TW202516078A - Silicone – (meth)acrylate copolymer composition containing a silicone additive and methods for the preparation and use thereof - Google Patents

Abstract

An emulsion formulation includes a silicone – (meth)acrylate copolymer, a manganese ion source, a phenolic compound, and a silicone additive. The emulsion formulation can be coated on textiles and dried to impart both durable water repellency and softness to the textiles.

Description

Polysilicone-(meth)acrylate copolymer composition containing polysilicone additive and preparation method and use thereof

Cross-reference to related applications

This application claims the benefit of U.S. Provisional Patent Application Serial No. 63/588056, filed on October 5, 2023, pursuant to 35 U.S.C. §119(e). U.S. Provisional Patent Application Serial No. 63/588056 is hereby incorporated herein by reference.

Provided is a composition comprising a polysilicone-(meth)acrylate copolymer (copolymer), a manganese ion source, and a phenolic compound, and a method for preparing the composition. An aqueous emulsion of the composition can be combined with an aqueous emulsion of a polysilicone additive to form an emulsion formulation suitable for treating textiles to impart durable water repellency and softness thereto.

Fluorocarbon materials have dominated the market for water-repellent textile treatment applications due to their ability to provide excellent, long-lasting water repellency. However, regulatory and customer pressures are driving industry demand for non-fluorocarbon textile treatments. Previously disclosed non-fluorocarbon textile treatments suffer from poor durability, where the water repellency of treated textiles is significantly reduced after multiple washes.

An emulsion formulation suitable for treating textiles comprises: (I) a polysilicone-(meth)acrylate copolymer, (II) an additive, (III) a water-dispersible crosslinking agent, (IV) a surfactant, (V) water, a manganese ion source, and a phenolic compound. The textiles can be treated by coating the emulsion formulation on the textiles and heating the textiles.

The process for forming an emulsion formulation suitable for treating textiles comprises: combining the following materials: a first aqueous emulsion comprising (I) a polysilicone-(meth)acrylate copolymer, a manganese ion source, and a phenolic compound; a second aqueous emulsion comprising (II) an additive, (III) a water-dispersible crosslinking agent, and optionally one or more additional starting materials as described below. Alternatively, the process for preparing the emulsion formulation described above may comprise: 1) preparing starting material (I) the polysilicone-(meth)acrylate copolymer by emulsion polymerization of starting materials, wherein the starting materials comprise: 80 wt % to 98.75 wt % of formula (A) 0.25 ^wt % to 15 wt % ^of the formula (B) wherein R ² , D ² , and R ³ are as described above; 1 wt % to 5 wt % of formula (C) a crosslinkable (meth)acrylate monomer, wherein R ⁷ , D ³ , D ⁴ , subscript v, and R ⁸ are as described above; wherein the total amount of the starting materials (A), (B), and (C) is 100% by weight, based on the combined amount of the starting materials (A), (B), and (C) shown above. The starting materials in step 1) of the process for preparing the composition further include: (D) a surfactant; (E) water; (F) an initiator; (H) a chain transfer agent; (K) a manganese ion source; and (L) a phenolic compound; thereby forming a first aqueous emulsion comprising (I) the polysilicone-(meth)acrylate copolymer; 2) providing a second aqueous emulsion comprising (II) the additive, (D') a surfactant, and (E') water; and 3) Mixing materials, the materials comprising the first aqueous emulsion prepared in step 1), the second aqueous emulsion from step 2), (III) the water-dispersible crosslinking agent, and optionally one or more additional starting materials selected from the group consisting of an additional surfactant, wax, biocide, additional water, flame retardant, wrinkle reducer, antistatic agent, and penetrant. (I) Polysilicone-(meth)acrylate copolymer

Polysilicone-(meth)acrylate copolymer (copolymer) comprises the following unit formula: wherein each R ¹ is an independently selected alkyl group of 16 to 24 carbon atoms; each R ² is independently selected from the group consisting of H and methyl; each D ² is a divalent hydrocarbon group of 2 to 12 carbon atoms; each R ³ is a group of formula OSi(R ⁴ ) ₃ ; wherein each R ⁴ is independently selected from the group consisting of R and DSi(R ⁵ ) ₃ ; wherein each R is an independently selected monovalent hydrocarbon group of 1 to 12 carbon atoms, and each D is independently selected from the group consisting of oxygen atoms, (poly) epoxyalkyl groups of 1 to 12 units, and divalent hydrocarbon groups of 2 to 4 carbon atoms; each R ⁵ is independently selected from the group consisting of R and DSi(R ⁶ ) ₃ ; wherein each R ⁶ is independently selected from R and DSiR ₃ ; with the restriction that R ⁴ , R ⁵ , and R ⁶ are selected so that the polysilicone-(meth)acrylate macromer unit with subscript x has at least 6 silicon atoms; each R ⁷ is independently selected from the group consisting of oxygen atoms and NH; D ³ is a divalent hydrocarbon group of 1 to 12 carbon atoms; D ⁴ is an alkylene group or a divalent alkylene arylene group of 2 to 4 carbon atoms; subscript v represents the number of units of formula (OD ⁴ ) in the unit with subscript y, and the value of subscript v is 0 to 12; each R ⁸ is a crosslinkable group; each R ⁹ is a monovalent hydrocarbon group of 1 to 14 carbon atoms; each R ¹⁰ is independently selected from the group consisting of halogen (e.g., chlorine), acetate, or monovalent hydrocarbon groups of 1 to 14 carbon atoms; subscripts w, x, y, z1, and z2 represent the relative weight of each unit in the copolymer, with subscript x having a value of 0.25 to 15; subscript w having a value of 80 to 98.75; subscript y having a value of 1 to 5; subscript z1 having a value of 0 to 18.75; and subscript z2 having a value of 0 to 18.75, and the number (w + x + y + z1 + z2) = 100. The copolymer further comprises a terminal portion.

In the above unit formula, ^R1 has 16 to 24 carbon atoms. Alternatively, ^R1 may have 16 to 22 carbon atoms, or 18 to 24 carbon atoms, or 18 to 22 carbon atoms. ^R1 may be selected from the group consisting of stearyl, eicosyl, and behenyl. Alternatively, ^R1 may be stearyl.

In the above unit formula, each R ³ is a group of formula OSi(R ⁴ ) ₃ ; wherein each R ⁴ is independently selected from the group consisting of R and DSi(R ⁵ ) ₃ ; wherein each R is an independently selected monovalent hydrocarbon group of 1 to 12 carbon atoms, and each D is independently selected from the group consisting of: an oxygen atom, a (poly)epoxyalkylene group of 1 to 12 units, and a divalent hydrocarbon group of 2 to 4 carbon atoms; each R ⁵ is independently selected from the group consisting of R and DSi(R ⁶ ) ₃ ; wherein each R ⁶ is independently selected from the group consisting of R and DSiR ₃ ; with the limiting condition that R ⁴ , R ⁵ , and R ⁶ are selected so that the polysilicone-(meth)acrylate macromer unit with subscript x has at least 6 silicon atoms. Alternatively, ^R4 , ^R5 , and ^R6 are selected so that the unit has at least 6 silicon atoms per unit, or 6 to 20 silicon atoms, or 7 to 19 silicon atoms, or 8 to 18 silicon atoms, or 9 to 17 silicon atoms, or 10 to 16 silicon atoms.

In the polysilicone-(meth)acrylate macromer unit, each R is a monovalent alkyl group of 1 to 12 carbon atoms. The monovalent alkyl group of R can be an alkyl group, such as an alkyl group of 1 to 6 carbon atoms. Alternatively, the alkyl group can have 1 to 3 carbon atoms, or 1 to 2 carbon atoms. Alternatively, each R group can be a methyl group.

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 alkylene group of 2 to 4 carbon atoms. Each D ² is a divalent alkylene group of 2 to 12 carbon atoms. Alternatively, D ² may have 2 to 10, or 3 to 5, or 3 carbon atoms. Each D ³ is a divalent alkylene group of 1 to 12 carbon atoms. Alternatively, each D ³ may be an alkylene group; or an ethylene group. ^{D 4} is an alkylene group of 2 to 4 carbon atoms or a divalent alkylene aryl group.

The divalent hydrocarbon group of ^D4 may be, for example, an alkylene group, such as an ethylene group, a propylene group, or a butylene group; an arylene group, such as a phenylene group, or an alkylarylene group, such as: or , wherein each subscript u is independently 1 to 6, or 1 to 2. Alternatively, the divalent hydrocarbon group may be an alkylene group, or the divalent hydrocarbon group may be an ethylene group. The divalent hydrocarbon groups of ^{D 2} and D ³ may be as described above, or may be methylene. The divalent hydrocarbon group of D may be an alkylene group, such as an ethylene group, a propylene group, or a butylene group. Alternatively, each D may be an ethylene group.

The (poly) epoxyalkylene group of D may have 2 to 4 carbon atoms per unit, for example having the formula ^D5 ( ^OD6 ) _v'- OR, wherein ^D5 is an alkylene group of 2 to 4 carbon atoms, ^D6 is 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) epoxyalkylene groups include ethylene oxide-propylene oxide.

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

In the above unit formula, each R ⁷ is independently selected from the group consisting of oxygen atoms and NH. Alternatively, each R ⁷ can be oxygen.

In the above unit formula, each R ⁸ is a crosslinkable group. Each R ⁸ can be independently selected from the group consisting of: hydroxyl, amino, epoxy, urea, and acetyloxy. Alternatively, each R ⁸ can be independently selected from the group consisting of hydroxyl and urea, or each R ⁸ can be a hydroxyl.

In the above unit formula, each R ⁹ is a monovalent alkyl group, which does not contain an aliphatic unsaturated group and can be a straight chain, a branched chain, or a ring (i.e., a monocyclic or polycyclic), or a combination thereof. ^{R 9} can be an alkyl group or an aryl group, which can be a monocyclic or polycyclic group, and optionally has a straight chain or a branched chain group. Examples of suitable alkyl groups for R ⁹ can include methyl, tert-pentyl, butyl (including tert-butyl), cyclohexyl, isodecyl, isoborneol, and 2-ethylhexyl. Examples of suitable aryl groups include phenyl, naphthyl, anthracenyl, and benzyl.

In the above unit formula, R ¹⁰ may be a halogen atom, an acetate, or a monovalent alkyl group, as described above for R ^9. The halogen atom may be bromine (Br), chlorine (Cl), fluorine (F), or iodine (I); or Br, Cl, or F; or Br or Cl; or Cl.

In the above unit formula, the subscripts w, x, y, and z are the relative weights of each unit, and the amount (w + x + y + z) can total 100. The value of subscript w is 80 to 98.75. Alternatively, subscript w can be at least 80, or at least 81, or at least 82, or at least 83, or at least 84, or at least 85. At the same time, subscript w can be at most 98.75, or at most 98, or at most 97, or at most 96, or at most 97, or at most 96, or at most 95, or at most 94, or at most 93, or at most 92, or at most 91, or at most 90. Alternatively, subscript w can be 80 to 98, or 81 to 97, or 82 to 96, or 82 to 95, or 85 to 90.

The value of subscript x is 0.25 to 15. Alternatively, subscript x is at least 0.25, or at least 0.5, or at least 0.75, or at least 1, or at least 2, or at least 3, or at least 4, or at least 5. Also, subscript x can be at most 15, or at most 14, or at most 13, or at most 12, or at most 11, or at most 10. Alternatively, subscript x can be 1 to 14, or 2 to 13, or 3 to 12, or 4 to 11, or 5 to 10, or 5 to 15; or 10.

The value of subscript y is 1 to 5. Alternatively, subscript y can be at least 1, or at least 1.25, or at least 1.5, or at least 2, or at least 1.75. Also, subscript y can be at most 5, or at most 4, or at most 3, or at most 2.75, or at most 2.5, or at most 2.25. Alternatively, subscript y can be 1 to 3, or 1 to 2, or 1.5 to 2.5, or 1.75 to 2.25, or 2.

Subscript z1 may be 0. Alternatively, subscript z1 may be at least 0.5, or at least 1, or at least 2; at the same time, subscript z1 may be at most 18.75, or at most 15, or at most 10, or at most 8, or at most 5. Alternatively, subscript z1 may be 0 to 18.75, or > 0 to 18.75, or 0.5 to 7, or 1 to 6, or 2 to 5.

Subscript z2 may be 0. Alternatively, subscript z2 may be at least 0.5, or at least 1, or at least 2; at the same time, subscript z2 may be at most 8, or at most 7, or at most 6, or at most 5, or at most 4. Alternatively, subscript z2 may be 0 to 8, or > 0 to 8, or 0.5 to 7, or 1 to 6, or 2 to 5.

The total number of units per copolymer molecule is not particularly limited. The units shown above may be in any order, for example, the copolymer may be a random copolymer or a block copolymer.

Those skilled in the art will recognize that copolymers can be prepared by free radical polymerization, via the procedure described below, and that this procedure will form the terminal moieties of the copolymers. The copolymers further comprise terminal moieties, which may be derived from initiators, chain transfer agents, or both, as described, for example, in Odian, George (2004). Principles of Polymerization (4th ed.). New York: Wiley-Interscience. ISBN 978-0-471-27400-1.

The copolymer can be prepared by a process comprising: 1) a copolymerization starting material comprising: 80 wt % to 98.75 wt % of a compound of formula (A) wherein R ¹ is an alkyl group of 16 to 24 carbon atoms as described above, and R ² is selected from the group consisting of H and methyl, as described above; 0.25 wt % to 15 wt % of formula (B) a polysilicone-(meth)acrylate macromer of , wherein each R ³ is a group of formula OSi(R ⁴ ) ₃ ; each R ⁴ is independently selected from the group consisting of R and DSi(R ⁵ ) 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)epoxyalkylene group of 1 to 12 units, and a divalent hydrocarbon group of 2 to 4 carbon atoms; each R ⁵ is independently selected from the group consisting of R and DSi(R ⁶ ) ₃ ; wherein each R ⁶ is independently selected from the group consisting of R and DSiR ₃ ; with the proviso that R ⁴ , R ⁵ , and R ⁶ are selected so that the macromer has at least 6 silicon atoms per molecule, as described above; 1 to 5 wt% of formula (C) a cross-linkable (meth)acrylate monomer, R ⁷ is independently selected from oxygen and NH, D ³ is a divalent hydrocarbon group of 1 to 12 carbon atoms, D ⁴ is a divalent group of 2 to 4 carbon atoms, subscript v is 0 to 12, and R ⁸ is a cross-linkable group, each as described above; (D) a surfactant; (E) water; (F) an initiator; (H) a chain transfer agent; (K) a manganese ion source; and (L) a phenolic compound; thereby forming an aqueous emulsion comprising (I) a polysilicone-(meth)acrylate copolymer, (D) a surfactant, (E) water, (K) a manganese ion source, and (L) a phenolic compound.

In step 1), the emulsion polymerization process may include forming an emulsion comprising starting materials (A), (B), (C), (D), (E), (K), and (L) (and optionally (H), and/or (J)), and thereafter adding (F) an initiator and performing copolymerization. Without wishing to be bound by theory, it is believed that during the process of combining and emulsifying (A), (B), (C), (D), (E), (H), and (J), the starting materials (K) and (L) may inhibit the formation of acrylic acid free radicals, the formation of which may affect the formation of the copolymer during the copolymerization in step 1).

The procedure for preparing an emulsion formulation suitable for preparing textile products may include practicing step 1) described above, thereby forming a first aqueous emulsion comprising a polysilicone-(meth)acrylate copolymer, a surfactant, water, a manganese ion source, and a phenolic compound; and 2) combining the first aqueous emulsion prepared in step 1), a second aqueous emulsion comprising (II) an additive (as introduced above and described in detail below), (III) a water-dispersible crosslinking agent (as introduced above and described in detail below), and optionally one or more additional starting materials.

Alternatively, one or more additional starting materials may be added in step 1) to produce the copolymer. For example, (J) an additional non-crystallizable monomer different from each of (A), (B), and (C) may be added in step 1).

Step 1) of the above procedure may comprise: forming an emulsion comprising starting materials (A), (B), (C), (D), (E), (F), (H), (K), and (L) (and optionally (J)). If starting material (A) is solid at room temperature, the starting materials may be heated to a temperature and for a time sufficient to melt starting material (A), for example 30°C to 50°C for 5 minutes to 15 minutes. The resulting starting materials may be mixed under shear to form an aqueous emulsion. Mixing under shear may be performed by any convenient means for forming aqueous emulsions, such as sonication and subsequent microfluidization. Apparatus for mixing under shear, such as ultrasonic generators, homogenizers, microfluidizers and high-speed mixers are known in the art and are commercially available. Without wishing to be bound by theory, it is believed that mixing under shear can be used to obtain submicron particle sizes in emulsions. In step 1), starting materials comprising (A), (B), (C), and (F) (and (H) and (J) when present) are copolymerized with starting materials (D), (E), (K), and (L) in an aqueous emulsion to form (I) a polysilicone-(meth)acrylate copolymer.

Step 2) of the above-mentioned procedure for making an emulsion formulation can be carried out by any convenient means, such as mixing in a jacketed container equipped with a stirrer. Step 1) and step 2) can be carried out sequentially in the same container. Alternatively, step 1) and step 2) can be carried out in different equipment. Step 1) and/or step 2) can be carried out at room temperature or at elevated temperature, for example, up to 100°C, or 40°C to 80°C. Alternatively, heating can be carried out in step 1) and step 2) can be carried out at room temperature. Alternatively, one or both of steps 1) and 2) can be carried out at low temperature and high pressure (e.g., up to 5 atmospheres).

Prior to step 1), the starting materials comprising (A), (B), (C), (H), (K), (L), and (when present) (J) may be combined under aerobic or anaerobic conditions, optionally by heating for a longer period of time. For example, the starting materials comprising (A), (B), (C), (H), (K), (L), and (when present) (J) may be emulsified with (D) and (E) prior to adding the initiator and copolymerization in step 1). In step 1), combining the starting materials and copolymerizing in the above-described procedure may be carried out on a commercial scale under anaerobic or aerobic conditions, optionally at elevated temperatures, for example up to 100°C, or 40°C to 80°C, or 45°C to 50°C. The copolymerization can be carried out in a batch process with a residence time of 15 minutes to 24 hours, or 30 minutes to 12 hours, or 40 minutes to 8 hours, or 40 minutes to 2 hours. For the purpose of this application, aerobic or anaerobic conditions mean that oxygen is not required to be present in the gas in the headspace of the reactor in which the copolymerization is carried out, or oxygen is not required to be dissolved in the liquid in which the copolymerization is carried out. The remainder of the gas in the headspace can be an inert gas, such as nitrogen or argon.

Alternatively, the composition comprising a copolymer, a manganese ion source, and a phenolic compound described above may be prepared by a method comprising dissolving one or more of the starting materials (such as (A), (B), (C), (H), (K), (L), and (when present) (J)) in an organic solvent (such as a monohydric alcohol) and copolymerizing the starting materials (A), (B), (C), (F), (H), and (when present) (J) in a procedure such as that disclosed in U.S. Patent No. 10,047,199 to Iimura et al. by varying the appropriate starting materials and their amounts. The resulting composition may be solvent-based. All or a portion of the solvent may be removed by any convenient means, such as by stripping or distillation under heating and, optionally, reduced pressure. The resulting composition comprising the copolymer, the manganese ion source, and the phenolic compound can be emulsified using (D) a surfactant and (E) water. The starting materials used to prepare the composition and the emulsion formulation comprising the composition are further described below.

The starting material (A) is a crystallizable monomer of formula (A-1): , wherein R ¹ and R ² are as described above. Examples of crystallizable monomers for the starting material (A) include stearyl (meth)acrylate, eicosyl (meth)acrylate, behenyl (meth)acrylate, and combinations thereof. Alternatively, when R ² is hydrogen, the starting material (A) may be an acrylate selected from stearyl acrylate, eicosyl acrylate, behenyl acrylate, and combinations thereof. Crystallizable monomers suitable for the starting material (A) are commercially available, for example, from Millipore Sigma in St. Louis, Missouri, USA and BASF SE in Ludwigshafen, Germany. Crystallizable means that the melting point of the starting monomer is ≥ 25°C ± 5°C.

Starting material (A) is used in an amount of 80% to 98.75% by weight of the combined weight of starting materials (A), (B), and (C), and (when present) (J). The amount of starting material (A) may be at least 80%, or at least 81%, or at least 82%, or at least 83%, or at least 84%, or at least 85%, on the same basis. At the same time, the amount of starting material (A) may be at most 98.75%, or at most 98%, or at most 97%, or at most 96%, or at most 97%, or at most 96%, or at most 95%, or at most 94%, or at most 93%, or at most 92%, or at most 91%, or at most 90%, on the same basis. Alternatively, the amount of starting material (A) may be 80% to 98%, or 81% to 97%, or 82% to 96%, or 82% to 95%, or 85% to 90%; on the same basis.

The starting material (B) is a polysilicone-(meth)acrylate macromer of formula (B-1): , wherein R ² , D ² , and R ³ are as described above.

Alternatively, the starting material (B) may comprise formula (B-2): , wherein R ² , R ⁴ , and R ⁵ are as described above.

Alternatively, the starting material (B) may comprise a macromonomer selected from the group consisting of: (Si10) 3-(5-((1,1,1,3,5,5,5-heptamethyltrisiloxane-3-yl)oxy)-1,1,1,3,7,9,9,9-octamethyl-3,7-bis((trimethylsilyl)oxy)pentasiloxane-5-yl)propyl methacrylate; having the formula 3-(1,5-bis(2-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxane-3-yl)ethyl)-3-(((2-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxane-3-yl)ethyl)dimethylsilyl)oxy)-1,1,5,5-tetramethyltrisiloxane-3-yl)propyl methacrylate (Si16); and combinations thereof. The starting material (B) can be prepared by known methods, such as those disclosed in PCT Publication WO2020/142388 and U.S. Patent No. 6,420,504.

Starting material (B) is used in an amount of 0.25% to 15% by weight of the combination of starting materials (A), (B), and (C), and (when present) (J). Alternatively, starting material (B) may be used in an amount of at least 0.25%, or at least 0.5%, or at least 0.75%, or at least 1%, or at least 2%, or at least 3%, or at least 4%, or at least 5% on the same basis. At the same time, starting material (B) may be present in an amount of up to 15%, or up to 14%, or up to 13%, or up to 12%, or up to 11%, or up to 10% on the same basis. Alternatively, the amount of starting material (A) may be 1% to 14%, or 2% to 13%, or 3% to 12%, or 4% to 11%, or 5% to 10%, or 5% to 15%; or 10%, on the same basis as above. Starting material (C) cross-linkable (meth)acrylate monomer

The starting material (C) is a crosslinkable (meth)acrylate monomer of formula (C-1): , wherein R ² , R ⁷ , D ³ , R ⁸ , and subscript v are as described above. Examples of suitable crosslinkable (meth)acrylates for the starting material (C) include (2-acetylacetoxy)ethyl methacrylate, hydroxybutyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxyethyl caprolactone (meth)acrylate, hydroxypropyl (meth)acrylate, ureido (meth)acrylate, glycidyl (meth)acrylate (GMA), poly(ethylene glycol) (meth)acrylate (PEGMA), and combinations thereof. The ureido (meth)acrylate monomer may have the following formula: , wherein R ¹¹ is an oxygen atom or an NH moiety. Examples of ureido monomers are known in the art and are disclosed, for example, in U.S. Patent No. 9,212,292 to Pressley et al. Other crosslinkable (meth)acrylate monomers are known in the art and are commercially available, for example, from BASF SE. Other crosslinkable (meth)acrylates are commercially available as Sipomer WAM1 and 2.

Starting material (C) is used in an amount of 1% to 5% by weight of the combination of starting materials (A), (B), and (C), and (when present) (J). The amount of starting material (C) may be at least 1%, or at least 1.25%, or at least 1.5%, or at least 2%, or at least 1.75%, on the same basis. At the same time, the amount of starting material (C) may be up to 5%, or up to 4%, or up to 3%, or up to 2.75%, or up to 2.5%, or up to 2.25%, on the same basis. Alternatively, the amount of starting material (C) may be 1% to 3%, or 1% to 2%, or 1.5% to 2.5%, or 1.75% to 2.25%, or 2%; on the same basis. Starting material (D) Surfactant

The starting material (D) is a surfactant. The surfactant can be selected from the group consisting of: (D-1) a cationic surfactant, (D-2) a nonionic surfactant, and (D-3) a combination of a cationic surfactant and a nonionic surfactant. The cationic surfactant that can be used herein includes compounds containing a quaternary ammonium hydrophilic portion with a positive charge in the molecule, such as a quaternary ammonium salt, which can be represented by the formula (D-1-1): R ¹² R ¹³ R ¹⁴ R ¹⁵ N ⁺ X' ^- , wherein R ¹² to R ¹⁵ are alkyl groups containing 1 to 30 carbon atoms, or alkyl groups derived from tallow, coconut oil, or soybeans; and X' is a halogen, for example, chlorine or bromine. Alternatively, the quaternary ammonium compound may be alkyl trimethyl ammonium and dialkyl dimethyl ammonium halides or acetates, having at least 8 carbon atoms in each alkyl substituent. Dialkyl dimethyl ammonium salts may be used and are represented by the formula (D-1-2): R ¹⁶ R ¹⁷ N ⁺ (CH ₃ ) ₂ X' ^- , wherein R ¹⁶ and R ¹⁷ are alkyl groups containing 12 to 30 carbon atoms, or alkyl groups derived from tallow, coconut oil, or soybeans; and X' is a halogen. Monoalkyl trimethyl ammonium salts may be used and are represented by the formula (D-1-3): R ¹⁸ N ⁺ (CH ₃ ) ₃ X" ^- , wherein R ¹⁸ is an alkyl group containing 12 to 30 carbon atoms, or alkyl groups derived from tallow, coconut oil, or soybeans; and X" is a halogen or acetate.

Representative halogenated quaternary ammonium salts are dodecyltrimethylammonium chloride/lauryltrimethylammonium chloride (LTAC), cetyltrimethylammonium chloride (CTAC), hexadecyltrimethylammonium chloride, behenyldimethylammonium bromide, hexacosyldimethylammonium chloride, hexacosyldimethylammonium bromide, octacosyldimethylammonium chloride, di-eicosyldimethylammonium chloride and di-docosyldimethylammonium chloride. These quaternary ammonium salts are commercially available under the trade names ADOGEN ^™ , ARQUAD ^™ , TOMAH ^™ and VARIQUAT ^™ .

Other suitable cationic surfactants that may be used include fatty acid amines and amides and their salts and derivatives, such as aliphatic fatty amines and their derivatives. Commercially available cationic surfactants of this type include compositions sold under the following names: ARQUAD ^™ T27 W, ARQUAD ^™ 16-29 from Akzo Nobel Chemicals Inc., Chicago, Illinois; and Ammonyx Cetac-30 from Stepan Company, Northfield, Illinois, USA.

The amount of (D-1) cationic surfactant may be 0.1% to 5% by weight of the starting material (I) polysilicone-(meth)acrylate copolymer in the aqueous emulsion. Alternatively, the amount of cationic surfactant may be at least 0.1%, or at least 0.2%, or at least 0.3%, or at least 0.4%, or at least 0.5%; at the same time, the amount of cationic surfactant may be up to 5%, or up to 4%, or up to 3%, or up to 2%, or up to 1%, which is calculated on the same basis. Alternatively, the amount of cationic surfactant may be 0.2% to 4%, or 0.3% to 3%, or 0.4% to 2.5%, or 0.5% to 2%, which is calculated on the same basis.

The starting material (D-2) is a non-ionic surfactant. Some suitable non-ionic surfactants that can be used include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, alkyl glucosides, polyoxyethylene fatty acid esters, sorbitan fatty acid esters, and polyoxyethylene sorbitan fatty acid esters. Commercially available nonionic surfactants include compositions such as (i) 2,6,8-trimethyl-4-nonyl polyoxyethylene ether sold under the names TERGITOL ^™ TMN-6 and TERGITOL ^™ TMN-10; (ii) C11-15 dialkyl polyoxyethylene ether 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 Dow Chemical Company of Midland, Michigan, USA; octylphenyl polyoxyethylene (40) ether sold under the name TRITON ^™ X405 by Dow Chemical Company; (iii) MAKON™ X406 sold under the name MAKON ^™ X407 by Stepan Company. (iv) ethoxylated alcohols sold under the name Trycol 5953 by Henkel Corp./Emery Group of Cincinnati, Ohio, USA; (v) ethoxylated alcohols sold under the name BRIJ ^™ L23 and BRIJ ^™ L4 by Croda Inc. of Edison, New Jersey, USA, (vi) alkyl-hydroxylated alcohol polyglycol ethers such as GENAPOL ^™ UD 050 and GENAPOL ^™ UD110, (vii) alkyl polyglycol ethers based on C10-Guerbet alcohol and ethylene oxide such as LUTENSOL ^™ XP 79.

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

Other suitable non-ionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenol ethers, polyoxyethylene lauryl ethers, polyoxyethylene sorbitan monooleate, polyoxyethylene alkyl esters, polyoxyethylene sorbitan alkyl esters, polyethylene glycols (such as polyethylene glycols having 23 ethylene oxide units), polypropylene glycol, diethylene glycol, ethoxylated trimethyl nonanol, and polyoxyalkylene glycol-modified polysiloxane surfactants. Commercially available nonionic surfactants that can be used include compositions such as 2,6,8-trimethyl-4-nonylpolyethyleneoxyethanol (6EO) and (10EO) sold under the trademarks TERGITOL ^™ TMN-6 and TERGITOL ^™ TMN-10; alkyleneoxypolyethyleneoxyethanol (C 11-15 diol ethoxylates 7EO, 9EO, and 15EO) sold under the trademarks TERGITOL ^™ 15-S-7, TERGITOL ^™ 15-S-9, TERGITOL ^™ 15-S-15; other C _11-15 diol ethoxylates sold under the trademarks TERGITOL ^™ 15-S-12, 15-S-20, 15-S-30, 15-S-40; and _2,6,8 -trimethyl-4-nonylpolyethyleneoxyethanol (6EO) and (10EO) sold under the trademarks TERGITOL™ TMN-6 and TERGITOL ^™ TMN-10. X-405; and alcohol ethoxylates with the trademark ECOSURF ^™ EH, such as ECOSURF ^™ EH-40. All of these surfactants are sold by The Dow Chemical Company.

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

The nonionic surfactant may also be a polysiloxane polyether (SPE). The polysiloxane polyether as an emulsifier may have a rake-type structure in which polyoxyethylene or polyoxyethylene-polyoxypropylene copolymer units are grafted onto a siloxane backbone, or the SPE may have an ABA block copolymer structure in which A represents a polyether portion of an ABA structure and B represents a siloxane portion. Suitable SPEs include DOWSIL ^™ OFX-5329 Fluid available from Dow Silicones Corporation of Midland, Michigan, USA. Alternatively, the nonionic surfactant may be selected from polyoxyalkylene-substituted polysiloxanes, polysiloxane amides, polysiloxane esters, and polysiloxane glycosides. Such silicone-based surfactants are useful in forming such aqueous emulsions and are known in the art and are described, for example, in U.S. Patents 4,122,029 to Gee et al., 5,387,417 to Rentsch, and 5,811,487 to Schulz et al.

The starting material (D-2) non-ionic surfactant may be delivered in the form of a diluent, and the amount of the diluent used may be sufficient to provide 0.1% to 6% of the surfactant based on the weight of the starting material (I) polysilicone-(meth)acrylate copolymer in the aqueous emulsion. Alternatively, the amount of the non-ionic surfactant may be at least 0.1%, or at least 0.2%, or at least 0.3%, or at least 0.4%, or at least 0.5%; at the same time, the amount of the non-ionic surfactant may be up to 5%, or up to 4%, or up to 3%, or up to 2%, or up to 1% on the same basis. Alternatively, the amount of the non-ionic surfactant may be 0.2% to 4%, or 0.3% to 3%, or 0.4% to 2.5%, or 0.5% to 2%; they are calculated on the same basis. Alternatively, the starting materials (D-1) cationic surfactant and (D-2) non-ionic surfactant may be present in a combined amount of ≤ 10% based on the weight of the starting material (I) polysilicone-(meth)acrylate copolymer in the aqueous emulsion. Starting material (E) water

Starting material (E) is water. Water is generally not limited, for example, water can be processed or unprocessed. Examples of procedures that can be used to purify water include distillation, filtration, deionization, and a combination of two or more thereof, so that water can be deionized, distilled, and/or filtered. Alternatively, water can be unprocessed (for example, tap water, i.e., provided by a municipal water system or well water, used without further purification). In step 1) of the above procedure, the amount of water is sufficient to form an aqueous emulsion for emulsion polymerization. Additional water can be added after step 1). For example, the first aqueous emulsion and/or the second aqueous emulsion prepared as described above can be diluted with additional water to obtain the desired amount of starting material before the textile is treated with the emulsion formulation. In step 1), water may be added in an amount of 20% to 97%, or 30% to 90%, or 40% to 80%, or 50% to 97%, or 50% to 90%, or 60% to 80%; based on the combined weight of all starting materials in step 1). Alternatively, water may be added in an amount of at least 20%, or at least 30%, or at least 40%, or at least 50%, or at least 60%; at the same time, the amount of water may be up to 97%, or up to 96%, or up to 95%, or up to 80%, which is calculated on the same basis.

Without wishing to be bound by theory, it is believed that starting materials (A), (B), and (C), and (when present) (J) copolymerize to form (I) a polysilicone-(meth)acrylate copolymer, which is described herein as starting material (I). It is further believed that starting materials (D) a surfactant and (E) water do not participate in the copolymerization reaction, however, copolymers including one or both of starting materials (D) and (E) are not excluded from the scope herein. Starting material (I) polysilicone-(meth)acrylate copolymer

The polysilicone-(meth)acrylate copolymer may be prepared by emulsion copolymerization of starting materials comprising (A), (B), (C), and (F) described above. Alternatively, the polysilicone-(meth)acrylate copolymer may be a reaction product of starting materials consisting essentially of starting materials (A), (B), (C), and (F) (and, when present, (H) a chain transfer agent and/or (J) an additional monomer). Alternatively, the polysilicone-(meth)acrylate copolymer may be a reaction product of starting materials consisting of starting materials (A), (B), (C), and (F) (and, when present, (H) and/or (J)). Without wishing to be bound by theory, it is believed that neither of the starting materials (D) and (E) copolymerizes with the starting materials (A), (B), and (C), but merely acts as a vehicle for the copolymerization. However, nothing herein should exclude the possibility that a portion of one or more of the starting materials (D) and/or (E), or any other starting materials added during the process, may participate in the copolymerization of the starting materials comprising (A), (B), (C), and (F).

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

Starting material (III) is a water-dispersible crosslinker (crosslinker) that can be added to an emulsion formulation for treating textiles, for example to promote the curing of (I) polysilicone-(meth)acrylate copolymer and (II) additive. Starting material (III) can be combined with the first aqueous emulsion prepared in step 1). Alternatively, starting material (III) can be combined with the second aqueous emulsion in step 2) of the procedure to prepare an emulsion formulation suitable for treating textiles. Alternatively, the first aqueous emulsion and the second aqueous emulsion can be combined to form a third aqueous emulsion, and thereafter (III) the water-dispersible crosslinker can be added thereto. Suitable water-dispersible crosslinkers include blocked isocyanates and diols. The term "blocked isocyanates" covers monoisocyanates, diisocyanates, and polyisocyanates in which the isocyanate groups have reacted with a blocking agent which releases the isocyanate and the blocking agent upon heating. Suitable blocking agents are known in the art, such as amines, amides, compounds with active hydrogen atoms, alcohols or oximes. Blocked isocyanates are commercially available, such as ARKOPHOB ^™ DAN and ARKOPHOB ^™ SR from Archroma in Reinach, Switzerland; RUCO-GUARD ^™ WEB from Rudolf GmbH in Geretsreid, Bayern, Germany, and PHOBOL ^™ UXN Extender and PHOBOL ^™ XAN Extender from Archroma. The diols include, for example, 1,2-propylene glycol; 1,3-propylene glycol; 1,2-butylene glycol; 1,3-butylene glycol; 1,4-butylene glycol; 2,3-butylene glycol; 2-methyl-1,2-propylene glycol; 1,5-pentanediol; 2-methyl-2,3-butylene glycol; 1,6-hexanediol; 1,2-hexanediol; 2,5-hexanediol; 2-methyl-2,4-pentanediol; 2,3-dimethyl-2,3-butylene glycol; 2-ethylhexanediol; 1,2-octanediol; 1,2-decanediol; 2,2,4-trimethylpentanediol; 2-butyl-2-ethyl-1,3-propylene glycol; and 2,2-diethyl-1,3-propylene glycol. Examples of suitable crosslinking agents are known in the art and disclosed in, for example, U.S. Patent Application 2017/0204558 to Knaup; U.S. Patent No. 9,777,105 to Hamajima et al., beginning at col. 11, line 54, which are hereby incorporated by reference herein to describe suitable crosslinking agents. The exact amount of crosslinking agent (III) depends on various factors, including the type and amount of (I) polysilicone-(meth)acrylate copolymer formed in step 1) and the textile to be treated, however, the weight of crosslinking agent (III) may be sufficient to provide 0.25% to 3.75% by weight on the fabric, or 0.25% to 1%, or 0.25% to 0.5% on the same basis. Alternatively, the amount of crosslinking agent may be 9.1% to 30% based on the combined weight of all starting materials in the emulsion formulation suitable for treating the textile, excluding water. Alternatively, the amount of (III) crosslinking agent may vary depending on factors such as the type of fabric to be treated. For example, when the textile to be treated is a polyester, the amount of (III) crosslinking agent may be 9.2% to 20.1%. Alternatively, when the textile to be treated is a polyamide, such as nylon, the amount of (III) crosslinking agent may be 9.1% to 30.7%. Starting Materials (H) Chain Transfer Agent

Additional starting materials that may be added in step 1) of the above procedure include (H) a chain transfer agent. Suitable chain transfer agents include mercaptans, such as alkyl mercaptans, for example n-octyl mercaptan, n-dodecyl mercaptan, dodecyl mercaptan (dodecyl mercaptan), and/or 2,2-dimethyldecyl mercaptan. Alternatively, the chain transfer agent may be water-soluble, such as hydroxyacetic acid and/or 2-hydroxyethanol. Suitable chain transfer agents are known in the art and are disclosed, for example, in "Radical Polymerization in Industry", Peter Nesvadba, Performance Chemical Research, GASF Schweiz AG, Basel, Switzerland, Encyclopedia of Radicals in Chemistry, Biology and Materials, Online © 2012 John Wiley & Sons, Ltd.

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

Also in the above step 1) is added starting material (F) initiator. Suitable initiators include azo compounds and peroxide compounds. For example, the azo compound may be an aliphatic azo compound, such as 1-tri-amyl azo-l-cyanocyclohexane, azo-bis-isobutyronitrile and 1-tri-butyl azo-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, for example, under the trade name VAZO ^™ WSP from The Chemours Company of Wilmington, Delaware, USA. The peroxide compound may be a peroxide or a hydroperoxide, such as tertiary butyl peroctoate, tertiary butyl perbenzoate, diisopropylbenzene peroxide, di-tertiary butyl hydroperoxide, tertiary butyl hydroperoxide, isopropylbenzene hydroperoxide, di-tertiary amyl hydroperoxide, and combinations of two or more thereof. In addition, a diperoxide initiator may be used alone or in combination with other initiators. Such diperoxide initiators include, but are not limited to, 1,4-bis-(tertiary butylperoxycarbon)cyclohexane, 1,2-di(tertiary butylperoxy)cyclohexane, and 2,5-di(tertiary butylperoxy)-3-hexyne. Suitable peroxide compounds are known in the art and are commercially available from various sources, such as Sigma-Aldrich, Inc. Alternatively, the starting agent may comprise isoascorbic acid.

The initiator can be used alone as the starting material (F). Alternatively, the starting material (F) can be a redox pair comprising an initiator as an oxidizing component and a reducing component. Alternatively, a redox pair comprising isoascorbic acid and a hydrophobic organic hydroperoxide (such as tertiary amyl hydroperoxide or tertiary butyl hydroperoxide) can be used as the starting material (F). Examples of suitable initiators and/or redox pairs for the starting material (F) are disclosed in U.S. Patent No. 6,576,051 to Bardman et al. (starting at col. 11, line 16). How to add the initiator 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 of the initiator is added at once at the start of step 1). Alternatively, when a redox couple is used, the initiator can be added in doses over time.

Alternatively, the initiator may further comprise iron (II) sulfate heptahydrate, potassium persulfate, or a combination thereof. The initiator (F) may be used in an amount sufficient to provide 0.01% to 3%, or 0.1% to 1.5%, based on the weight of the polysilicone-(meth)acrylate copolymer. Starting Material (J) Additional Monomer

Starting material (J) is an optional additional monomer that can be added in step 1). Starting material (J) is a non-crystallizable monomer different from starting materials (A), (B), and (C) described above. When present, the additional monomer can be used in an amount of > 0 to 18.75 wt % based on the weight of (I) polysilicone-(meth)acrylate copolymer. Suitable monomers include (meth)acrylate monomers, such as methyl methacrylate, triamyl methacrylate, butyl (meth)acrylate (such as tributyl methacrylate), cyclohexyl (meth)acrylate, isodecyl (meth)acrylate, isoborneol (meth)acrylate, 2-naphthyl acrylate, benzyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and combinations of two or more thereof. Alternatively, the additional monomer can be styrene or vinyl chloride. Suitable monomers for the starting material (J) are known in the art and are commercially available, for example, from Polysciences, Inc. Alternatively, the additional monomer (J) may be selected from the group consisting of isoborneol methacrylate (IBMA), isoborneol acrylate (IBA), and combinations thereof. The additional monomer is optionally present and may be present in an amount of 0 to 18.75% by weight of the combined weight of the starting materials (A), (B), and (C), and (when present) (J). Alternatively, the (J) additional monomer may be present in an amount of at least 0.5%, or at least 1%, or at least 2%; also, the additional monomer may be present in an amount of up to 18.75%, or up to 15%, or up to 10%, or up to 8%, or up to 5%, based on the same basis. Alternatively, (J) the amount of additional monomer may be > 0 to 18.75%, or 0.5% to 7%, or 1% to 6%, or 2% to 5%, based on the same basis. Starting Materials (K) Manganese Ion Source

The starting material (K) is a manganese ion source, which may be a manganese (II) compound. Suitable manganese compounds include manganese (II) acetate, manganese (II) nitrite, manganese (II) propionate, manganese (II) oxide, manganese (II) hydroxide, manganese (II) chloride, manganese (II) phosphate, manganese (II) perchlorate, hydrates thereof (e.g., manganese (II) tetrahydrate), and combinations thereof. Alternatively, the manganese ion source may include manganese (II) acetate, or manganese (II) tetrahydrate, or combinations thereof. Suitable manganese ion sources may be purchased 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 selection and amount of other starting materials used, however, the amount can be 0.1 ppm to 5,000 ppm based on the combined weight of starting materials (A), (B), and (C). Alternatively, the amount of manganese ion source can be >0 ppm, or at least 0.5 ppm, or at least 1 ppm, or at least 1.5; at the same time, the amount of manganese ion source can be up to 10 ppm, or up to 5 ppm, or up to 4 ppm, or up to 3 ppm, or up to 2 ppm, based on the combined weight of all starting materials in the emulsion formulation used to treat the textile. (L) Phenolic compounds

The starting material (L) is a phenolic compound. Suitable phenolic compounds include hydroquinone (HQ), dihydroxybenzene (catechol), resorcinol, dihydroxyxylene, methoxyphenols (such as guaiacol, p-methoxyphenol (also known as methyl ether of hydroquinone or MeHQ)), tertiary butyl hydroquinone (tBuHQ), gallol, methyl gallol, cresol, phenol, xylenol, and combinations thereof. Alternatively, the phenolic compound may be selected from the group consisting of HQ, MeHQ, tBuHQ, and combinations of two or more thereof. Suitable phenolic compounds are commercially available, for example, from Millipore Sigma in St. Louis, Missouri, USA. The amount of the phenolic compound source depends on various factors, including the selection and amount of other starting materials used, however, the amount can be 5 ppm to 5,000 ppm based on the combined weight of the starting materials (A), (B), and (C). Alternatively, the amount of the phenolic compound can be at least 5 ppm, or at least 50 ppm, or at least 100 ppm, or at least 150 ppm; at the same time, the amount of the phenolic compound can be up to 500 ppm, or up to 400 ppm, or up to 350 ppm, or up to 320 ppm, based on the combined weight of all starting materials in the emulsion formulation used to treat the textile.

Optionally, additional starting materials may be added after step 1) and/or after step 2) of the process to prepare an emulsion formulation suitable for treating textiles. The starting materials may be selected from the group consisting of: (VI) additional surfactants (as described above for starting material (D)), (VII) wax, (VIII) biocides, (IX) additional water (as described above for starting material (E)), (X) flame retardants, (XI) wrinkle reducers, (XII) antistatic agents, (XIII) penetrants, or a combination of two or more additional starting materials. Starting Material (VII) Wax

Starting material (VII) is a wax, which can be optionally added to provide improved water repellency or softness to the textile to which the emulsion formulation is to be applied. The amount of the wax will vary depending on factors including the type of wax selected, the desired benefit, and the fabric to be treated with the emulsion formulation. However, the amount of the wax can be 0 to 75%, or 0 to 50%, or 25% to 50%, based on the weight of the (I) polysilicone-(meth)acrylate copolymer. Alternatively, when used, the amount of the wax can be > 0%, or at least 10%, or at least 25%, and at the same time, the amount of the wax can be up to 75%, or up to 50%, on the same basis. Examples of suitable waxes include waxes (e.g., n-alkanes, isoalkanes, and/or cycloalkanes), polysiloxanes, such as polysiloxanes with long-chain alkyl groups (e.g., alkylmethyl polysiloxanes) and/or amino-polysiloxanes, and combinations of two or more thereof. Suitable waxes are disclosed, for example, in U.S. Patent Application No. 2017/0204558 to Knaup and U.S. Patent No. 10,844,151 to Probst et al. Waxes can be provided in the form of water-based dispersions, such as Michelman Wax 743 from Michelman of Cincinnati, Ohio, USA, and others. Other waxes are also commercially available, such as Sasol Wax from Hamburg, Germany, and silicone waxes such as DOWSIL ^™ AMS-C30, available from Dow Silicones Corporation in Midland, Michigan, USA. Starting Materials (VIII) Biocide

Starting material (VIII) is an optional biocide. The amount of biocide will vary depending on factors including the type of biocide selected and the desired benefit. However, when used, the amount of biocide may be > 0% to 5% based on the combined weight of all starting materials in the emulsion formulation. Starting material (VIII) is exemplified by (M-1) a fungicide, (M-2) a herbicide, (M-3) an insecticide, (M-4) an antimicrobial agent, or a combination thereof. Suitable biocides are disclosed, for example, in U.S. Patent 9,480,977. Starting material (XIII) penetrant

The starting material (XIII) is a penetrant. Suitable penetrants are exemplified by glycol ethers, which are commercially available from The Dow Chemical Company and include DOWANOL ^™ DPM, TPM, PPh, EPh, Methyl CARBITOL ^™ , and Butyl CARBITOL ^™ . (II) Additives

The emulsion formulation suitable for treating textiles further comprises (II) an additive in an amount sufficient to impart softness to the textile without significantly reducing water repellency, the additive being selected from: (II-1) an alkyl polysiloxane of 1 to 18 carbon atoms, wherein each R ¹⁹ is an independently selected monovalent saturated alkyl group having 1 to 18 carbon atoms, and the average value of subscript a is 20 to 300, or (II-2) a combination comprising: 60 to 70 wt % of (II-1) alkyl polysiloxane, based on the combined weight of all starting materials in the (II-2) combination; 29 to 39 wt % of (II-2-1) polysilicone having a hardness of ≥ 20 as measured by a type A durometer according to JIS K 6249:2003, based on the combined weight of all starting materials in the (II-2) combination; and 0 to 2 wt % of (II-2-2) amino-functional polyorganosiloxane having 100 to 20,000 carbon atoms, based on the combined weight of all starting materials in the (II-2) combination. g/mol, and has a kinematic viscosity of 10 to 100,000 ^mm2 /s at 25°C as measured by the method of JIS K 2283:2000, wherein the equivalent means the molecular weight of the amino-functional polyorganosiloxane per 1 mol of nitrogen atom. Alternatively, the (II-2-2) amino-functional polyorganosiloxane may be present in an amount of 1% to 2% on the same basis.

(II-1) Alkyl polysiloxane has the formula , wherein each R ¹⁹ is an independently selected monovalent saturated alkyl group having 1 to 18 carbon atoms, and the average value of subscript a is 20 to 300. The monovalent saturated alkyl group of ^{R 19} can be an alkyl group, or an alkyl group of 1 to 6 carbon atoms. Alternatively, the alkyl group can have 1 to 3 carbon atoms, or 1 to 2 carbon atoms. Alternatively, each R ¹⁹ can be a methyl group. Suitable alkyl polysiloxanes, such as bis-trimethylsiloxy terminated polydimethylsiloxanes are known in the art and are commercially available, for example, as XIAMETER ^™ 200 Fluids from DSC.

Alternatively, the (II) additive may include a (II-2) combination, which includes: 60 to 70 wt% of the above (II-1) alkyl polysiloxane, based on the combined weight of all starting materials in the (II-2) combination; 29 to 39 wt% of (II-2-1) polysilicone resin, based on the combined weight of all starting materials in the (II-2) combination, which has a hardness of ≥ 20 measured by a type A durometer according to JIS K 6249:2003; and 1 to 2 wt% of (II-2-2) amino-functional polyorganosiloxane, based on the combined weight of all starting materials in the (II-2) combination, which has a functional group equivalent of 100 to 20,000 g/mol and a surface area of 10 to 100,000 mm ² measured by the method of JIS K 2283:2000 at 25°C. /s kinematic viscosity, where equivalent means the molecular weight of amino-functional polyorganosiloxane per 1 mol of nitrogen atom.

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

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

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

The emulsion formulation suitable for treating textiles comprises: (I) a polysilicone-(meth)acrylate copolymer, (K) a manganese ion source, (L) a phenolic compound, (II) an additive, (III) a water-dispersible crosslinking agent, (IV) a surfactant (described above as starting material (D)), and (V) water (described above as starting material (E)). The emulsion formulation may optionally further comprise an additional starting material selected from the group consisting of: (VII) wax, (VIII) biocide, (IX) additional water, (X) flame retardant, (XI) wrinkle reducer, (XII) antistatic agent, (XIII) penetrant, and a combination of two or more of the starting materials (VII), (VIII), (IX), (X), (XI), (XII), and (XIII), which may be added during the preparation of the first aqueous emulsion comprising (I) polysilicone-(meth)acrylate copolymer, or thereafter during the preparation of the emulsion formulation. Such additional starting materials and their amounts are as described above. In addition, the emulsion formulation described herein may be formulated with starting materials that do not contain fluorocarbons. For example, the emulsion formulation may be free of any starting materials containing fluorine atoms covalently bonded to carbon atoms.

Additional starting materials may optionally be used in the procedures described above. For example, when making copolymers, chelating agents may be used. Procedures for treating textiles

The emulsion formulation prepared as described above can be used to treat textiles. For example, the method for treating textiles comprises: I) coating the textile with the emulsion formulation described above, and II) heating the textile. Step I) can be performed by any convenient method, such as filling, impregnating, or spraying the textile with the emulsion formulation. However, the method should be sufficient to deliver 0.25% to 7.5% by weight of the weight on the fabric of (I) polysilicone-(meth)acrylate copolymer; 0.01% to 0.5% by weight of the weight on the fabric of (II) additive; and 0.05% to 0.5% by weight of the weight on the fabric of (III) water-dispersible crosslinking agent, each based on the weight of the textile. When the (II) additive is the (II-2) combination, the amount of the (I) polysilicone-(meth)acrylate copolymer and the amount of the (II-2) combination are sufficient to provide a (I) : (II-2) weight ratio of 2:1 to <200:1.

Step II) can be carried out by any convenient method, such as placing the textile in an oven. The textile can be heated to remove all or part of the water and/or cure the emulsion formulation. The exact temperature depends on various factors, including the temperature sensitivity of the selected textile type and the desired drying time. However, heating can be carried out at a temperature of >100°C to remove water. Alternatively, the temperature can be >100°C to 200°C for a period of time sufficient to remove all or part of the water, de-block the blocked isocyanate crosslinking agent, and/or cure the (I) polysilicone-(meth)acrylate copolymer and (II) additive.

The textiles to be treated are not particularly limited. Suitable textiles include textiles of natural origin, such as cotton, silk, linen and/or wool; textiles from synthetic sources, such as rayon, acetate, polyester, polyamide (such as nylon), polyacrylonitrile, and polyolefins, such as polyethylene and/or polypropylene, and combinations of two or more thereof (such as blends, such as polyester/cotton blends). The form of the textile is also not particularly limited. The emulsion formulations described herein are suitable for use with any form of textile, such as woven, knitted, carpet, or non-woven textile. Persistent water repellency test:

The Bundesmann test can be performed using the ISO 9865 method. Surface grade data can be collected after 0, 1, 10, and 20 washes using the SDL Atlas M230 Bundesmann test equipment. The instrument can be calibrated so that after 150 seconds, the volume collected in each cup is between 190 and 210 mL. Surface grades can be assigned based on images from the ISO 9865 method using semi-increments as intermediate assignments. Surface ratings can be repeated and reported as averages. Pass values can be ≥ 4.5 to 5. Problem to be solved

Silicone-(meth)acrylate hybrid copolymers can impart excellent long-lasting water resistance to various textiles, however, they may have the disadvantage of reduced aesthetics due to hardness and poor hand feel. Known compositions for treating textiles, such as those disclosed in U.S. Patent Application Publication 2020/0332148, can impart sufficient aesthetics but lack long-lasting water repellency for some applications. In addition, there is a need to produce commercial-scale quantities of non-fluorocarbon textile treatments and keep monomer emulsions stable for longer processing times at higher temperatures while maintaining excellent performance properties. Solution

Without wishing to be bound by theory, it is believed that the present invention provides an emulsion formulation that, when used to treat textiles, imparts softness and hand as well as good durable water repellency as measured by the Bodman test described herein. More specifically, the fabric can have a Bodman surface rating of ≥ 4.5 after initial treatment and can maintain a surface rating of ≥ 4.5 after 1, 5, 10, and 20 washes. Without wishing to be bound by theory, it is believed that the use of a manganese ion source and a phenolic compound will result in better monomer emulsion stability and will impart improved post-polymerization emulsion formulation water repellency to the fabric (compared to a monomer emulsion that does not contain one or both of the manganese ion source and the phenolic compound). Definition and Use of Terms

Unless otherwise indicated, all amounts, ratios, and percentages herein are by weight. The invention content and the invention abstract are incorporated herein by reference. Unless the context of the specification indicates otherwise, the articles "a/an" and "the" each refer to one or more. The transitional phrases "comprising", "consisting essentially of", and "consisting of" are used as described in the Manual of Patent Examining Procedure, Ninth Edition, Revised Edition 08.2017, last revised in January 2018 in Sections §2111.03 I., II., and III. The use of "for example", " eg ", "such as", and "including" to list illustrative examples is not limited to the examples listed. Therefore, "for example" or "such as" means "for example, but not limited to" or "such as, but not limited to", and includes other similar or equivalent examples. Abbreviations used herein have the definitions in Table Z. Table Z - Abbreviations Abbreviation Definition ℃ Celsius DSC Dow Silicones Corporation of Midland, Michigan, USA ℉ Fahrenheit g Grams GPC Gel permeation chromatography was used to measure the molecular weight of the copolymers described in the above reference examples. HEMA Hydroxyethyl Methacrylate m meter (Meth)acrylate Includes acrylates, methacrylates, or compounds of both. min minute mL mL Mp Peak average molecular weight MW Molecular weight measured by GPC in grams per mole Oz/Lin Yd Ounces per Linear Yard ppm Per million psi Pounds per Square Inch PTFE Polytetrafluoroethylene RPM Revolutions per minute RT Room temperature 25℃±2℃ u microliter um Micrometer

The present invention has been described in an illustrative manner, and it should be understood that the terms used are intended to be in the nature of words of description rather than limitation. For any Markush group relied upon herein to describe a particular feature or aspect, different, special and/or unexpected results may be obtained from each member of the respective Markush group, independent of all other Markush members. Each member of the Markush group may be relied upon individually and/or in combination and provides sufficient support for specific embodiments that fall within the scope of the appended claims.

In addition, any range and sub-range relied upon to describe the present invention are independent and collectively fall within the scope of the accompanying patent application, and are understood to describe and contemplate all ranges including the entire and/or partial values thereof, even if these values are not explicitly written in the specification. Those skilled in the art will readily recognize that the listed ranges and sub-ranges fully describe and enable various embodiments of the present invention, and such ranges and sub-ranges may be further described as the relevant half, third, fourth, fifth, and any other sub-ranges included within the range. As just one example, the range of "16 to 24" can be further divided into the lower third, i.e., 16 to 18; the middle third, i.e., 19 to 21, and the upper third, i.e., 22 to 24, or the range "16 to 24" includes the sub-range "18 to 22", each of which is individually and collectively within the scope of the attached patent application, and can be individually and/or collectively relied upon and provide sufficient support for specific embodiments within the scope of the attached patent application. In addition, for language that defines or modifies a range, such as "at least", "greater than", "less than", "no more than" and similar language, it should be understood that such language includes sub-ranges and/or upper or lower limits.

without

without

Claims (15)

An emulsion formulation suitable for treating textiles, wherein the emulsion formulation comprises: (I) a polysilicone-(meth)acrylate copolymer comprising the following unit formula: wherein each R ¹ is an independently selected alkyl group of 16 to 24 carbon atoms; each R ² is independently selected from the group consisting of H and methyl; each D ² is a divalent hydrocarbon group of 2 to 12 carbon atoms; each R ³ is a group of formula OSi(R ⁴ ) ₃ ; wherein each R ⁴ is independently selected from the group consisting of R and DSi(R ⁵ ) ₃ ; wherein each R is an independently selected monovalent hydrocarbon group of 1 to 12 carbon atoms, and each D is independently selected from the group consisting of oxygen atoms, (poly) epoxyalkyl groups of 1 to 12 units, and divalent hydrocarbon groups of 2 to 4 carbon atoms; each R ⁵ is independently selected from the group consisting of R and DSi(R ⁶ ) ₃ ; wherein each R ⁶ is independently selected from R and DSiR ₃ ; with the restriction that R ⁴ , R ⁵ , and R ⁶ are selected so that the polysilicone-(meth)acrylate macromer unit with subscript x has at least 6 silicon atoms; each R ⁷ is independently selected from the group consisting of oxygen atoms and NH; D ³ is a divalent hydrocarbon group of 1 to 12 carbon atoms; D ⁴ is an alkylene group or a divalent alkylene arylene group of 2 to 4 carbon atoms; subscript v represents the number of units of formula (OD ⁴ ), and the value of subscript v is 0 to 12; each R ⁸ is a crosslinkable group; each R ⁹ is a monovalent hydrocarbon group of 1 to 14 carbon atoms; each R ¹⁰ is independently selected from the group consisting of halogen, acetate group, or monovalent hydrocarbon group of 1 to 14 carbon atoms; subscripts w, x, y, z1, and z2 represent the relative weight of each unit in the copolymer, the value of subscript x is 0.25 to 15; the value of subscript w is 80 to 98.75; the value of subscript y is 1 to 5; the value of subscript z1 is 0 to 18.75; and the value of subscript z2 is 0 to 18.75, and the number (w + x + y + z1 + z2) = 100; and the proviso that the copolymer further comprises a terminal portion; (K) a manganese ion source; (L) a phenolic compound; (II) an additive selected from the group consisting of: (II-1) an alkyl polysiloxane of (II-1), wherein each R ¹⁹ is an independently selected monovalent saturated alkyl group having 1 to 18 carbon atoms, and the average value of subscript a is 20 to 300, or (II-2) a combination comprising, based on the combined weight of all starting materials in the combination (II-2), 60 to 70 wt % of the alkyl polysiloxane of (II-1), 29 to 39 wt % of a polysilicone resin (II-2-1) having a hardness of ≥ 20 as measured by a type A durometer according to JIS K 6249:2003, and 0 to 2 wt % of an amino-functional polyorganosiloxane (II-2-2) having 100 to 20,000 carbon atoms, based on the combined weight of all starting materials in the combination (II-2). g/mol, and having a kinematic viscosity at 25°C of 10 to 100,000 ^mm2 /s as measured by the method of JIS K 2283:2000, wherein the equivalent weight means the molecular weight of the amino-functional polyorganosiloxane per 1 mol of nitrogen atom; (III) a water-dispersible crosslinking agent in an amount sufficient to crosslink the starting materials (I) and (II); (IV) a surfactant; and (V) water. The emulsion formulation of claim 1, wherein R ¹ is stearyl, subscript w=95, D ² is -(CH ₂ ) ₃ -, each R ³ is -OSi(CH ₃ ) ₂ (CH ₂ ) ₂ Si(OSi(CH ₃ ) ₃ ), subscript x=3, R ⁷ is O, subscript v=0, R ⁸ is OH, subscript y=2, subscript z1=0, and subscript z2=0. The emulsion formulation of claim 1 or claim 2 further comprises one or more additional starting materials selected from the group consisting of: (VI) additional surfactant, (VII) wax, (VIII) biocide, (IX) flame retardant, (X) wrinkle reducer, (XI) antistatic agent, and (XII) penetrant. In the emulsion formulation of claim 3, (II) the additive is (II-2), and the emulsion formulation further comprises (XII) the penetrant. The emulsion formulation of any one of claims 1 to 4, wherein (III) the water-dispersible crosslinking agent comprises a blocked isocyanate. An emulsion formulation as claimed in any one of claims 1 to 5, wherein (I) the polysilicone-(meth)acrylate copolymer is present in an amount sufficient to provide 0.25 to 7.5% by weight on the fabric; (II) the additive is present in an amount sufficient to provide 0.01 to 0.5% by weight on the fabric; and (III) the water-dispersible crosslinking agent is present in an amount sufficient to provide 0.05 to 0.5% by weight on the fabric, with the proviso that when the additive is the combination of (II-2), the amount of (I) the polysilicone-(meth)acrylate copolymer and the amount of (II-2) the combination are sufficient to provide a weight ratio of (I): (II-2) of 2:1 to <200:1. The emulsion formulation of any one of claims 1 to 6, wherein the manganese ion source comprises manganese (II) acetate, manganese (II) acetate tetrahydrate, or a combination thereof. The emulsion formulation of any one of claims 1 to 7, wherein the phenolic compound is selected from the group consisting of hydroquinone, monomethyl ether of hydroquinone, tertiary butyl hydroquinone, and a combination of two or more thereof. A process for preparing an emulsion formulation as claimed in any one of claims 1 to 8, the process comprising: 1) preparing a starting material (I) the polysilicone-(meth)acrylate copolymer by emulsion polymerization of starting materials, wherein the starting materials comprise: 80 wt % to 98.75 wt % of (A) 0.25 ^wt % to 15 wt % ^of the formula (B) wherein R ² , D ² , and R ³ are as described above; 1 wt % to 5 wt % of formula (C) a crosslinkable (meth)acrylate monomer, wherein R ⁷ , D ³ , D ⁴ , subscript v, and R ⁸ are as described above; wherein the total amount of the starting materials (A), (B), and (C) is 100% by weight based on the combined amount of the starting materials (A), (B), and (C); and the starting materials (A), (B), and (C) are copolymerized in the presence of additional starting materials, wherein the additional starting materials include: a chain transfer agent; an additional monomer that is optionally different from the starting materials (A), (B), and (C); and a manganese ion source, and a phenolic compound; (D) a surfactant; (E) water; and (F) an initiator; thereby forming a first aqueous emulsion comprising (I) the polysilicone-(meth)acrylate copolymer; 2) Providing a second aqueous emulsion comprising (II) the additive, (D') a surfactant, and (E') water; and 3) mixing materials comprising the first aqueous emulsion prepared in step 1), the second aqueous emulsion from step 2), (III) the water-dispersible crosslinking agent, and optionally one or more additional starting materials selected from the group consisting of an additional surfactant, wax, a biocide, additional water, a flame retardant, a wrinkle reducer, an antistatic agent, and a penetrant. The process of claim 9, wherein the starting material (A) is selected from the group consisting of stearyl acrylate, stearyl methacrylate, behenyl methacrylate, and behenyl acrylate. The process of claim 9 or claim 10, wherein the starting material (B) has the formula . A process as claimed in any one of claims 9 to 11, wherein the starting material (B) is selected from the group consisting of: 3-(5-((1,1,1,3,5,5,5-heptamethyltrisiloxane-3-yl)oxy)-1,1,1,3,7,9,9,9-octamethyl-3,7-bis((trimethylsilyl)oxy)pentasiloxane-5-yl)propyl methacrylate; Methacrylate 3-(1,5-bis(2-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxane-3-yl)ethyl)-3-(((2-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxane-3-yl)ethyl)dimethylsilyl)oxy)-1,1,5,5-tetramethyltrisiloxane-3-yl)propyl ester; and combinations thereof. The process of any one of claims 9 to 12, wherein in the starting material (C), each R ⁸ is independently selected from the group consisting of a hydroxyl group, an amine group, an epoxide group, a urea group, and an acetyloxy group. A process as in any one of claims 9 to 14, wherein the starting material (D) and the starting material (D') are each independently selected from the group consisting of: a cationic surfactant, a non-ionic surfactant, and a combination thereof. A process for treating a textile, the process comprising: I)     coating the textile with an emulsion formulation as in any one of claims 1 to 6 or an emulsion formulation prepared by the process of any one of claims 9 to 14; and II)    heating the textile.