulsion, wherein the silicone - (meth) acrylate copolymer is in the discontinuous oil phase dispersed in a continuous aqueous phase comprising water. The water in the textile treatment composition may be provided, in whole or in part, by the process used to make (A) the silicone - (meth)acrylate copolymer, e.g., the water used for hydrolysis of monomers and / or water may be introduced with (B) the crosslinker, for example, when the crosslinker is delivered in an aqueous dispersion or emulsion, as described above. Additional water may optionally be added to dilute the textile treatment composition to a desired concentration of components (A), (B), and (C). The water is not generally limited, and may be utilized neat (i.e., absent any carrier vehicles and / or solvents), and / or pure (i.e., free from, or substantially free from, minerals and / or other impurities). For example, the water may be processed or unprocessed prior to use as described herein. Examples of processes that may be used for purifying the water include distilling, filtering, deionizing, reverse osmosis, 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, provided by a municipal water system or well water, used without further purification). The water may be utilized in any amount, which will be selected by one of skill in the art, depending on various factors, e.g., the equipment and process conditions used to treat fabric with the textile treatment composition, however, the amount of water may be 90% to < f 00%, alternatively 91% to 99%, alternatively 94% to 98%, based on combined weights of all components in the textile treatment composition.

[0044] The textile treatment composition comprising components (A), (B), (C), and (D)described above may optionally further comprise an additional component. The additional component may be selected from the group consisting of (E) a surfactant, (F) a manganese ion source (that differs from (C) the catalyst), (G) a phenolic compound, (H) a wax, (I) a biocide, (J) a flame retardant, (K) a wrinkle reducing agent, (L) an antistatic agent, (M) a penetrating agent, and a combination of two or more of (E), (F), (G), (H), (I), (J), (K), (L), and (M). Furthermore, the textile treatment composition described herein may be formulated with components that are fluorocarbon-free. For example, the textile treatment composition may be free of any component that contains a fluorine atom covalently bonded to a carbon atom.(E) Surfactant

[0045] The textile treatment composition may optionally further comprise component (E), a surfactant. The surfactant may be introduced with (A) the copolymer and / or (B) the crosslinker, both of which may be delivered in aqueous emulsions or dispersions. The surfactant may be selected from the group consisting of (E-l) a cationic surfactant, (E-2) a nonionic surfactant, and (E-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 (E-l-1): R11R12R13R14N+X’" where R11to R14are alkyl groups containing 1-30 carbon atoms, 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 (E-l-2): R16R17N+(CH3)9X’_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 (E- 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.

[0046] Representative quaternary ammonium halide salts are dodecyltrimethyl ammonium chloride / lauryl trimethyl ammonium chloride (LT AC), cetyltrimethyl ammonium chloride (CT AC), 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™.

[0047] 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.

[0048] The amount of (E-l) the cationic surfactant may be 0.1% to 5%, based on weight of (A) the silicone - (meth) acrylate copolymer in the textile treatment composition. 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.

[0049] Component (E-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 are 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; 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 BRU™ L23 and BRU™ L4 by Croda Inc. of Edison, New Jersey, 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.

[0050] 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 composed of a central hydrophobic chain of polyoxypropylene (polypropylene oxide)) flanked by two hydrophilic chains of polyoxyethylene (polyethyleneoxide)). 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.

[0051] 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 (Ci i_ 15 secondary alcohol ethoxylates 7EO, 9EO, and 15EO) sold under the trademarks TERGITOL™ 15-S-7, TERGITOL™ 15-S-9, TERGITOL™ 15-S-15; other C ] ] ] secondary alcohol ethoxylates sold under the trademarks TERGITOL™ 15-S-12, 15-S-20, 15-S-30, 15-S-40; octylphenoxy poly ethoxy 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.

[0052] 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 BRU™ 35L by ICI Surfactants, of Wilmington, Delaware, USA; and RENEX™ 30, a polyoxyethylene ether alcohol also sold by ICI Surfactants.

[0053] The nonionic surfactant may also be a silicone polyether (SPE). The silicone poly ether as an emulsifier may have a rake type structure wherein the polyoxyethylene or polyoxyethylene-polyoxypropylene copolymeric units are grafted onto the siloxane backbone, or the SPE can have an ABA block copolymeric structure wherein A represents the polyether portion and B the siloxane portion of an ABA structure. Suitable SPE’s include DOWSIL™ OFX-5329 Fluid from The Dow Chemical Company. Alternatively, the nonionic surfactant may be selected from polyoxyalkylene-substituted silicones, silicone alkanolamides, silicone esters and silicone glycosides. Such silicone-based surfactants may be used to form such aqueous emulsions and are known in the art, and have been described, for example, in US Patent 4122029 to Gee et al., US Patent 5387417 to Rentsch, and US Patent 5811487 to Schulz et al.

[0054] Component (E-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 (A)the silicone - (meth) acrylate copolymer in the textile treatment composition. 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, (E-l) the cationic surfactant and (E- 2) the nonionic surfactant may be present in combined amounts < 10%, based on weight of (A) the silicone - (meth) acrylate copolymer in the textile treatment composition.Component (F) Manganese Ion Source

[0055] Component (F) is a manganese ion source, which may be introduced into the textile treatment composition in the aqueous emulsion containing the copolymer when the manganese ion source is used during production of the copolymer and / or the aqueous emulsion used to deliver the copolymer. The amount of manganese ion source is in addition to the amount of (C) the catalyst, when (C) the catalyst comprises a manganese compound. The manganese ion source may be a manganese (II) compound. Suitable manganese compounds for component (F) 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 components used, however the amount may be 0.1 ppm to 5,000 ppm based on combined weights of components (A), (B), and (C) in the textile treatment composition.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 components in the textile treatment composition.(G) Phenolic Compound

[0056] Component (G) is a phenolic compound, which may be introduced into the textile treatment composition via the aqueous emulsion containing the copolymer when the phenoliccompound source is used during production of the copolymer and / or the aqueous emulsion used to deliver the copolymer. Suitable phenolic compounds include hydroquinone (HQ), dihydroxybenzene (catechol), resorcinol, dihydroxyxylene, methoxyphenols such as guaiacol, p- methoxyphenol (also called methyl ether of hydroquinone or MeHQ), tert-butyl 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 components used, however the amount may be 5 ppm to 5,000 ppm based on combined weights of components (A), (B), and (C). Alternatively, the amount of the phenolic compound may be at least 5 ppm, alternatively at least 50 ppm, alternatively at least 100 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 components in the textile treatment composition.(H) Wax

[0057] Component (H) is a wax, which may optionally be added to the textile treatment composition to provide improved water repellency or softness to the textile to which the textile treatment composition will be applied. The amount of wax will vary depending on factors including the type of wax selected, the benefit desired, and the textile to be treated with the textile treatment composition. However, the amount of wax may be 0 to 75%, alternatively 0 to 50%, alternatively 25% to 50% based on weight of (A) 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.g., 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 US Patent Application 20170204558 to Knaup and US Patent 10844151 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 The Dow Chemical Company.(I) Biocide

[0058] Component (I) 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 components in the textile treatment composition. Component (I) is exemplified by (1-1) a fungicide, (1-2) an herbicide, (1-3) a pesticide, (1-4) an antimicrobial agent, or a combination thereof. Suitable biocides are disclosed, for example, in US Patent 9480977.(M) Penetrating Agent

[0059] Component (M) is a penetrating agent. Suitable penetrating agents are exemplified by glycol ethers, which are commercially available from The Dow Chemical Company and include DOW ANOL™ DPM, TPM, PPh, EPh, Methyl CARBITOL™, and Butyl CARBITOL™.

[0060] When selecting components to add to the textile treatment composition described above, there may be overlap between types of components because certain components described herein may have more than one function. The components used in the textile treatment composition may be distinct from one another. Furthermore, the textile treatment composition described herein may be formulated with components that are fluorocarbon-free. For example, the textile treatment composition may be free of any component that contains a fluorine atom covalently bonded to a carbon atom.

[0061] The textile treatment composition may be prepared by any convenient means in any convenient equipment. For example, the textile treatment composition may be prepared by mixing, under ambient conditions (e.g., at RT and atmospheric pressure): an aqueous emulsion comprising (A) the silicone - (meth) acrylate copolymer and water and optionally with one or more of (E) surfactant, (F) manganese ion source, and (G) phenolic compound; an aqueous dispersion or emulsion of (B) the crosslinker and water and optionally with (E) surfactant; and (C) the catalyst. One or more of components (H), (I), (J), (K), (L), and (M) may also be included and mixed.Process for Treating Textiles

[0062] The textile treatment composition prepared as described above may be used for treating a textile to impart water repellency. For example, a method for treating a textile comprises: I) coating the textile with the textile treatment composition 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 textile treatment composition. However, the method should be sufficient to deliver amounts of (A) the silicone - (meth)acrylate copolymer, (B) the crosslinker, and (C) the catalyst sufficient to impart water repellency to the textile, according to the methods described below. The method may be sufficient to deliver on fabric weight of 0.25 weight % to5 weight %, alternatively 2 weight % to 4 weight %, alternatively 1 weight % to 3 weight %, and alternatively 1% to 2%, of (A) the silicone - (meth) acrylate copolymer and on fabric weight of 0.1% to 0.75%, alternatively 0.1% to 0.35%, of (B) the crosslinker, both based on weight of the textile. The method may be sufficient to deliver an amount of (C) the catalyst of > 0 to 10%, alternatively 0.25% to 10%, alternatively 0.5% to < 10%, alternatively 0.5% to 7.5%, and alternatively 1% to 5% of the catalyst based on weight of the crosslinker (solids), i.e., weight of the N-heterocycle blocked isocyanate compound, excluding water and other components of any dispersion used to deliver the N-heterocycle blocked isocyanate compound.

[0063] 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 textile treatment composition. The exact temperature depends on various factors including the temperature sensitivity of the type of textile selected, the deblocking temperature of the crosslinker, 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, and alternatively 110 °C to 160 °C, for a time sufficient to remove all or a portion of the water, deblock the blocked isocyanate crosslinker, and / or cure (A) the silicone - (meth) acrylate copolymer. The heating time may depend on various factors including the temperature selected, however the time may be 1 min to 5 min, alternatively 2 min to 3 min.

[0064] 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 textile treatment composition described herein is suitable for use on textiles in any form, e.g., woven fabrics, knitted fabrics, or nonwoven textiles.EXAMPLES

[0065] The following examples are provided to illustrate the invention to one skilled in the art and are not to be construed to limit the scope of the invention set forth in the appended claims. Components used in these examples are summarized above in Table 1 and below in Table 2. Table 2 - Components used in the Examples

[0066] In this Reference Example 1, textile treatment compositions were prepared by mixing the components in the amounts shown below in Tables 3 and 4.Table 3 - Comparison of PHOBOL EXTENDER XAN (oxime blocked) and PHOBOLEXTENDER UXN (N-heterocycle blocked) CrosslinkersTable 4 - Samples containing Water Repellent (A-l) and Different Crosslinkers0067] In this reference example 2, fabric samples were treated according to the following procedure: All the fabric pieces were washed / dried before coating. Each textile treatment composition was then poured into a Mathis HVF padder (roll speed of 2m / min at 60psi) for coating. Each fabric piece was passed through the coater until no more dry spots were observed(generally twice) then placed through a forced air Mathis LTF oven at 160 °C for 3 min. Each fabric piece was weighed both before coating and after coating to get the actual weight coated. 8 replicates were made per sample for each condition tested (0 washes and after 1 wash). The targeted coat weight was 2% of coating on fabric.

[0068] In this reference example 3, the coated fabric samples 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 39 g 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 at 140 °F).

[0069] In this reference example 4, the coated fabric samples prepared according to reference examples 2 and 3 were evaluated for initial water repellency (i.e., water repellency after 0 washes according to reference example 2) and water repellency after 1 wash (according to reference example 3). Certain samples were evaluated for durable water repellency, i.e., water repellency after 10 to 20 washes, according to reference example 3. Water repellency was evaluated according to the Bundesmann test, which was carried out using the ISO 9865 method. An SDL Atlas M230 Bundesmann test apparatus was used to collect face rating and water absorption data. The instrument was calibrated so that each cup collected 190 mL to 210 mL after 150 s. Face Ratings were assigned on a scale of 1 to 5 using half increments as intermediate assignments, with 5 being the best repellency (smallest water beads) and 1 being the worst (largest water beads). The fabric was weighed before and after testing to determine the water percent absorption. The results are shown below in Tables 5 and 6.Table 5 - ResultsTable 6 - Additional Examples comparing PHOBOL XAN and PHOBOL UXN Crosslinkers

[0070] The data in Table 5 for Comparative Examples 1 and 3 (Comp 1 vs Comp 3) displayed the difference between the oxime blocked and N-heterocycle blocked isocyanate crosslinkers, namely initial water repellency (after treating the fabric but not washing it, i.e., 0 washes). The inventors surprisingly found that when an N-heterocycle-blocked isocyanate crosslinker was used instead of an oxime-blocked isocyanate crosslinker, initial water repellency suffered a detriment when Water Repellent (A-l) in Table 2, above, (which contained a silicone - (meth) acrylate copolymer) was used as the water repellent. Comparative Example 4 (Comp 4) showed the same detriment on a different fabric as Comp 3, demonstrating that the inventors found a new problem to be solved. Comparative Example 2 (Comp 2) showed that adding a catalyst did not improve initial water repellency of the coating made with Water Repellent (A-l) and the oxime blocked crosslinker in Comp 1. Comparative Example 5 (Comp 5) demonstratedthe catalyst was not needed to obtain durability performance (i.e., water repellency after washing the treated fabric). Even at a small amount of the Zn catalyst provided an improvement in initial water repellency (increased face rating and decreased % absorption) as compared to the sample with the same type and amount of water repellent and crosslinker (but with no Zinc catalyst), see Comp 3 vs Ex 1). Working Examples 1 to 8 demonstrated a suitable range for the amount of catalyst. The inventors surprisingly found an optimum amount ranging from 0.25% to 10%, alternatively 1% to 5% of catalyst relative to solids of the crosslinker. Working examples 9 and 10 demonstrated that the addition of catalyst improved initial water repellency on multiple fabrics.

[0071] Examples 11-16 demonstrated the addition of catalyst in combination with the N- heterocycle-blocked crosslinker did not detrimentally affect durability of the water repellency (after washing and drying the fabric for 1 to 20 wash cycles) on multiple fabrics. Comparatives Examples 6-9 unexpectedly demonstrated the addition of catalyst did not provide the same benefit (i.e., improving the initial water repellency) to fabrics treated with acrylic water repellents that did not include silicone (e.g., Neoseed 7080).

[0072] In this reference example 5, the coated fabric samples prepared according to reference examples 2 and 3 were evaluated for initial water repellency (i.e., water repellency after 0 washes according to reference example 2) using the American Association of Textile Chemists and Colorists (AATCC) AATCC-22 spray test to screen different crosslinkers. The results are shown below in Table 7.Table 7 - Spray Test Screening to Compare Different Crosslinkers

[0073] The data in Table 7 showed that use of different commercially available crosslinkers with a silicone - (meth (acrylate copolymer in a textile treatment composition suffered from the drawback of providing poor initial water repellency that could be improved by adding a catalyst, according to this invention. For example, Comparative Example 14 and Working Example 17 show that when 5% zinc (II) acetate tetrahydrate was added to the textile treatment composition with Crosslinker B-4 Baybond 3674 shown above in Tables 1 and 2, initial water repellency improved, even without washing the treated fabric. Comparative Example 15 and Working Example 18 showed that when 5% zinc (II) acetate tetrahydrate was added to the textile treatment composition with Crosslinker B-3 Baybond 7270, initial water repellency improved even without washing the treated fabric. Similar results were shown with Crosslinker B-2 Imprafix AH in Comparative Example 16 and Working Example 19 and with Crosslinker B-5 Permuthane XR-9163 in Comparative Example 19 and Working Example 20.DEFINITIONS AND USAGE OF TERMS

[0074] 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 singular includes the plural 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., IE, and III. The use of “for example,” “e. . ,” “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 8.Table 8 - Abbreviations

Claims

CLAIMS:

1. A textile treatment composition comprising:(A) a silicone - (meth) acrylate copolymer comprising unit formula (Al)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 selected from the group consisting of R and a group of formula OSi(R4)3; wherein each R4is independently selected from the group consisting of R and DSi(R5)a, wherein 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; wherein each R6is independently selected from the group consisting of R and DSiRs; with the proviso that R4, R5, and R6are selected such that the silicone - (meth)acrylate macromonomer unit with subscript x has at least4 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 R15is independently selected from the group consisting of an oxygen atom and NH; each D’ is an independently selected divalent hydrocarbon group of 1 to 12 carbon atoms; each D1is an alkylene group of 2 to 4 carbon atoms or a divalent alkylarylene group; subscript v2 represents the number of units of formula (OD1) in the unit with subscript y2, and subscript v2 has a value of 0 to 20; each R16is independently selected from the group consisting of a hydroxyl group and an alkoxy 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, and a monovalent hydrocarbon group of 1 to 14 carbon atoms; subscripts w, x, y, y2, zl, and z2 represent relative weights of each unit in the copolymer of unit formula (Al), subscript w has a value of 80 to 98.75; subscript x has a value of 0.25 to 15; subscript y has a value of 1 to 5; subscript y2 has a value of 0 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 + y2 + zl + z2) = 100; and the copolymer further comprises a terminal moiety;(B) a crosslinker comprising a nitrogen containing heterocycle-blocked isocyanate;> 0 to 10 weight %, based on weight of the nitrogen containing heterocycle-blocked isocyanate, of (C) a catalyst comprising a metal acetate or a metal acetylacetonate, wherein the metal is selected from the group consisting of manganese, zinc, and zirconium; and(D) water.

2. The textile treatment composition of claim 1 or claim 14, wherein (A) the silicone - (meth) acrylate copolymer comprises unit formula (A2):wherein R1, R2, R, D2, D3, D4, R7, R8, R9, R10, and subscript v are as described above; each R3is a group of formula OSi(R4)3; wherein each R4is independently selected from the group consisting of R and DSi(R5)3, wherein 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; wherein each R6is independently selected from the group consisting of R and DSiR3; 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; subscripts w, x, y, zl, and z2 represent relative weights of each unit in the copolymer of unit formula (A2), subscript w has a value of 80 to 98.75; subscript x has a value of 0.25 to 15; subscript y has a value of 1 to 5; subscript zl has a value of 0 to 18.75; subscript z2 has a value of 0 to 18.75; and a quantity (w + x + y + zl + z2) = 100.

3. The textile treatment composition of claim 1 or claim 2, wherein the nitrogen containing heterocycle-blocked isocyanate comprises an nitrogen containing heterocycle blocking group and an isocyanate compound, wherein the isocyanate compound comprises at least one unit selected from the group consisting of bis(4-isocyanatophenyl)methane; 2,4- diisocyanato- 1 -methylbenzene; 1 -isocyanato-3-isocyanatomethyl-3 ,5 ,5-trimethylcyclohexane; bis(4-isocyanatocyclohexyl)methane; l,3-bis(l-isocyanaot-l-methylethyl)-benzene; 1-(isocyanato- 1 -melhylethyl )-3-( I -methyl- 1 -ethenyl jbenzene; l,4-bis(isocyanatomethyl)benzene; 1 ,4-bis-(isocyanatomethyl)-cyclohexane; and 1 ,6-diisocyanatohexane.

4. The textile treatment composition of claim 3, wherein the isocyanate compound is monomeric.

5. The textile treatment composition of claim 3, wherein the isocyanate compound is polymeric.

6. The textile treatment composition of any one of claims 1 to 5, wherein the nitrogen containing heterocycle-blocking group is 3,5-dimethylpyrazole, 2,6-dimethylpyrazine or caprolactam.

7. The textile treatment composition of any one of claims 1 to 6 or 14, wherein (C) the catalyst is selected from the group consisting of manganese (II) acetate, manganese (II) acetate tetrahydrate, manganese (II) acetylacetonate, manganese (III) acetylacetonate, zinc acetate hydrate, zinc (II) acetate, zinc (II) acetate dihydrate, zinc(II) acetylacetonate, zinc (II) acetylacetonate hydrate, zirconium acetate, and zirconium (IV) acetylacetonate.

8. The textile treatment composition of claim 7, wherein (C) the catalyst is selected from the group consisting of zinc acetate hydrate, zinc (II) acetate, zinc (II) acetate dihydrate, zinc(II) acetylacetonate, zinc (II) acetylacetonate hydrate, zirconium acetate, and zirconium (IV) acetylacetonate.

9. The textile treatment composition of any one of claims 1 to 8 or 14, wherein the textile treatment composition comprises:(A) the silicone - (meth) acrylate copolymer;(B) the crosslinker;0.001 weight % to 0.1 weight %, based on combined weights of starting materials (A), (B), (C), and (D), of (C) the catalyst; and(D) water.

10. The textile treatment composition of any one of claims 1 to 9 or 14, further comprising an additional component selected from the group consisting of (E) a surfactant, (F) a manganese ion source (that differs from (C) the catalyst), (G) a phenolic compound, (H) a wax, (I) a biocide, (J) a flame retardant, (K) a wrinkle reducing agent, (L) an antistatic agent, (M) a penetrating agent, and a combination of two or more of components (E), (F), (G), (H), (I), (J), (K), (L), and (M).

11. A method for making the textile treatment composition of any one of claims 1 to 10 or 14, wherein the method comprises:1) mixing components comprising:an aqueous emulsion comprising (A) the silicone - (meth) acrylate copolymer, I a surfactant, and (D) water; an aqueous emulsion or dispersion comprising (B) the crosslinker and (D) water; and(C) the catalyst.

12. The method of claim 11, wherein the components further comprise an additional component selected from the group consisting of (E) a surfactant, (F) a manganese ion source (that differs from (C) the catalyst), (G) a phenolic compound, (H) a wax, (I) a biocide, (J) a flame retardant, (K) a wrinkle reducing agent, (L) an antistatic agent, (M) a penetrating agent, and a combination of two or more of components (E), (F), (G), (H), (I), (J), (K), (L), and (M).

13. A process for treating a textile, the process comprising:I) coating the textile with the textile treatment composition of any one of claims 1 to 10 or 14, andII) heating the textile at a temperature of > 100 °C to 200 °C.

14. A textile treatment composition comprising:(A) a silicone - (meth) acrylate copolymer comprising unit formula (Al), wherein 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 selected from the group consisting of R and a group of formula OSi(R4)3; wherein each R4is independently selected from the group consisting of Rand DSi(R5)s, wherein 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; wherein each R6is independently selected from the group consisting of R and DSiRs; with the proviso that R4, R5, and R6are selected such that the silicone - (meth)acrylate macromonomer unit with subscript x has at least 4 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 R15is independently selected from the group consisting of an oxygen atom and NH; each D’ is an independently selected divalent hydrocarbon group of 1 to 12 carbon atoms; each D1is an alkylene group of 2 to 4 carbon atoms or a divalent alkylarylene group; subscript v2 represents the number of units of formula (OD1) in the unit with subscript y2, and subscript v2 has a value of 0 to 20; each R16is independently selected from the group consisting of a hydroxyl group and an alkoxy 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, and a monovalent hydrocarbon group of 1 to 14 carbon atoms;subscripts w, x, y, y2, zl, and z2 represent relative weights of each unit in the copolymer of unit formula (Al), subscript w has a value of 80 to 98.75; subscript x has a value of 0.25 to 15; subscript y has a value of 1 to 5; subscript y2 has a value of 0 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 + y2 + zl + z2) = 100; and the copolymer further comprises a terminal moiety;(B) a crosslinker selected from the group consisting of PHOBOL™ EXTENDER UXN, Imprafix™ AH, BAYBOND™ XL 7270, BAYBOND™ XL 3674, Permuthane™ XR-9163, and Permutex™ XR 22-903;> 0 to 10 weight %, based on weight of the nitrogen containing heterocycle blocked isocyanate, of (C) a catalyst comprising a metal acetate or a metal acetylacetonate, wherein the metal is selected from the group consisting of manganese, zinc, and zirconium; and(D) water.

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