Textile treatment for imparting oil repellency includes use of a non-crystalline silicone – (METH)acrylate copolymer, a crystalline polymer, and a blocked isocyanate

Abstract

A textile treatment emulsion can be made by mixing an aqueous emulsion including a non-crystalline silicone – (meth)acrylate copolymer, an aqueous composition including a crystalline component, and an aqueous composition containing a blocked isocyanate. The textile treatment emulsion can be applied on fabric and heated, thereby increasing oil repellency of the fabric.

Description

TEXTILE TREATMENT FOR IMPARTING OIL REPELLENCY INCLUDES USE OF A NONCRYSTALLINE SILICONE - (METH)ACRYLATE COPOLYMER, A CRYSTALLINE POLYMER, AND A BLOCKED ISOCYANATECROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application claims priority under 35 USC § 1 19(e) to US Provisional Patent Application Number 63 / 593716 filed on 27 October 2023, US Provisional Patent Application Number 63 / 674322 filed on 23 July 2024; US Provisional Patent Application Number 63 / 674323 filed on 23 July 2024, US Provisional Patent Application Number 63 / 674325 filed on 23 July 2024, US Provisional Patent Application Number 63 / 674328 filed on 23 July 2024, and US Provisional Patent Application Number 63 / 674329 filed on 23 July 2024. US Provisional Patent Application Numbers 63 / 593716, 63 / 674322, 63 / 674323, 63 / 674325, 63 / 674328, and 63 / 674329 are hereby incorporated by reference.FIELD

[0002] A textile treatment emulsion contains a non-crystalline silicone - (meth)acrylate copolymer, a crystalline component, and a crosslinker. The textile treatment emulsion is useful for imparting oil repellency to textiles.INTRODUCTION

[0003] Per- and Polyfluorinated Substances (PFAS) dominated the textile coating market for many years; however, customers and regulatory bodies desire the elimination of PFAS due to environmental regulations. There is an ongoing need in the textiles industry to find an alternative to PFAS that imparts oil repellency to textiles and that is compatible with the current capital infrastructure because plasma treatments and engineered surface structures typically cannot be done at mills with existing equipment.

[0004] W02023019044 discloses a silicone - (meth)acrylate copolymer emulsion that can impart water repellency to textiles. However, this publication does not address oil repellency. US 11746268 discloses a surface treatment agent that is an aqueous dispersion containing a fluorine-free polymer having repeating units derived from a fluorine-free (meth)acrylic acid ester monomer, a wax, an aqueous medium, and an emulsifier.SUMMARY

[0005] A method for preparing a textile treatment emulsion comprises: I) mixing starting materials comprising i ) an aqueous copolymer emulsion comprising a non-crystalline silicone - (meth) acrylate copolymer, a nonionic surfactant, and water; ii) an aqueous composition comprising a crystalline component, a nonionic surfactant, and water; and iii) an aqueous additive comprising a blocked isocyanate and water. The textile treatment emulsion may beused in a method for imparting oil repellency to a textile.DETAILED DESCRIPTION

[0006] Starting material i ), the aqueous copolymer emulsion comprising the non-crystalline silicone - (meth)acrylate copolymer, the nonionic surfactant, and water, introduced above, may be prepared as described in US Provisional Patent Application Number 63 / 593716, which is hereby incorporated by reference. Tn starting material i), the non-crystalline silicone - (meth) acrylate copolymer comprises unit formula:each R1is an independently selected monovalent hydrocarbon group of 1 to 12 carbon atoms; each D2is an independently selected divalent hydrocarbon group of 2 to 12 carbon atoms; and each R2is independently selected from the group consisting of H and methyl; 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 DSiRs; with the proviso that R4, R5, and R6are selected such that the silicone - (meth)acrylate co-macromonomer unit with subscript b2 has at least 5 silicon atoms; subscripts a, bl, and b2 represent weight fractions of units in the copolymer, and subscripts a, bl, and b2 have values such that 0.25 < a < 1; and 0 < (bl + b2) < 0.75. A quantity (a + bl + b2) = 1 based on combined weights of the macromonomers used to prepare the copolymer, as described below. The non-crystalline silicone - (meth)acryl te copolymer may have a weight average molecular weight measured by GPC of > 181,000 g / mol. Alternatively, the non-crystalline silicone - (meth) aery late copolymer may have a weight average molecular weight measured by GPC of at least 200,000 g / mol; alternatively at least 210,000 g / mol; alternatively at least 212,000 g / mol; alternatively at least 225,000 g / mol; alternatively at least 230,000 g / mol; and alternatively at least 234,000 g / mol; while at the same time, weight average molecular weight may be up to 2,000,000 g / mol; alternatively up to 1,000,000 g / mol; alternatively up to 950,000 g / mol; alternatively up to925,000 g / mol; alternatively up to 912,000 g / mol, alternatively up to 900,000 g / mol, alternatively up to 850,000 g / mol; alternatively up to 800,000 g / mol; and alternatively up to 750,000 g / mol; and alternatively up to 721,000 g / mol. Alternatively, the non-crystalline silicone - (meth)acrylate copolymer may have a weight average molecular weight of 212,000 g / mol to 912,000 g / mol, measured by GPC using the same test method described below for the crystalline silicone - (meth)acrylate copolymer of unit formula (ii-2).

[0007] One skilled in the art would recognize that the non-crystalline silicone - (meth)acrylate copolymer (copolymer) above may be prepared by radical polymerization, via a method as described below, and that this method would form a terminal moiety for the copolymer. The copolymer with the unit formula above 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.

[0008] The copolymer may be prepared via a method comprising:1) copolymerizing starting materials comprising: (A) a silicone - (meth)acrylate macromonomerindependently selected monovalent hydrocarbon group of 1 to 12 carbon atoms; D2is a divalent hydrocarbon group of 2 to 12 carbon atoms; and R2is selected from the group consisting of H and methyl; optionally (B) a silicone - (meth)acrylate co-macromonomer, wherein (B) the silicone - (meth)acrylate co-macromonomer has a formula selected from the group consisting of formula (B-l), formula (B-2), and a combination of both formula (B-l) and formula (B-2),divalent hydrocarbon group of 2 to 12 carbon atoms; and R2is selected from the groupconsisting of H and methyl; formula (B-2) isR2is selected from the group consisting of H and methyl; D2is a divalent hydrocarbon group of 2 to 12 carbon atoms, and each R3is a group of formula OSi(R4h; 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 DSiRs; with the proviso that R4, R5, and R6are selected such that the silicone - (meth)acrylate co-macromonomer of formula (B-2) has at least 5 silicon atoms per molecule; wherein starting material (A) is present in an amount of > 25 weight % to 100 weight %, based on combined weights of starting materials (A) and (B); and wherein starting material (B) is present in an amount of 0 to < 75 weight %, based on combined weights of starting materials (A) and (B); and wherein starting materials (A) and (B) are copolymerized in the presence of an additional starting material, wherein the additional starting material comprises (C) an initiator. The additional starting material used in step 1) may optionally further comprise one or more of (H) a chain transfer agent; (I) a manganese ion source; (J) a phenolic compound; and a chelating agent.

[0009] Step 1) of the method for making the copolymer may comprise an emulsion polymerization reaction. The additional starting materials used in this emulsion polymerization method further comprise (D) a surfactant and (E) water. In step 1), the emulsion polymerization described above may comprise forming an emulsion comprising starting material (A) the silicone - (meth)acrylate macromonomer, (B) the silicone - (meth) acrylate co-macromonomer (when present), (D) the surfactant, (E) water, and optionally one or more of (H) the chain transfer agent, (I) the manganese ion source, and (J) the phenolic compound and thereafter adding (C) the initiator and copolymerizing. Without wishing to be bound by theory, it is thought that during processing to combine and emulsify (A) the silicone - (meth)acrylate macromonomer, (B) the silicone - (meth)acrylate co-macromonomer (when present), (D) the surfactant, and (E) the water, and when present (H) the chain transfer agent, starting materials (I) the manganese ion source and / or (J) the phenolic compound may inhibit formation of acrylic radicals that can impact the formation of the copolymer during copolymerization in step 1).These starting materials may be mixed under shear to form i) the aqueous copolymer 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 rotor-stators, sonolators, 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) the silicone - (meth)acrylate macromonomer, (B) the silicone - (meth)acrylate co-macromonomer (when present), (C) the initiator (and when present (H) the chain transfer agent) copolymerize to form (F) the silicone - (meth) acrylate copolymer, thereby forming starting material z) the aqueous copolymer emulsion, which comprises (F) the silicone - (meth) acrylate copolymer, (D) the surfactant, and (E) the water, and optionally (I) manganese ion source and (J) the phenolic compound (when used).

[0010] The method described herein may optionally further comprise one or more additional steps. For example, before step 1) the starting materials comprising (A) the silicone - (meth) acrylate macromonomer and, when present, (B) the silicone - (meth) acrylate co- macromonomer and / or (H) the chain transfer agent may be combined under aerobic or anaerobic conditions, optionally with heating for extended times. For example, the starting materials comprising (A) the silicone - (meth)acrylate macromonomer and (B) the silicone -(meth) acrylate co-macromonomer, and when present one or more of (H) the chain transfer agent, (I) manganese ion source, and / or (J) the phenolic compound, may be emulsified with (D) the surfactant and (E) the water before adding (C) the initiator and copolymerizing in step 1). In step 1), combining the starting materials and copolymerizing in the method described above may be performed on a commercial scale under anaerobic or aerobic conditions optionally at elevated temperature, e.g., up to 100 °C, alternatively 25 °C to 60 °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 48 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 where copolymerizing takes place, 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. Anaerobic conditions means that the gas in the headspace contains no more than 2% oxygen.

[0011] Alternatively, the non-crystalline silicone - (meth)acrylate copolymer described above may be prepared by a method comprising dissolving one or more of the starting materials, such as (A) the silicone - (meth)acrylate macromonomer and optionally one or more of (B) thesilicone - (meth)acrylate co-macromonomer, (H) the chain transfer agent, (I) the manganese ion source, and (J) the phenolic compound, in an organic solvent (such as a monohydric alcohol) and copolymerizing starting materials (A) the silicone - (meth) acrylate macromonomer and when present (B) the silicone - (meth) acrylate co-macromonomer and (H) the chain transfer agent in a method such as that disclosed in US Patent 10047199 to limura et al. by varying appropriate starting materials and their amounts. The resulting copolymer may be solvent borne. All or a portion of the solvent may be removed by any convenient means, such as by stripping or distillation with heat and optionally reduced pressure. The resulting copolymer may be emulsified using (D) the surfactant and (E) the water.

[0012] If a surfactant, other than a nonionic surfactant, is used in the method to make the copolymer, as described above, the method may further comprise isolating the copolymer from the solvent or the emulsion described above, and thereafter, the copolymer may be emulsified with a nonionic surfactant and water to form starting material i).

[0013] Regardless of the method used to make the copolymer, e.g. , either via emulsion polymerization or by emulsifying the copolymer prepared in solvent (after solvent removal), the product prepared in step 1) is starting material z) the aqueous copolymer emulsion, which comprises the silicone - (meth) acrylate copolymer, the nonionic surfactant, and the water. Starting material i) the aqueous copolymer emulsion may optionally further comprise (I) the manganese ion source and / or (J) the phenolic compound. The starting materials used in the method for making z ) the aqueous copolymer emulsion are further described below.

[0014] Starting material (A) used herein is a silicone - (meth) acrylate macromonomer. The silicone - (meth)acrylate macromonomer has formula (A-l):each R1is an independently selected monovalent hydrocarbon group of 1 to 12 carbon atoms; D2is a divalent hydrocarbon group of 2 to 12 carbon atoms; and R2is selected from the group consisting of H and methyl.

[0015] In formula (A-l), each R1is an independently selected monovalent hydrocarbon group of 1 to 12 carbon atoms. The monovalent hydrocarbon group for R1may 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 R1group may be methyl.

[0016] In formula (A-l), 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. Thedivalent hydrocarbon group for D2may be exemplified by an alkylene group such as ethylene, propylene, or butylene. Alternatively, the divalent hydrocarbon group for D2may be propylene. Alternatively, D2may be linear, e.g., -(CH2)2- or -(CH2)3-. Alternatively, D2may be -(CH2)3-. Alternatively, when D2comprisesstarting material (A) comprises formula (A-2):described above.

[0017] Starting material (A) may comprise 3-(l,l,l,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl methacrylate of formulaStarting material (A) may be prepared by known methods, such as those disclosed in US PatentApplication Publication US20220112322 and US Patent 6420504, both of which are hereby incorporated by reference.

[0018] Starting material (B) is a silicone - (meth) acrylate co-macromonomer (co- macromonomer) that may optionally be copolymerized with (A) the silicone - (meth)acrylate macromonomer described above. Starting material (B), the co-macromonomer, may comprise formula (B-l), where formula (each R1is an independently selected monovalent hydrocarbon group of 1 to 12 carbon atoms; D2is a divalent hydrocarbon group of 2 to 12 carbon atoms; and R2is selected from the group consisting of H and methyl, each as described and exemplified above for formula (A-l).Alternatively, when D2comprises -(CHi)i-, formula (B-l) may comprise:are as described above. Alternatively, formula (B-2) may comprise 3-(l,l,l,3,5,5,5-heptamethyltrisiloxan-3- yl)propyl methacrylate of formula

[0019] Alternatively, in addition to, or instead of, formula (B-l) shown above, starting material (B) the co-macromonomer may comprise a silicone - (meth)acrylate co-macromonomer of formula (divalent hydrocarbon group of 2 to 12 carbon atoms; and R2is selected from the group consisting of H and methyl, each as described above for formula (A-l). In formula (B-2), each R3is a group of formula OSi(R4) ; 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 co-macromonomer of formula (B-2) has at least 6 silicon atoms per molecule. Alternatively, R4, R5, and R6are selected such that the unit has at least 5 silicon atoms, alternatively 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 molecule.

[0020] In formula (B-2), 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 to2 carbon atoms. Alternatively, each R group may be methyl.

[0021] In formula (B-2), 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.

[0022] The divalent hydrocarbon group for D may 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 for D may be alkylene, and alternatively the divalent hydrocarbon group for D may be ethylene.

[0023] The (poly)alkylene oxide group for D may have 2 to 4 carbon atoms per unit, e.g., have formula DS(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.

[0024] 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, e.g. , ethylene, in the same unit.

[0025] Alternatively, formula (B-2) may comprise formula (B-2-1):are as described above.

[0026] Alternatively, formula (B-2) may comprise formula (B-2-2):are as described above.

[0027] Alternatively, formula (B-2) may comprise formula (B-2-3):D, and R are as described above.

[0028] Alternatively, formula (B-2) may comprise a co-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-(l,5-bis(2-(l,l,l,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. The co-macromonomer of formula (B-2) as described and exemplified above may be prepared by known methods, such as those disclosed in US Patent Application Publication US20220112322 and US Patent 6420504, both of which are hereby incorporated by reference.

[0029] Starting material (A) the silicone - (meth)acrylate macromonomer, and starting material (B) the silicone - (meth)acrylate co-macromonomer are used in the following amounts when making the copolymer: starting material (A) is used in an amount of > 25 weight % to 100 weight %, based on combined weights of starting materials (A) and (B); and starting material (B) is used in an amount of 0 to < 75 weight %, based on combined weights of starting materials (A) and (B). Alternatively, starting material (A) may be used in an amount > 25 %, alternatively at least 40 %, alternatively at least 50%, alternatively at least 63%, and alternatively at least 75%, based on combined weights of starting materials (A) and (B); while at the same time the amount of starting material (A) may be up to 100%, alternatively up to 99%, alternatively up to 95%, alternatively up to 75%, alternatively up to 63%, alternatively up to 50%, and alternatively up to 40%, on the same basis. Alternatively, the amount of starting material (A) may be 100%, and the amount of starting material (B) may be 0. Alternatively, starting material (B) may be present, and the amount of starting material (B) may be > 0%, alternatively at least 1%, alternatively up to 5%, alternatively up to 10%, alternatively up to 15%, alternatively up to 20%, and alternatively at least 25%; while at the same time the amount of starting material (B) may be up to 60%, alternatively up to 50%, alternatively up to 37%, and alternatively up to 25%, on the same basis.

[0030] The starting materials used to make the copolymer may optionally be free of crosslinkable groups, for example, the starting materials that copolymerize in step 1) of the method described herein may be free of crosslinkable (meth) acrylate monomers such as organic (meth) acrylate monomers having crosslinkable groups. For example, the starting materials used in step 1) may be free of crosslinkable organic (meth)acrylate monomers such as (2-acetoacetoxy)ethyl methacrylate, hydroxybutyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxyethylcaprolactone (meth)acrylate, hydroxypropyl (meth)acrylate, ureido (meth)acrylate, and glycidyl (meth) acrylate (GMA). The starting materials used in step 1) may be free of organosilyl monomers having crosslinkable groups, such as alkenyltrialkoxysilanes (e.g., 3- (trimethoxysilyl)propyl (meth)acrylate, vinyltriethoxysilane and vinyltrimethoxysilane).

[0031] Starting material (A), and when present starting material (B) are copolymerized in the presence of an additional starting material. The additional starting material comprises (C) an initiator. Alternatively, the starting materials that copolymerize in step 1) may consist of starting materials (A) the macromonomer, (B) the co-macromonomer, and (C) the initiator, and when present (H) the chain transfer agent. Alternatively, the starting materials used in step 1 ) may consist essentially of, or may consist of, (A) the macromonomer, (B) the co-macromonomer, (C) the initiator, (D) the surfactant, and (E) the water, and when present (H) the chain transfer agent, (I) the manganese ion source, and (J) the phenolic compound, and these starting materials are described further below.

[0032] Starting material (C), the initiator, is also added in step 1) of the method for making the copolymer 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-1- cyanocyclohexane, azo-bis-isobutyronitrile and 1-t-butylazo-cyanocyclohexane, 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 art 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, diperoxide 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. of St. Louis, Missouri, USA. Alternatively, the initiator may comprise isoascorbic acid.

[0033] An initiator may be used alone as starting material (C). Alternatively, starting material (C) may be a redox pair, which comprises an initiator as the oxidizing component and a reducing component. Alternatively, a redox pair including isoascorbic acid and an organic hydroperoxide such as t-amyl hydroperoxide or t-butyl hydroperoxide may be used as starting material (C).Examples of suitable initiators and / or redox pairs for starting material (C) are disclosed in US Patent 6576051 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.

[0034] Alternatively, the initiator may optionally further comprise iron(II) sulfate heptahydrate, potassium persulfate, or a combination thereof. The initiator (C) may be used in an amount sufficient to provide 0.01% to 3%, alternatively 0.1% to 1.5%, based on weight of (F) the non-crystalline silicone - (meth)acrylate copolymer.

[0035] Starting material (D) is a surfactant. The surfactant used in the method for preparing the copolymer 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 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 (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-l-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.

[0036] Representative quaternary ammonium halide salts are dodecyltrimethyl ammonium chloride / lauryltrimethyl ammonium chloride (LTAC), cetyltrimethyl ammonium chloride (CTAC), hexadecyltrimethyl 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™.

[0037] 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.

[0038] The amount of (D- 1 ) the cationic surfactant may be 0.1 % to 5%, based on weight of the non-crystalline silicone - (meth) acrylate copolymer. 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. When used in the method for making the copolymer, the cationic surfactant is thereafter removed in order to prepare starting material i) the aqueous copolymer emulsion comprising the non-crystalline silicone - (meth)acrylate copolymer, the nonionic surfactant, and water, described further below.

[0039] 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 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, 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™ O10, BRIJ™ L23 and BRIJ™ 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, and (ix) sorbitan stearate sold under the name Span 60 from Sigma Aldrich.

[0040] 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 (polypropylene 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.

[0041] 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 (Cn-i5 secondary alcohol ethoxylates 7EO, 9EO, and 15EO) sold under the trademarks TERGITOL™ 15-S-7, TERGITOL™ 15-S-9, TERGITOL™ 15-S-15; other Ci 1-15 secondary alcohol ethoxylates sold under the trademarks TERGITOL™ 15-S-12, 15-S-20, 15-S-3O, 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.

[0042] 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 by Sigma Aldrich, Inc.; and RENEX™ 30, a polyoxyethylene ether alcohol available from Fisher Scientific.

[0043] 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 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 copolymer 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.

[0044] 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 the silicone - (meth)acrylate copolymer in i) the aqueous copolymer 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%, alternatively at least 1%, alternatively at least 2%, alternatively at least 3%, alternatively at least 4%; while at the same time the amount of nonionic surfactant may be up to 10%, alternatively up to 9%, alternatively up to 8%, alternatively up to 7%, alternatively 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 1% to 10%, alternatively 2% to 10%, alternatively 3 to 10%, alternatively 5% to 9%, alternatively 6% to 8%, and alternatively 7%; on the same basis.

[0045] 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 method for making the copolymer described above. Additional water may be added after step 1). For example, the aqueous copolymer emulsion prepared as described above may be diluted with additional water to achieve a desired amount of starting materials. The water may be added in an amount of 10% 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.

[0046] The non-crystalline silicone - (meth)acrylate copolymer, (F), may be prepared by emulsion polymerization of starting materials comprising (A) the macromonomer and (C) the initiator (and optionally (B) the co-macromonomer) described above. Alternatively, the noncrystalline silicone - (meth) acrylate copolymer may be a reaction product of starting materials consisting essentially of starting materials (A) the macromonomer and (C) the initiator (and when present, (B) the co-macromonomer and / or (H) the chain transfer agent). Alternatively, the non-crystalline silicone - (meth)acrylate copolymer is a reaction product of starting materials consisting of starting materials (A) and (C), (and, when present, (B) and / or (H)). Withoutwishing to be bound by theory, it is thought that none of starting materials (D) the surfactant, (E) the water, (I) the manganese ion source, and (J) the phenolic compound, copolymerize with starting materials (A) and (C), (and when present (B) and / or (H)), but that starting materials (D) and (E) 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) and (C), and any optional starting materials (e.g.. starting materials (B) and / or (H)), when present.

[0047] The method described above may optionally comprise step 2) adding an additional starting material. The additional starting material may be selected from the group consisting of (K) a biocide, (L) additional water (which may be the same as starting material (E)), (M) a flame retardant, (N) a wrinkle reducing agent, (O) an antistatic agent, (P) a penetrating agent, (Q) an additive such as a softening agent, (R) a catalyst, such as a condensation reaction catalyst, and a combination of two or more thereof. Step 2) of this method may optionally further comprise adding additional nonionic surfactant.

[0048] An additional starting material that may be added in step 1) of the method 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, BASF Schweiz AG, Basel, Switzerland, Encyclopedia of Radicals in Chemistry, Biology and Materials, Online © 2012 John Wiley & Sons, Ltd. Starting material (H) is optional and may be added in an amount of 0 to 1%, based on combined weights of starting material (A), and when present starting material (B). Alternatively, (H) the chain transfer agent may be used in an amount of 0.5% to 0.6% on the same basis.

[0049] Starting material (I) is an optional manganese ion source, which may be a manganese (III) compound or a manganese (II) compound. Alternatively, starting material (I) may be a manganese (II) compound. Suitable manganese (II) 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) acetate tetrahydrate) and combinations thereof. Alternatively, the manganese ion source may comprise manganese (II) acetate or manganese (II) acetate tetrahydrate, or a combination thereof. Suitable manganese ion sources are commerciallyavailable 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 starting material (A), and when present starting material (B). 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 starting material i ) the aqueous copolymer emulsion.

[0050] Starting material (J) is an optional phenolic compound. Suitable phenolic compounds include hydroquinone (HQ), 2-methylhydroquinone, 2-t-butylhydroquinone, dihydroxybenzene (catechol), 4-di-t-butyl dihydroxybenzene (4-di-t-butyl 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, butylated hydroxyl toluene, N-nitroso phenylhydroxylamine, butylated hydroxy anisole, 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. 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 material (A) and when present starting material (B). 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 starting materials in starting material i ) the aqueous copolymer emulsion.

[0051] Alternatively, another inhibitor may be used in addition to, or instead of, (I) the manganese ion source and (J) the phenolic compound described above. For example, the inhibitor may comprise, or may be, nitrobenzene; 2,2-diphenyl-l-picrylhydrazyl (DPPH); phenothiazine; N,N-diethylhydroxylamine; (2,2,6,6-tetramethylpiperidin- l-yl)oxidanyl (TEMPO); 4-hydroxy-(2,2,6,6-tetramethylpiperidin-l-yl)oxidanyl (4-hydroxy TEMPO); or a combination of two or more thereof.

[0052] Starting material (K) 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 i ) the aqueous copolymer emulsion. Starting material (K) is exemplified by (K-l) a fungicide, (K-2) an herbicide, (K-3) a pesticide, (K-4) an antimicrobial agent, or a combination thereof. Suitable biocides are disclosed, for example, in US Patent 9480977.

[0053] The aqueous copolymer emulsion may optionally further comprise starting material (P), 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™.

[0054] The aqueous copolymer emulsion may optionally further comprise an amount sufficient to impart softness to a textile without significantly decreasing water and / or oil repellency of (Q) a softening additive selected from (Q-l) an alkylpolysiloxane of unit formula (R193SiO)2(R192SiO2 / 2)aa, wherein each R19is an independently selected monovalent saturated hydrocarbon group having 1 to 18 carbon atoms, and subscript aa has an average value of 20 to 300, or (Q-2) a combination comprising 60% to 70%, based on combined weights of all starting materials in (Q-2), the combination, of (Q-l) the alkylpolysiloxane, 29% to 39%, based on combined weights of all starting materials in (Q-2), the combination, of (Q-2-1) a silicone resin having a hardness > 20 measured by Type A durometer according to JIS K 6249:2003, and 0 to 2 weight %, based on combined weights of all starting materials in (Q-2), the combination, of (Q-2-2) an amino-functional polyorganosiloxane having a functional group equivalent of 100 to 20,000 g / mol, wherein the equivalent means molecular weight of the amino-functional polyorganosiloxane per 1 mole of nitrogen atoms, and having a kinematic viscosity at 25 °C of 10 to 100,000 mm2 / s measured by the method of JIS K 2283:2000. Alternatively, (Q-2-2) the amino-functional polyorganosiloxane may be present in an amount of 1% to 2%, on the same basis.

[0055] In the (Q-l) alkylpolysiloxane of the formula shown above, each R19is an independently selected monovalent saturated hydrocarbon group having 1 to 18 carbon atoms, and subscript aa has an average value of 20 to 300. The monovalent saturated hydrocarbon group for R19may be an alkyl group, alternatively 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 R19may be methyl. Suitable alkylpolysiloxanes, e.g., bis-trimethylsiloxy- terminated polydimethylsiloxanes, are known in the art and are commercially available, e.g., as XIAMETER™ 200 Fluids from The Dow Chemical Company.

[0056] Alternatively, (Q) the softening additive may comprise a (Q-2) combination comprising: 60 to 70 weight %, based on combined weights of all starting materials in (Q-2), the combination, of (Q-l) the alkylpolysiloxane described above, 29% to 39%, based on combinedweights of all starting materials in (Q-2), the combination, of (Q-2-1) a silicone resin having a hardness > 20 measured by Type A durometer according to JIS K 6249:2003, and 1 to 2 weight %, based on combined weights of all starting materials in (Q-2), the combination, of (Q-2-2) an amino-functional polyorganosiloxane having a functional group equivalent of 100 to 20,000 g / mol, wherein the equivalent means molecular weight of the amino-functional polyorganosiloxane per 1 mole of nitrogen atoms, and having a kinematic viscosity at 25 °C of 10 to 100,000 mm2 / s measured by the method of JIS K 2283:2000.

[0057] Starting material (Q) the softening additive may be delivered in an additional aqueous emulsion, which comprises (Q) the softening additive, (D’) a nonionic surfactant (which may be as described above for starting material (D-2) the nonionic surfactant) and (E’) water (which may be as described above for starting material (E)). The additional aqueous emulsion may be prepared by known methods, such as those described in US Patent Application Publication 20200332148, by varying the types and amounts of starting materials as described herein.

[0058] Starting material (R) is an optional 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) acetate tetrahydrate (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. The amount of starting material (R) depends on various factors including the types and amounts of the noncrystalline silicone - (meth) acrylate copolymer, whether a blocked isocyanate is used, and the types and amounts of other optional additional starting materials, however, the amount of the catalyst 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 amount of blocked isocyanate (solids), when used. Alternatively, the aqueous copolymer emulsion prepared as described above, or the textile treatment emulsion prepared as described below, may comprise 0.001 % to 0.1 %, of (R) the catalyst, based on combined weights of all starting materials used.

[0059] When selecting starting materials to add to z ) the aqueous copolymer emulsion prepared as in step 1), and when present step 2), described above, there may be overlap between types of starting materials because certain starting materials described herein may have more than onefunction. For example, manganese (11) acetylacetonate may be an inhibitor or a condensation reaction catalyst. The starting materials used in aqueous copolymer emulsion (prepared as described above) and in the textile treatment emulsion (prepared as described below) may be distinct from one another.

[0060] Step 2) of the method described above for making the aqueous copolymer emulsion may be performed by any convenient means, such as mixing using 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) may be 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. Alternatively, step 2) may be absent and any additional starting materials may be combined with i) the aqueous copolymer emulsion prepared in step 1) later.Method for Preparing the Textile Treatment Emulsion

[0061] The aqueous copolymer emulsion prepared as described above is used to prepare the textile treatment emulsion described herein. The method for preparing the textile treatment emulsion comprises: step I) mixing starting materials comprising starting material i) and starting material ii), wherein starting material i) is the aqueous copolymer emulsion comprising the noncrystalline silicone - (meth) acrylate copolymer, the nonionic surfactant, and the water, as described above; and starting material ii) is an aqueous composition comprising a crystalline component, a second nonionic surfactant, and water; and wherein starting material i ) and starting material ii ) are used in amounts sufficient to provide a weight ratio of the non-crystalline silicone - (meth)acrylate copolymer : the crystalline component (non-crystalline : crystalline actives ratio) of 1:3 to 3:1. Alternatively, the non-crystalline : crystalline actives ratio) may be 1:3 to 1:1 (copolymer : crystalline component weight ratio, Alternatively, the non-crystalline : crystalline actives ratio may be 1 : 1 to 3 : 1. The non-crystalline : crystalline actives ratio) represents the relative amounts of solids (actives) delivered by the emulsions, i.e., the weight of the non-crystalline silicone - (meth) acrylate copolymer delivered in starting material i) : the weight of crystalline component delivered in starting material ii).

[0062] The aqueous copolymer emulsion for starting material i ) is as described above. Starting material ii ) is the aqueous composition comprising the crystalline component, the second nonionic surfactant, and water. The second nonionic surfactant and the water in starting material ii) may be as described above for starting materials (D-2) and (E), respectively. The nonionic surfactants in starting materials z ) and ii ) may be the same or different. The crystallinecomponent is a polymer having a Tc of 25 °C to 130 °C, alternatively Tc of 34 °C to 117 °C. Alternatively, the crystalline component may have a Tc of 34 °C to 60 °C, alternatively 34 °C to 50 °C, and alternatively 38 °C to 45 °C. Said crystalline component may be organic, or may be an organic polymer or macromolecule with a pendant polyorganosiloxane moiety. Alternatively, said crystalline component may be organic.

[0063] In one embodiment, the crystalline component may be an alkyl urethane. Suitable alkyl urethanes and emulsions thereof (which are suitable for use as starting material ii ) herein) are known in the art and may be made by known methods such as those disclosed in EP 3 198 072 Bl (corresponding to US Patent 10246608, which is hereby incorporated by reference). For example, the aqueous composition may comprise a hydrophobic compound (e.g., alkyl urethane compound) having at least one linkage of Formula (I): -NHC(O)-X- (I), wherein the linkage of Formula (I) comprises 30 to 100% by mol of the total urethane linkages in the hydrophobic compound; X is the residue of a cyclic or acyclic sugar alcohol which is substituted with at least two -R’ ; -C(O)R’ ; -(CH2CH2O)n(CH(CH3)CH2O)mC(O)R’ ; or mixtures thereof; where the cyclic or acyclic sugar alcohol is selected from glucose, glyceraldehyde, erythrose, arabinose, ribose, allose, altrose, mannose, xylose, lyxose, gulose, galactose, talose, fructose, ribulose, mannoheptulose, sedoheptulose, threose, erythritol, threitol, glucopyranose, mannopyranose, talopyranose, allopyranose, altropyranose, idopyranose, gulopyranose, glucitol, mannitol, sorbitol, arabitol, xylitol, ribitol, galactitol, fucitol, iditol, inositol, dipentaerythritol, volemitol, gluconic acid, glyceric acid, xylonic acid, galactaric acid, ascorbic acid, gluconic acid lactone, glyceric acid lactone, xylonic acid lactone, glucosamine, galactosamine, or mixtures thereof; wherein each subscript n is independently 0 to 20; each subscript m is independently 0 to 20; a quantity (m+n) is greater than 0; each R’ is independently a linear or branched alkyl group having 5 to 29 carbons optionally comprising at least 1 unsaturated bond. Emulsions of alkyl urethanes suitable as starting material ii ) are commercially available. For example, Zelan R3 from The Chemours Company PC, LLC of Wilmington, Delaware, USA, may be used herein as starting material ii). The alkyl urethane may have a Tc of 25 °C to 130 °C, alternatively 34 °C to 117 °C, alternatively 34 °C to 50 °C, and alternatively 38 °C to 45 °C.

[0064] Alternatively, the crystalline component may be crystalline polymer exemplified by a polyolefin, such as a polyethylene homopolymer or copolymer of ethylene and another olefin. The polyethylene may be, for example, polyethylene homopolymer, or an ethylene / octene- 1 copolymer or ethylene / hexene- 1 copolymer. The polyethylene may be linear low density, low density or high density polyethylene. Alternatively, the polyolefin may be high density polyethylene. Suitable polyolefins are commercially available and include DOW™ HDPE DMDA-8965 NT 7. An emulsion of the polyolefin may be prepared, for example, by feedingthe polyolefin and a nonionic surfactant, such as a polyvinyl alcohol, into a mixing apparatus, such as a twin screw extruder, with heating to melt these starting materials. Water may then be added to the apparatus to form an emulsion with a desired percentage of solids.

[0065] Alternatively, the crystalline component may be a crystalline (meth)acrylate-based (co)polymer. Suitable crystalline (meth)acrylate-based (co)polymers include those that have Tc of 25 °C to 130 °C, alternatively 34 °C to 1 17 °C, alternatively 34 °C to 59 °C, alternatively 37 °C to 59 °C, alternatively 37 °C to 42 °C, and alternatively 38 °C. The crystalline (meth)acrylate-based (co)polymer may be a poly(meth)acrylate. Aqueous emulsions containing poly(meth)acrylates, which are suitable for use as starting material ii) herein, are known in the art and are commercially available, such as NEOSEED NR-7080 and NEOSEED NR-7090 from Nicca; and PHOBOTEX RSY from Huntsman. Alternatively, aqueous emulsions containing poly(meth)acrylates suitable for use as starting material ii) may be prepared as described in the EXAMPLES, below.

[0066] Alternatively, the crystalline component may be a crystalline (meth)acrylate-based (co)polymer. A suitable aqueous emulsion of a the crystalline (meth)acrylate-based (co)polymer is commercially available as DOWSIL™ IE-9100 Emulsion from The Dow Chemical Company. Alternatively, aqueous emulsions containing the crystalline (meth)acry late-based (co)polymer, which are suitable for use as starting material ii), may be prepared as described in the EXAMPLES, below.

[0067] Alternatively, starting material ii) may be an aqueous emulsion comprising the crystalline (meth)acrylate-based (co)polymer (introduced above), a surfactant, and water. The crystalline (meth)acrylate-based (co)polymer may be organic (i.e., not silicon containing). For example, the crystalline (meth)acrylate-based (co)polymer may comprise a homopolymer of stearyl acrylate or other (meth) acrylate monomer. Alternatively, the crystalline (meth)acrylate based (co)polymer may comprise a copolymer of two or more organic (meth)acrylate based monomers, such as stearyl acrylate and 2-hydroxyethyl methacrylate. Alternatively, the crystalline (meth)acrylate-based (co)polymer may comprise a crystalline silicone - (meth) acrylate copolymer, which comprises a (meth)acrylate backbone and has a crystalline pendant group and a polyorganosiloxane pendant group.

[0068] The crystalline (meth)acrylate-based (co)polymer may comprise unit formula (ii-1 -.wherein each R21is an independently selected alkyl group of 16 to 24 carbon atoms; each R2is independently selected from the group consisting of H and methyl (as described above); each D2is a divalent hydrocarbon group of 2 to 12 carbon atoms (as described above); each R23is independently selected from the group consisting of R and a group of formula OSi(R24)3; wherein each R24is independently selected from the group consisting of R and DSi(R25)3, wherein each R is an independently selected monovalent hydrocarbon group of 1 to 12 carbon atoms (as described above), 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 (as described above); each R25is independently selected from the group consisting of R and DSi(R26)3; wherein each R26is independently selected from the group consisting of R and DS1R3; with the proviso that R24, R25, and R26are 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 R35is 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 R36is 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 groupconsisting 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 weight fractions of each unit in the crystalline (meth)acrylate-based (co)polymer comprising unit formula (ii-1 ), subscript w has a value of 0.5 to 1; subscript x has a value of 0 to 0.15; subscript y has a value of 0 to 0.05; subscript y2 has a value of 0 to 0.05; subscript zl has a value of 0 to 0.5; and subscript z2 has a value of 0 to 0.5, with the proviso that a quantity (y + y2 + zl + z2) < 0.5, and a quantity (w + x + y + y2 + zl + z2) = 1 based on combined weights of monomers used to prepare the crystalline (meth)acrylate based (co)polymer. The (co)polymer further comprises a terminal moiety.

[0069] In unit formula (ii-1) above, the unit with subscript w is the crystalline monomer unit. In this unit, R21has 16 to 24 carbon atoms. Alternatively, R21may have at least 16, alternatively at least 17, alternatively at least 18 carbon atoms, while at the same time R21may have up to 24, alternatively up to 23, and alternatively up to 22 carbon atoms. Alternatively, R21may 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. R21may be selected from the group consisting of stearyl, eicosyl, and behenyl. Alternatively, R21may be stearyl or behenyl, and alternatively each R21may be stearyl.

[0070] In unit formula ii-1) above, the unit with subscript x is a silicone - (meth)acrylate macromonomer unit. In the silicone - (meth)acrylate macromonomer unit, each R23is independently selected from the group consisting of R and a group of formula -OSi(R24)3; 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 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 may be methyl. In unit formula (ii-1), each R24is independently selected from the group consisting of R (as defined above) and DSi(R25)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 R25is independently selected from the group consisting of R and DSi(R26)3; wherein each R26is independently selected from the group consisting of R and DSilty with the proviso that R23, R24, R25, and R26are selected such that the silicone - (meth)acrylate macromonomer unit with subscript x has at least 4, alternatively at least 6 silicon atoms, alternatively at least 7 silicon atoms, alternatively at least 8 silicon atoms, alternatively at least 9 silicon atoms, and alternatively at least 10 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 to10 silicon atoms. Alternatively, R23, R24, R25, and R26may be selected such that the silicone - (meth) aery late macromonomer unit has 4 to 16, alternatively 4 to 10, alternatively 6 to 16, and alternatively 6 to 10 silicon atoms, per unit.

[0071] In unit formula (ii-1), 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 as described above. Alternatively, the divalent hydrocarbon group for D may be alkylene, such as ethylene, propylene, or butylene. Alternatively, each D may be ethylene.

[0072] In unit formula ii-1'), 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 independently a divalent hydrocarbon group of 1 to 12 carbon atoms. Alternatively, each D3may be an alkylene group; alternatively, ethylene. D4and D1are each independently an alkylene group of 2 to 4 carbon atoms or a divalent alkylarylene group.

[0073] 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: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., -(CH?) - or -(CFfo -.

[0074] In unit formula (ii-1) above, each R7is independently selected from the group consisting of an oxygen atom and NH. Alternatively, each R7may be oxygen.

[0075] In unit formula (zz-7) 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.

[0076] In unit formula (z'z-7) above, each R35is an oxygen atom or NH, alternatively oxygen. Each R36is selected from the group consisting of -OH and alkoxy. Alternatively, the alkoxygroup for R36may be -OCH3.

[0077] In unit formula (ii-1) 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.

[0078] In unit formula (ii-1) 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.

[0079] In unit formula (ii-1) above, subscripts w, x, y, y2, zl, and z2 are weight fractions of each unit, and a quantity (w + x + y + y2 + zl + z2) = 1 (based on combined weights of monomers used to make the crystalline (meth) acrylate based (co)polymer). Subscript w has a value of 0.50 to 1. Alternatively, subscript w may be at least 0.5, alternatively at least 0.7, alternatively at least 0.71, alternatively at least 0.72, alternatively at least 0.73, alternatively at least 0.74, alternatively at least 0.75, alternatively at least 0.76, alternatively at least 0.77, alternatively at least 0.78, alternatively at least 0.79, alternatively at least 0.8, alternatively at least 0.81, alternatively at least 0.82, alternatively at least 0.83, alternatively at least 0.84, alternatively at least 0.85, alternatively at least 0.86, alternatively at least 0.87, and alternatively at least 0.88; while at the same time, subscript w is up to 1, alternatively up to 0.98, alternatively up to 0.97, alternatively up to 0.96, alternatively up to 0.95, alternatively up to 0.94, alternatively up to 0.93, alternatively up to 0.92, alternatively up to 0.91, alternatively up to 0.90, alternatively up to 0.89, and alternatively up to 0.88. Alternatively, subscript w may be 0.75 to 1, alternatively 0.95 to 0.98.

[0080] In unit formula (ii-1) above, the unit with subscript x is the silicone - (meth)acrylate macromonomer unit, which is optional. When the crystalline (meth)acrylate based (co)polymer does not contain silicon atoms (e.g., referred to herein as an organic crystalline (meth)acrylate based (co)polymer), subscript x = 0. Subscript x has a value of 0 to 0.5, alternatively 0 to 0.3, and alternatively 0 to 0.25. Alternatively, when the silicone - (meth) acrylate macromonomer unit is present, subscript x > 0, alternatively subscript x may be at least 0.01, alternatively at least 0.02, alternatively at least 0.03, alternatively at least 0.04, alternatively at least 0.05, alternatively at least 0.06, alternatively at least 0.07, alternatively at least 0.08, alternatively at least 0.09, and alternatively at least 0.1; while at the same time, subscript x may be up to 0.3, alternatively up to 0.25, alternatively up to0.2, alternatively up to 0.19, alternatively up to 0.18,altematively up to 0.17, alternatively up to 0.16, alternatively up to 0.15, alternatively up to 0.14, alternatively up to 0.13, alternatively up to 0.12, alternatively up to 0.11, and alternatively up to 0.1. Alternatively, subscript x may be > 0 to 0.25, alternatively 0.03 to 0.25, alternatively 0.03 to 0.1, alternatively 0.05 to 0.95.

[0081] In unit formula (z'z-7) above, the unit with subscript y is optional, and subscript y has a value of 0 to 0.05. Alternatively, subscript y may be at least 0.01 , alternatively at least 0.012, alternatively at least 0.015, alternatively at least 0.0175, and alternatively at least 0.02; while at the same time, subscript y may be up to 0.05, alternatively up to 0.04, alternatively up to 0.03, alternatively up to 0.0275, alternatively up to 0.025, and alternatively up to 0.0225. Alternatively, subscript y may be 0 to 0.03, alternatively 0.01 to 0.03, alternatively 0.01 to 0.02, alternatively 0.015 to 0.025, alternatively 0.0175 to 0.0225, and alternatively 0.02.

[0082] In unit formula (ii-1) above, the unit with subscript y2 is optional, and subscript y2 has a value of 0 to 0.05. Alternatively, subscript y2 may be at least 0.01, alternatively at least 0.0125, alternatively at least 0.015, alternatively at least 0.0175, and alternatively at least 0.02; while at the same time, subscript y2 may be up to 0.05, alternatively up to 0.04, alternatively up to 0.03, alternatively up to 0.0275, alternatively up to 0.025, and alternatively up to 0.0225. Alternatively, subscript y2 may be 0 to 0.03, alternatively 0.01 to 0.02, alternatively 0.015 to 0.025, alternatively 0.0175 to 0.0225, and alternatively 0.02. Alternatively, subscript y2 may be 0 and the unit may be absent from the copolymer.

[0083] In unit formula (ii-1) above, the unit with subscript zl is optional, and subscript zl may be 0. Alternatively, subscript zl may be at least 0.005, alternatively at least 0.01, and alternatively at least 0.02; while at the same time, subscript zl may be up to 0.018, alternatively up to 0.015, alternatively up to 0.01, alternatively up to 0.08, and alternatively up to 0.05. Alternatively, subscript zl may be 0 to 0.018, alternatively > 0 to 0.018, alternatively 0.005 to 0.07, alternatively 0.01 to 0.06, and alternatively 0.02 to 0.05.

[0084] In unit formula (ii-1) above, the unit with subscript z2 is optional, and subscript z2 may be 0. Alternatively, subscript z2 may be at least 0.005, alternatively at least 0.01, and alternatively at least 0.02; while at the same time, subscript z2 may be up to 0.08, alternatively up to 0.07, alternatively up to 0.06, alternatively up to 0.05, and alternatively up to 0.04. Alternatively, subscript z2 may be 0 to 0.08, alternatively > 0 to 0.08, alternatively 0.005 to 0.07, alternatively 0.01 to 0.06, and alternatively 0.02 to 0.05.

[0085] The total number of units per molecule of the crystalline (meth)acrylate based (co)polymer of unit formula (ii-1) is not specifically restricted. However, the crystalline (meth)acrylate based (co)polymer 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 eachmonomer and the chain transfer agent. Alternatively, the crystalline (meth)acrylate based (co)polymer may have a number average molecular weight of 100,000 g / mol to 4,000,000 g / mol; alternatively 200,000 g / mol to 3,000,000 g / mol measured by GPC using the method described below. The units shown above may be in any order, e.g., when the crystalline (meth)acrylate based (co)polymer has more than one type of unit (e.g., when one or more of subscripts x, y, y2, zl , and z2 is greater than 0 and / or different (meth)acrylate monomers, such as stearyl acrylate and HEMA are used to make the (co)polymer), then the crystalline (meth)acrylate based (co)polymer may be a random copolymer or a block copolymer.

[0086] One skilled in the art would recognize that the crystalline (meth)acrylate based (co)polymer 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 crystalline (meth)acrylate based (co)polymer. The crystalline (meth)acrylate based (co)polymer 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 crystalline (meth)acrylate based (co)polymer may be prepared as described in PCT Publication WO / 2022 / 197350 corresponding to US Patent Application Serial No. 18 / 258663; PCT Publication WO / 2023 / 019044 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 by varying amounts of the starting materials. Each of PCT Publication WO / 2022 / 197350 corresponding to US Patent Application Serial No. 18 / 258663; PCT Publication WO / 2023 / 019044 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 is hereby incorporated by reference.

[0087] Alternatively, the crystalline (meth) aery late based (co)polymer may be a crystalline silicone - (meth)acrylate copolymer comprising unit formula (ii-2);wherein each R21is 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 R23is the group of formula OS i( R24)3 ; wherein each R24is independently selected from the group consisting of R and DSi(R25h, wherein each R is the 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 oxide group of 1 to 12 units, and the divalent hydrocarbon group of 2 to 4 carbon atoms; each R25is independently selected from the group consisting of R and DSi(R26)3; wherein each R26is independently selected from the group consisting of R and DSiRy with the proviso that R24, R25, and R26are 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 (ii-2), subscript w has a value of 0.80 to 0.9875; subscript x has a value of 0.0025 to 0.15; subscript y has a value of 0.01 to 0.05; subscript zl has a value of 0 to 0.1875; and subscript z2 has a value of 0 to 0.01875, and a quantity (w + x + y + zl + z2) = 1. The copolymer further comprises a terminal moiety.

[0088] In unit formula (ii-2) above, R21, R2, R, D2, D3, D4, R7, R8, R9, and R10, are as described and exemplified above for unit formula (ii-1 ).

[0089] In unit formula (ii-2) above, each R23is the group of formula OSi(R24)3; where each R24is independently selected from the group consisting of R and DSi(R25)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(R26h; where each R26is independently selected from the group consisting of R and DSiR?; with the proviso that R24, R25, and R26are selected such that the silicone - (meth)acrylate macromonomer unit with subscript x has at least 6 silicon atoms. Alternatively, R24, R25, and R26are 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 16silicon 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 (ii-1 ).

[0090] In unit formula (ii-2) above, subscripts w, x, y, zl, and z2 are relative weights of each unit, and a quantity (w + x + y + zl + z2) = 1 (based on combined weights of the monomers used to make the copolymer). Subscript w has a value of 0.8 to 0.9875. Alternatively, subscript w may be at least 0.8, alternatively at least 0.81, alternatively at least 0.82, alternatively at least 0.83, alternatively at least 0.84, and alternatively at least 0.85. At the same time, subscript w may be up to 0.9875, alternatively up to 0.98, alternatively up to 0.97, alternatively up to 0.96, alternatively up to 0.97, alternatively up to 0.96, alternatively up to 0.95, alternatively up to 0.94, alternatively up to 0.93, alternatively up to 0.92, alternatively up to 0.91, and alternatively up to 0.9. Alternatively, subscript w may be 0.8 to 0.98, alternatively 0.81 to 0.97, alternatively 0.82 to 0.96, alternatively 0.82 to 0.95, and alternatively 0.85 to 0.9.

[0091] In unit formula (zz-2)above, subscript x has a value of 0.0025 to 0.15. Alternatively, subscript w is at least 0.0025, alternatively at least 0.005, alternatively at least 0.0075, alternatively at least 0.01, alternatively at least 0.02, alternatively at least 0.03, alternatively at least 0.04, alternatively at least 0.05. At the same time, subscript x may be up to 0.15, alternatively up to 0.14, alternatively up to 0.13, alternatively up to 12, alternatively up to 11, and alternatively up to 10. Alternatively, subscript w may be 0.01 to 0.14, alternatively 0.02 to 0.13, alternatively 0.03 to 0.12, alternatively 0.04 to 0.11, alternatively 0.05 to 0.1, alternatively 0.05 to 0.15; and alternatively 0.1.

[0092] In unit formula (ii-2) above, subscript y has a value of 0.01 to 0.05. Alternatively, subscript y may be at least 0.01, alternatively at least 0.0125, alternatively at least 0.015, alternatively at least 0.02, and alternatively at least 0.0175. At the same time, subscript y may be up to 0.05, alternatively up to 0.04, alternatively up to 0.03, alternatively up to 0.0275, alternatively up to 0.025, and alternatively up to 0.0225. Alternatively, subscript y may be 0.01 to 0.03, alternatively 0.01 to 0.02, alternatively 0.015 to 0.025, alternatively 0.0175 to 0.0225, and alternatively 2.

[0093] In unit formula (ii-2) above, subscript zl may be 0. Alternatively, subscript zl may be at least 0.005, alternatively at least 0.01, and alternatively at least 0.02; while at the same time, subscript zl may be up to 0.1875, alternatively up to 0.15, alternatively up to 0.1, alternatively up to 0.08, and alternatively up to 0.05. Alternatively, subscript zl may be 0 to 0.1875, alternatively > 0 to 0.1875, alternatively 0.005 to 0.07, alternatively 0.01 to 0.06, and alternatively 0.02 to 0.05.

[0094] In unit formula (ii-2) above, subscript z2 may be 0. Alternatively, subscript z2 may beat least 0.005, alternatively at least 0.01, and alternatively at least 0.02; while at the same time, subscript z2 may be up to 0.08, alternatively up to 0.07, alternatively up to 0.06, alternatively up to 0.05, and alternatively up to 0.04. Alternatively, subscript z2 may be 0 to 0.08, alternatively > 0 to 0.08, alternatively 0.005 to 0.07, alternatively 0.01 to 0.06, and alternatively 0.02 to 0.05.

[0095] The total number of units per molecule of the crystalline silicone - (meth) acrylate copolymer of unit formula (ii-2) is not specifically restricted. However, this 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-bed shaker at ambient temperature for 2 hours. The solution may then be filtered through a 0.45 m PTFE syringe filter prior to injection. A Waters e2695 LC pump and autosampler, equipped with two 5 uM Agilent PLG gel Mixed C columns in series and Shodex RI501 differential refractive index detector was used to analyze the samples. The instrument was equilibrated for 30 min at 1 mL / min and samples were run at 1 mL / min. Agilent GPC software Cirrus version 3.3 may be used for data collection and for data reduction. A total of 16 polystyrene 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 polystyrene equivalent values. The units of the crystalline silicone - (meth)acrylate copolymer of unit formula (ii-2) may be in any order, e.g., the crystalline silicone - (meth) acrylate copolymer may be a random copolymer or a block copolymer.

[0096] One skilled in the art would recognize that the copolymer comprising unit formula (ii- 2) 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.

[0097] The crystalline (meth)acrylate based (co)polymer comprising unit formula ( ii-1 ) and / or the crystalline silicone - (meth) acrylate copolymer comprising unit formula (ii-2) 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 crystalline (meth)acrylate based (co)polymer, a surfactant, and water (and optionally a manganese ion source and a phenolic compound) may be prepared after formation of the crystalline (meth)acrylate based (co)polymer. The resulting aqueous emulsionmay comprise 20% to 97% of water and 0.1% to 10% of the surfactant, each based on weight of the crystalline (meth)acrylate based (co)polymer, with the balance to 100% being the crystalline (meth) acrylate based (co)polymer.

[0098] Starting material ii) further comprises a surfactant and water (in addition to the crystalline (meth)acrylate based (co)polymer). The surfactant may be selected from the group consisting of a cationic surfactant, a nonionic surfactant, and a combination of both the cationic surfactant and the nonionic surfactant, each as described and exemplified above as starting material (D) used in preparation of starting material i ), and the water is as described and exemplified above as starting material (E) used in preparation of starting material i). The amount of the cationic surfactant may be 0.1% to 5%, based on weight of the crystalline (meth) aery late based (co)polymer. Alternatively, the amount of cationic surfactant, when used, 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. The nonionic surfactant may be delivered in a dilution, and the amount used may be sufficient to provide 0.1% to 10% of the nonionic surfactant, based on weight of the crystalline (meth) acrylate based (co)polymer. 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, the cationic surfactant and the nonionic surfactant may be present in combined amounts < 10%, based on weight of the crystalline (meth) aery late based (co)polymer. The amount of water may be 90% to < 100%, alternatively 91% to 99%, alternatively 94% to 98%, based on combined weights of all components in starting material ii).

[0099] Starting material ii) described above may optionally further comprise an additional starting material. The additional starting material may be selected from the group consisting of a manganese ion source; a phenolic compound; another inhibitor; a biocide; additional water; a flame retardant; a wrinkle reducing agent; an antistatic agent; a penetrating agent; an additive such as a softening agent; a catalyst, such as a condensation reaction catalyst, and a combination of two or more thereof, where each of these additional starting materials are as described and exemplified above for starting material z).

[0100] Starting material iii) is the aqueous additive comprising the blocked isocyanate. The term “blocked isocyanate” 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 art such as amines, amides, compounds having an active hydrogen atom, alcohols, N-heterocyclic compounds, or oximes. Blocked isocyanates are commercially available, such as ARKOPHOB™ DAN and ARKOPHOB™ SR from Archroma of Pratteln, Switzerland; RUCO™-GUARD WEB and RUCO™-LINK XCR from Rudolf GmbH of Geretsreid, Bayern, Germany, and PHOBOL™ EXTENDER UXN and PHOBOL™ EXTENDER XAN rom Archroma. Alternatively, the blocked isocyanate may be an oxime blocked isocyanate, such as PHOBOL™ EXTENDER XAN™. Alternatively, the blocked isocyanate 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, 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 be2,6-dimethylpyrazine or a dimethylpyrazole, e.g., 3,5- dimethylpyrazole. Alternatively, the aqueous additive for use herein may be free of oxime compounds. Without wishing to be bound by theory, it is thought that the blocked isocyanate may be free of species that may interfere with the performance of the isocyanate in the textile treatment emulsion, such as silicones and amines (that are not within the blocking group). And, without wishing to be bound by theory, it is thought that the blocked isocyanate may be delivered in an emulsion or dispersion that is free of anionic surfactant. Suitable aqueous additives are commercially available and may be delivered in aqueous dispersions, and examples thereof are shown below in Table 0.Table 0 - Commercially Available Aqueous Additives

[0101] The exact amount of the blocked isocyanate compound depends on various factors including the type and amount of the non-crystalline silicone - (meth) acrylate copolymer and the textile to be treated, however, the weight of the blocked isocyanate may be sufficient to provide 0.1% to 3.75% of solids on fabric weight, alternatively 0.1% to 0.75%, alternatively 0.25% to 1%, and alternatively 0.25% to 0.5%, on the same basis; wherein solids refers to the amount of blocked isocyanate that may be delivered in an aqueous dispersion with other components, e.g., water and optionally a nonionic surfactant. Alternatively, the amount of starting material Hi) that may be mixed with starting materials z ) and ii ) may be sufficient to provide a weight ratio of non-crystalline silicone - (meth)acrylate copolymer and crystalline component combined : blocked isocyanate of 16:1 to 1:1, alternatively 16:1 to 2: 1, and alternatively 16: 1 to 1: 1.

[0102] This method for preparing the textile treatment emulsion may optionally further comprise one or more additional steps. For example, the method may further comprise step II) adding to the textile treatment emulsion, an additional starting material selected from the group consisting of the biocide, additional water, the flame retardant, the wrinkle reducing agent, the antistatic agent, the penetrating agent, the softening agent, the catalyst (each as described above), and a combination of two or more thereof; wherein each of these additional starting materials is as described above and may be added in step II) of the method for making the textile treatment emulsion, e.g., if not added in step 2) of the method for making starting material i) the aqueous copolymer emulsion described above. In the method for making the textile treatment emulsion herein, order of addition of the starting materials is not critical. Steps I) and II) may be done in any order. For example, step I) may be performed before step II). Alternatively, one or more of the additional starting materials from step II) may be combined with i) the aqueous copolymer emulsion, ii) the aqueous composition, and / or Hi) the aqueous additive before starting materials i ), ii ), and Hi ) are mixed.

[0103] The method for making the textile treatment emulsion may be performed by any convenient means, such as mixing using a jacketed vessel equipped with an agitator. When step II) is present, step I) and step II) may be performed concurrently or sequentially in the same vessel. Alternatively, steps I) and step II) may be performed in different equipment. Step I), and when present step II), may be performed at RT or elevated temperature, e.g., up to 100 °C, alternatively RT to 80°C, and alternatively RT.Method of Use

[0104] The textile treatment emulsion prepared as described above may be used for treating atextile. For example, a method for treating a textile comprises: 1 ) contacting the textile with the textile treatment emulsion described above, and 2 ) heating the textile. Step 1 ) may be performed by any convenient method, such as padding, exhausting, dipping, or spraying the textile with the textile treatment emulsion. However, the method should be sufficient to deliver a sufficient amount of the non-crystalline silicone - (meth)acrylate copolymer and the crystalline component sufficient to impart durable oil resistance properties to the textile, according to the methods described herein. The method may be sufficient to deliver on fabric weight of 0.25% to 10% of the non-crystalline silicone - (meth) acrylate copolymer and the crystalline component combined, based on weight of the textile.

[0105] Step 2 ) 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 optionally to cure the non-crystalline silicone - (meth)acrylate copolymer and / or the crystalline component. 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, and / or cure the non-crystalline silicone - (meth)acrylate copolymer and / or the crystalline component.

[0106] 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 emulsion described herein is suitable for use on textiles in any form, e.g., woven fabrics, knitted fabrics, or nonwoven textiles.EXAMPLES

[0107] The following examples are provided to illustrate the invention to those skilled in the art and are not to be construed so as to limit the invention set forth in the claims. Starting materials used in these examples are summarized below in Table 1.Table 1 - Starting Materials

[0108] In this Synthesis Example 1 , aqueous copolymer emulsions with non-crystalline silicone - (meth)acrylate copolymers were prepared as follows. All macromonomers, water and surfactant were added to a 400 mL widemouth jar in selections and amounts shown below in Table 2. A sonicator was used to make an emulsion (Fisherbrand Model 705 sonic dismembrator, amplitude 50, Power ~62 W, for 2 min). The aqueous emulsion was then transferred to a reactor and heated to 65 °C. After the aqueous emulsion came to temperature, Initiator 4 was added (0.26 g), and the reactor contents were stirred for 6 h. The reactor contents were then cooled down to room temperature and the resulting copolymer emulsions were each poured into a bottle. Emulsion 1 summarized below in Table 2 was made according to this example.

[0109] In this Synthesis Example 2, silicone - (meth)acrylate copolymer emulsions were prepared as follows. All starting materials were weighed into a 400 mL wide mouth jar in selections and amounts shown below in Table 2. A sonicator was used to make an emulsion (Fisherbrand Model 705 sonic dismembrator, amplitude 50 for 2 min). The resulting emulsion was then transferred to a 500 mL 4 neck flask equipped with a reflux condenser, nitrogen inlet, overhead stirrer (IKA RW20) and thermocouple probe. In this example, 0.4 g of a 2.5 % water solution of 4-methoxyphenol, 0.004 g of hydroquinone and 0.08 g of 0.7 % water solution of Mn(II)acetate tetrahydrate were used as inhibitors. This emulsion was stirred at 250 RPM using a Teflon blade and heated to 65 °C. After reaching temperature 0.25 g of Initiator 4 was added, and the reaction was run for 6 hours. The resulting material was then allowed to cool to 30 to 40 °C with slow stirring before pouring off. Emulsions 2, 3, 7, and 10 summarized below in Table 2 were made according to this example.Table 2 - Aqueous Silicone - (Meth)acrylate Copolymer Emulsions

[0110] In this Synthesis Example 3, aqueous compositions were prepared as follows. First, solutions A, B, and C were prepared. Solution A preparation: Added 0.0566 g of t- butylhydroperoxide (70% in water) and then enough water to make a 10 g solution. Solution B preparation: Added 0.0773 g of isoascorbic acid and then enough water to make a 10 g solution. Solution C preparation: Added 6 mg iron (II) sulfate heptahydrate and then enough water to make a 10 g solution.

[0111] Next, the starting materials summarized below in Table 3 were weighed into a 400 mL wide mouth jar. The stearyl acrylate and behenyl acrylate monomers were melted first and each added as a liquid. In addition, the emulsions were inhibited with Hydroquinone (50 ppm based on monomer), Mn(II) acetate*4H2O (1.5 ppm based on monomer) and methyletherhydroquinone (150 ppm based on monomer). A sonicator was used to make an emulsion (Fisherbrand sonic dismembrator, amplitude 50 for 2 min). The resulting coarse emulsion was then, optionally, passed through a microfluidizer (Microfluidics Microfluidizer 110Y) and set to 5,000 psi, twice. The resulting emulsion was then transferred to a 500 mL 4 neck flask equipped with a reflux condenser, nitrogen inlet, overhead stirrer (IKA RW20) and thermocouple probe. This emulsion was stirred at 250 RPM using a Teflon blade and heated to 45-60 °C. After reachingtemperature, Solution C was added (1.74 grams of prepared Solution C) and a redox initiator was then fed into the flask at 0.25 mL / min (Solutions A+B, prepared as described above in separate feeds). The reaction was run for 45 min. The resulting material was then allowed to cool to 30 to 40 °C with slow stirring before pouring off.Table 3 - Aqueous Compositions with Crystalline Components

[0112] In this Synthesis Example 4, Emulsion 8, the HD PE dispersion, with the polymer phase components and physical properties as shown in Table 4 was prepared. The HDPE Base Resin and PvOH Dispersant were each fed into a 25 mm diameter twin screw extruder using a controlled rate feeder at the given ratios listed in Table 4 at a total feed rate of 75.6 g / min. The HDPE Base Resin and dispersant were forwarded through the extruder and melted to form a liquid melt material where the melt zone temperature in the extruder was set to be 15 °C greater than the melting temperature of the PvOH Dispersant (which was the highest melting point component). An initial amount of water was then added into the extruder at a rate roughly equal to the feed rate of the PvOH Dispersant. In a later section of the extruder, additional dilution water was then added at a rate to give the emulsion with the percentage of solids as indicated in Table 4. The extruder speed used was 600 rpm. At the extruder outlet, a backpressure regulator was used to adjust the pressure inside the extruder barrel to a pressure adapted to reduce steam formation (generally the pressure was from 2 MPa to 4 MPa). The HDPE dispersion exited from the extruder and was filtered first through a 200 pm filter. The resultant filtered HDPE dispersion had a solids content measured in weight percent (%); and the solids particles of the HDPE dispersion had a volume mean particle size measured in pm. The solids content of the HDPE dispersion was measured using an infrared solids analyzer and the particle size of the solids particles of the polyester dispersion is measured using a COULTERTM LS-230 particle size analyzer (Beckman Coulter Corporation, Fullerton, CA). The solids content and the average particle size (PS) of the solids particles of the HDPE dispersion are indicated in Table 4.Table 4 - HDPE Dispersion

[0113] In this Synthesis Example 5, Emulsion 9 was prepared as follows. Paraffin wax with Tm58-62 °C (14.97 g), Brij 010 (0.6 g), Span 60 (0.66 g), and water (133.83 g) were loaded into a Primix AGI Homo Mixer 2M-3. The mixer was closed and heated at 70-80 °C. After the wax melted, stirring was started. The Primix mixer was set to 5000 RPM, and the contents were mixed for 30 min. The material was allowed to cool to < 55 °C with mixing, and then collected.

[0114] In this Reference Example 1 , textile treatment emulsions were prepared by adding each starting material in the amounts shown below in Table 5 into a 125 g Nalgene plastic bottle. The bottle was then inverted twice to mix the contents. In Table 5, Weight Ratio of Actives means weight of copolymer (active) in i) the aqueous copolymer emulsion : weight of crystalline component (active) in starting material ii ).Table 5 - Textile Treatment Emulsions

[0115] In this Reference Example 2, fabrics were treated with the textile treatment emulsions prepared as described above and shown in Table 5. Treatment was performed as follows: All the fabrics were washed / dried before coating. The textile treatment emulsion was then poured into beaker and then dip coated and passed through a Werner Mathis AG Textilmaschinen padder (tension setting of 70) for coating. After passing through once, the sample was placed in a forced air Mathis LTF oven at 160 °C for 3 min.

[0116] In this Reference Example 3, oil repellency was tested using a modified version of AATCC 118, i.e., the face rankings of A, B, C, and D were used as described in AATCC 118 (and as shown in Figure 3 of “Fluorine- free low surface energy organic coating for anti-stain applications” by Lei, et al, Progress in Organic Coatings 103 (2017)182-192, 184). Face ranking of A denoted a clear, well-rounded bead of oil; B denoted a rounding drop with partial darkening; C denoted wick was apparent and / or complete wetting; and D denoted complete wetting. The modifications to this test method were that the oil used was olive oil, and the time was extended from 10 sec to 1 min. A relatively large olive oil drop was used for this test, i.e., at least 250 uL per drop. For purposes of this application, a sample was deemed to have durable oil repellency if it had a rating of A or B after 1 min. Face rating of C or D represented unacceptably high oil absorbance by the fabric. Results are shown below in Table 6.Table 6 - Oil Repellency Results

[0117] In each of the working examples (Examples 1-18, above), a crystalline component (i.e., polymer with Tc of 34 °C to 1 17 °C measured according to the test method below) was used.The crystalline component may have various chemistries (e.g., (meth)acrylate, alkyl urethane, or polyolefin based), and without wishing to be bound by theory, it is thought that the working examples demonstrated that (in combination with the non-crystalline silicone - (meth)acrylate copolymer and the blocked isocyanate) the Tc of 34 °C to 117 °C of the crystalline component may provide a benefit to oil repellency performance as compared to other properties (e.g., chemistry) of the crystalline component.

[0118] The Tc was measured using a TA Instruments differential scanning calorimeter with the method as follows:1: Sampling interval 0.20 sec / pt2: Data storage: Off3: Equilibrate at 200.00°C4: Isothermal for 2.00 min5: Data storage: On6: Ramp 10.00°C / min to -90.00°C7: Isothermal for 5.00 min8: Mark end of cycle 19: Ramp 10.00°C / min to 200.00°C10: Mark end of cycle 211: Data storage: Off12: Equilibrate at 40.00°C13: End of method

[0119] The peak crystallization temperature, Tc, was measured from the data acquired in step 6 (on cooling). The Tc was determined using TA Universal Analysis software using the “integrate peak linear” function and designating the peak with the greatest change in Heat flow (or highest peak) as Tc. The same method was used for step 9 (on heating) to determine the peak melting temperature (or melting point). In both cases the boundaries of analysis were placed to incorporate the entire range of peak or peaks.

[0120] The inventors surprisingly found that forming a physical mixture (e.g., cold blending by mixing at RT) starting materials i), ii) and Hi) as described above in the amounts described herein afforded a textile treatment emulsion that imparted oil repellency to textiles. Examples 1- 3 and 6 in Table 6 demonstrated that blending starting material i) with starting material ii), which contained a crystalline component that had Tc = 34 °C - 38 °C, with an active ratio 1:3 provided textile treatment emulsions that imparted oil repellency to fabrics under the conditions tested. The materials used for starting material ii ) were all different products containing actives with different chemistries. For example, Zelan R3 contained a crystalline alkyl urethanemacromolecule, whereas Nicca 7080, Nicca 7090, and PHOBOTEX RSY contained crystalline polyacrylate materials. Without wishing to be bound by theory, it is thought that Tc of the active in starting material ii) may have had a larger impact on oil repellency than the specific chemistry of the active in starting material ii).

[0121] Example 17 utilized as starting material ii) a polyolefin dispersion which contained an active that had a Tc of 117 °C, which further supported the theory that Tc had a more significant impact on oil repellency than the specific chemistry of the active in starting material ii). Examples 15 and 16 used a Nylon fabric and showed that the textile treatment emulsion of the present invention was able to achieve oil repellency with this fabric, in addition to polyester fabric tested in other working examples. In addition, Example 16 showed that the ratio of actives in starting materials i) and ii) can be 3:1.

[0122] Comparative 1 did not contain a crystalline component and did not impart oil repellency to the textile under the conditions tested. Comparative 2 did not contain starting material iii ) (which contains the blocked isocyanate) and did not impart oil repellency to the textile under the conditions tested. Comparative 3 demonstrated that a sample prepared as described in US Patent 11746268 did not impart oil repellency to the textile under the conditions tested herein. Comparative 4 substituted starting material ii) with an aqueous emulsion including a non-crystalline, silicone polymer as the active, and Comparative 4 did not impart oil repellency to the fabric under the conditions tested. Comparative 5 demonstrated that using only starting materials ii) and iii) (without starting material i) containing the non-crystalline silicone - (meth)acrylate copolymer as an active) did not impart oil repellency to the fabric under the conditions tested. Comparative 6 showed that using an aqueous composition with an anionic dispersant as starting material ii) was detrimental to oil repellency performance under the conditions tested. Comparative 7 employed an aqueous emulsion of a copolymer of 75% SA and 25% 3MT-ALMA and did not provide oil repellency to the textile under the conditions tested. Comparative 7 and Example 4 demonstrated that copolymerizing the crystalline and noncrystalline actives did not provide oil repellency, however, forming a physical mixture of emulsions containing the non-crystalline silicone - (meth)acrylate copolymer and the crystalline component successfully imparted oil repellency to the fabric under the conditions tested.

[0123] In this Synthesis Example 6, PDMS resin 1 (as described in Example 1 of Patent Publication Number US20230038369 was prepared as follows: 0.88 g (10 mmol) of 3MT- ALMA, 0.31 g (1 mmol) of vinyl trimethoxysilane and 0.033g (0.1 mmol) of azobisisobutyronitrile were added to a round bottom flask with 47.95 g of dry xylenes at room temperature. The round bottom flask was equipped with a condenser, nitrogen inlet, overhead stirrer and thermocouple probe. The system was purged with nitrogen for 5 min and then the-M-solution was heated up to 65°C and then held for 24 h.

[0124] In this Synthesis Example 7, PDMS resin 2 was prepared as follows: An 80 DP amino terminated PDMS (30 g, 10 mmol), bisphenol A (2.28 g, 10 mmol) and paraformaldehyde (1.2 g, 40 mmol) were dissolved in 150 mL of chloroform in a 500 mL round bottom flask. The mixture was heated under reflux for 6 h to give a light yellow solution. After removing the solvent under vacuum, the residue was dissolved in 75 mL of methylene chloride. The material was washed with a saturated solution of NaHCCL (75 mL x 5). The water was then distilled off leaving a light yellow liquid product. PDMS resin 2 gelled by the next day, so this resin could not be coated on a textile.

[0125] The procedure for these comparative examples 8 and 9 , which included pre-treatment of fabric then treatment with the PDMS resin 1, was as follows: A Ixlcm PES or Nylon fabric was washed with 200 proof ethanol and then dried in an oven 80 °C for 10 min. Then a silica sol was prepared by hydrolysis of tetraethoxysilane (2.08 g, 10 mmol) in 60 mL of ethanol / 15 mL of DI water in the presence of ammonium hydroxide (2.75 mL). The fabric was dipped into the sol for 5 min and dried at room temperature (~30 min). This process was repeated 2 more times. The fabric was then soaked in a 5% suspension of Ludox HS silica (5 g of a 40% solution of Ludox HS-40 colloidal silica and 35 g of DI water) until saturated (~4 sec) and then dried overnight at 80 °C. The pretreated 1x1 cm PES or nylon fabric samples were dip coated 3 times into PDMS resin 1. The samples were cured for 1 h at 200 °C.

[0126] The procedure for these comparative examples 10 and 11 was as follows: A 1x1 cm PES or nylon fabric sample was dip coated 3 times into synthesis PDMS resin 1. The samples were cured for 1 h at 200 °C.

[0127] The procedure for these comparative examples 12 and 13 was as follows:A Ixlcm PES or Nylon fabric was washed with 200 proof ethanol and then dried in an oven 80 °C for 10 min. Then a silica sol was prepared by hydrolysis of tetraethoxysilane (2.08 g, 10 mmol) in 60 mL of ethanol / 15 mL of DI water in the presence of ammonium hydroxide (2.75 mL). The fabric was dipped into the sol for 5 min and dried at room temperature (~30 min). This process was repeated 2 more times. The fabric was then soaked in a 5% suspension of Ludox HS silica (5 g of a 40% solution of Ludox HS-40 colloidal silica and 35 g of DI water) until saturated (~4 sec) and then dried overnight at 80 °C.Table 7 - Results for Comparative Examples 8 to 13

[0128] Comp 8 and Comp 9 correspond to example 2 disclosed in US Patent Publication US20230038369. These received a failing oil repellency grade after 5 min in the modified AATCC method 118. Comp 10 and Comp 11 removed the sol gel and nanoparticle treatment and tested the 3MT-ALMA / vinyl trimethoxysilane copolymer, and these examples also failed the modified AATCC method 118 after 5 min. In contrast, the present invention, (e.g., as shown in working examples 1-18 in Table 6, above) had superior oil repellency after 1 minute using the modified AATCC method 118 described herein.

[0129] In this Comparative Example 14, the PES fabric was treated with 2 separate emulsions in 2 separate steps. First the fabric was coated with an emulsion of PHOBOL™ EXTENDER XAN (0.69 g XAN + 74.31 g DI water), described in the coating / curing methods in Reference Examples 2 and 3, above. In a second step the fabric was treated with an Emulsion 1 from Table 2, above, in which 5.75 g of the Emulsion 1 from Table 2 was combined with 69.25 g DI water using the same coating curing methods described above in Reference Example 2.

[0130] Comparative example 14 shows a pretreatment method of the blocked isocyanate (XAN) additive similarly described in example 2 in US Patent Publication US20230038369 (Comparative Examples 8 and 9 above). This comparative example 14 did not pass the modified AATCC method 1 18 after 10 sec and had worse oil repellency than Comparative Examples 8 and 9 above at 10 sec.

[0131] In this Comparative Example 15, 2.25 g of Daikin XF-5100 (available in the United States instead of XF-5003, 3%), 4.5 g of RUCODRY Eco Plus (6%) and 1.875 g of RUCO- LINK XCR (2.5%), both from Rudolf Group, with 66.125 g of water. The resulting sample was coated on PES according to the method of Reference Example 2 and evaluated via the modified AATCC 118 test in Reference Example 3. The treated fabric failed the oil repellency test at 30 sec.INDUSTRIAL APPLICABILITY

[0132] The examples above demonstrate that the textile treatment emulsion and method of the present invention impart durable oil repellency to textiles. Without wishing to be bound by theory, it is thought that the textile treatment emulsion of the present invention can impart both water repellency and oil repellency to textiles. The method for imparting oil repellency to atextile comprises: step 1 ) applying to a textile, the textile treatment emulsion prepared as described above; and step 2) drying the textile, thereby removing all or a portion of the water. However, this method may consist essentially of, or consist of, step 1 ) and step 2) because this invention provides the added benefit that only one application of the textile treatment emulsion is required, e.g., it is not necessary to repeat step 1) to reapply the textile treatment emulsion in order to impart oil repellency.DEFINITIONS AND USAGE OF TERMS

[0133] All amounts, ratios, and percentages herein are by weight, unless otherwise indicated. The amounts of all starting materials combined to make a composition or an emulsion totals 100%. 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., II., and III. The use of “for example,” “e.g. " “such as,” and “including” to list illustrative examples does not limit to only the listed examples. Thus, “for example” or “such as” means “for example, but not limited to” or “such as, but not limited to” and encompasses other similar or equivalent examples.“Crystalline” means having a Tc of > 25 °C measured by the test method described above. “Non-crystalline” means not having a Tc > 25 °C measured by the test method described above. The abbreviations used herein have the definitions in Table 8.Table 8 - Abbreviations

Claims

CLAIMS:

1. A method for making a textile treatment emulsion, wherein the method comprises:I) mixing starting materials comprising i ) an aqueous copolymer emulsion comprising a non-crystalline silicone - (meth)acrylate copolymer, a nonionic surfactant, and water, wherein the non-crystalline silicone - (meth) acrylate copolymer comprises unit formula:, wherein each R1is an independently selected monovalent hydrocarbon group of 1 to 12 carbon atoms; each D2is an independently selected divalent hydrocarbon group of 2 to 12 carbon atoms; each R2is independently selected from the group consisting of H and methyl; each R3is a group of formula OSi(R4)3; wherein each R4is independently selected from the group consisting of R andDSi(R5)3, wherein 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; and 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 non-crystalline silicone - (meth)acrylate co- macromonomer unit with subscript b2 has at least 5 silicon atoms; subscripts a, bl, and b2 represent weight fractions of units in thecopolymer, and subscripts a, bl, and b2 have values such that0.25 < a < 1; and0 < (bl + b2) < 0.75; ii) an aqueous composition comprising a crystalline component, a nonionic surfactant, and water, wherein the crystalline component has a crystallization temperature of > 25 °C; and wherein starting material i ) and starting material ii ) are used in amounts sufficient to provide a weight ratio of the non-crystalline silicone - (meth)acrylate copolymer : the crystalline component of 1:3 to 3: 1; andHi ) an aqueous additive comprising a blocked isocyanate and water; wherein Hi ) the aqueous additive is added in an amount sufficient to provide a weight ratio of the non-crystalline silicone - (meth)acrylate copolymer and the crystalline component, combined : blocked isocyanate of 16: 1 to 1:1.

2. The method of claim 1, wherein the weight ratio of the silicone - (meth) acrylate copolymer : the crystalline component is 1:3 to 1:1.

3. The method of claim 1 or claim 2, wherein the crystalline component is selected from the group consisting of an alkyl urethane, a polyolefin, a poly(meth)acrylate, and a poly(meth)acrylate having a pendant polyorganosiloxane moiety.The method of any one of claims 1 to 3, wherein the crystalline component has a crystallization temperature of 25 °C to 130 °C.

4. The method of any one of claims 1 to 3, wherein starting material ii) is selected from the group consisting of Zelan™ R3 from Chemours, NEOSEED™ NR-7080 from Nicca, NEOSEED™ NR-7090 from Nicca, PHOBOTEX RSY from Huntsman, DOWSIL™ IE-9100 Emulsion from Dow, and an aqueous emulsion of DOW™ DMDA-8965 NT7 High Density Polyethylene Resin from Dow, a polyvinyl alcohol, and water.

5. The method of any one of claims 1 to 4, wherein the weight ratio of the non-crystalline silicone - (meth)acrylate copolymer and the crystalline component combined : blocked isocyanate is 8:1.

6. The method of any one of claims 1 to 5, wherein the blocked isocyanate comprises an oxime blocked isocyanate or an N-heterocycle blocked isocyanate.

7. The method of any one of claims 1 to 6, wherein starting material i) is prepared by a method comprising:1) copolymerizing starting materials comprising(A) a silicone - (meth) acrylate macromonomer of formulaeach R1is an independently selected monovalent hydrocarbon group of 1 to 12 carbon atoms; D2is a divalent hydrocarbon group of 2 to 12 carbon atoms; and R2is selected from the group consisting of H and methyl; optionally (B) a silicone - (meth)acrylate co-macromonomer, wherein (B) the silicone - (meth)acrylate co-macromonomer has a formula selected from the group consisting of formula (B-l), formula (B-2), and a combination of both formula (B-l) and formula (B-2), wherein formula (where each R1is an independently selected monovalent hydrocarbon group of 1 to 12 carbon atoms; D2is a divalent hydrocarbon group of 2 to 12 carbon atoms; and R2is selected from the group consisting of H and methyl; formula (B-2) isselected from the group consisting of H and methyl; D2is a divalent hydrocarbon 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 DSiRy with the proviso that R4, R5, and R6are selected such that the silicone - (meth)acrylate co-macromonomer of formula (B-2) has at least 5 silicon atoms per molecule; where starting material (A) is present in an amount of > 25 weight % to 100 weight %, based on combined weights of starting materials (A) and (B); andwhere starting material (B) is present in an amount of 0 to < 75 weight %, based on combined weights of starting materials (A) and (B); and where starting materials (A) and (B) are copolymerized in the presence of an additional starting material, wherein the additional starting material comprises(C) an initiator; optionally a chain transfer agent; optionally a manganese ion source; and optionally a phenolic compound; and where one of conditions (i) or (ii) is met, wherein condition (i) is that step 1) further comprises adding a solvent before or during step 1), removing the solvent after forming the non-crystalline silicone - (meth)acrylate copolymer, and forming i ) the aqueous copolymer emulsion comprising the non-crystalline silicone - (meth)acrylate copolymer, the nonionic surfactant, and the water; and wherein condition (ii) is that step 1) comprises an emulsion polymerization reaction; the additional starting materials further comprise the nonionic surfactant and the water; and where the product of step 1) comprises i) the aqueous copolymer emulsion comprising the non-crystalline silicone - (meth) acrylate copolymer, the nonionic surfactant, and the water.

8. The method of any one of claims 1 to 7, further comprising:II) adding an additional starting material selected from the group consisting of a biocide, additional water, a flame retardant, a wrinkle reducing agent, an antistatic agent, a penetrating agent, a softening agent, a condensation reaction catalyst, and a combination of two or more thereof.

9. A textile treatment emulsion comprising: a non-crystalline silicone - (meth) acrylate copolymer comprising unit formula:, wherein each R1is an independently selected monovalent hydrocarbon group of 1 to 12 carbon atoms; each D2is an independently selected divalent hydrocarbon group of 2 to 12carbon atoms; each R2is independently selected from the group consisting of H and methyl; each R3is a group of formula OSi(R4)3; wherein each R4is independently selected from the group consisting of R and DSi(Rsh, wherein 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; and 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 non-crystalline silicone - (meth)acrylate co- macromonomer unit with subscript b2 has at least 5 silicon atoms; subscripts a, bl, and b2 represent weight fractions of units in the copolymer, and subscripts a, bl, and b2 have values such that0.25 < a < 1; and0 < (bl + b2) < 0.75; and a crystalline component having a crystallization temperature > 25 °C; wherein the non-crystalline silicone - (meth) acrylate copolymer and the crystalline component are present in amounts such that a weight ratio of the noncrystalline silicone - (meth)acrylate copolymer : the crystalline component is 3:1 to 1:3; a blocked isocyanate wherein the blocked isocyanate is present in an amount such that a weight ratio of the non-crystalline silicone - (meth)acrylate copolymer and the crystalline component combined : blocked isocyanate is 16:1 to 1:1; a nonionic surfactant; and water.

10. The textile treatment emulsion of claim 9, wherein crystalline component is selected from the group consisting of an alkyl polyurethane, a polyolefin, a poly(meth)acrylate, and a poly(meth)acrylate having a pendant polyorganosiloxane moiety.The textile treatment emulsion of claim 9 or claim 10, wherein the crystalline component has a crystallization temperature of 25 °C to 130 °C.

11. The textile treatment emulsion of claim 9 or claim 10, wherein the weight ratio of the non-crystalline silicone - (meth)acrylate copolymer and crystalline component combined : blocked isocyanate is 8: 1.

12. The textile treatment emulsion of any one of claims 9 to 1 1 , wherein the blocked isocyanate comprises an oxime blocked isocyanate or an N-heterocycle blocked isocyanate.

13. A method for imparting oil repellency to a textile, wherein the method comprises: step 1 ) applying to a textile, the textile treatment emulsion prepared by the method of any one of claims 1 to 8 or the textile treatment emulsion of any one of claims 9 to 12, and step 2 ) drying the textile, thereby removing all or a portion of the water.

14. The method of claim 13, wherein the method consists of step 1 ) and step 2).

15. An oil repellent textile prepared by the method of claim 13 or claim 14.

16. The method of any one of claims 1 to 8, wherein the non-crystalline silicone - (meth) acrylate copolymer has a weight average molecular weight > 181,000 g / mol measured by Gel Permeation Chromatography.

17. The method of claim 16, wherein the weight average molecular weight is 212,000 g / mol to 2,000,000 g / mol.

18. The textile treatment emulsion of any one of claims 9 to 12, wherein the silicone - (meth) acrylate copolymer has a weight average molecular weight > 181,000 g / mol measured by Gel Permeation Chromatography.

19. The textile treatment emulsion of claim 18, wherein the weight average molecular weight is 212,000 g / mol to 2,000,000 g / mol.

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