Silicone-(methyl) acrylate copolymer emulsion, preparation thereof and application of emulsion to endowing textiles with oil repellency

Abstract

The invention discloses a textile treatment emulsion preparation containing a silicone-(methyl) acrylate copolymer, a surfactant, water and blocked isocyanate and a preparation method of the textile treatment emulsion preparation. The textile treatment emulsion can be used in a process that includes coating the emulsion formulation on a textile and heating the textile to dry the emulsion formulation. According to the method, the textile has oil repellency.

Description

[0001] Cross-references to related applications This application claims priority to U.S. Provisional Patent Application No. 63 / 593716, filed October 27, 2023, and U.S. Provisional Patent Application No. 63 / 674322, filed July 23, 2024, pursuant to 35 USC §119(e). U.S. Provisional Patent Application Nos. 63 / 593716 and 63 / 674322 are incorporated herein by reference. Technical Field

[0002] An emulsion formulation suitable for treating textiles, a method for preparing the same, and its use are provided. More specifically, the emulsion formulation comprises a silicone-(meth)acrylate copolymer. This emulsion formulation can be used to treat textiles to impart durable oil repellency. Background Technology

[0003] For years, fluorinated materials have dominated the market for waterproof and oil-repellent textile coatings. However, regulatory and customer pressures are driving the industry to require textile treatments based on non-fluorocarbon compounds. Summary of the Invention

[0004] Silicone-(meth)acrylate copolymers contain the following unit formulas: , where each R 1 It is an independently chosen monovalent hydrocarbon group consisting of 1 to 12 carbon atoms; each D 2 It is an independently chosen divalent hydrocarbon group with 2 to 12 carbon atoms, and each R 2 Independently selected from the group consisting of H and methyl groups; each R 3 It is the formula OSi(R) 4 )3 groups; wherein each R 4 Independently select R and DSi(R) 5 The group consists of 3 groups, 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)oxyolefin group of 1 to 12 units, and a divalent hydrocarbon group of 2 to 4 carbon atoms; each R 5 Independently select R and DSi(R) 6 A group consisting of 3 groups; where each R 6 Independently select the group consisting of R and DSiR3; the condition is that R is selected. 4 R 5 and R 6The silicone-(meth)acrylate copolymer macromonomer unit with subscript b2 has at least 5 silicon atoms; the subscripts a, b1, and b2 represent the weight fractions of the units in the copolymer, and the values of the subscripts a, b1, and b2 are such that 0.25 < a ≤ 1 and 0 ≤ (b1 + b2) < 0.75. The emulsion formulation suitable for treating textiles contains a silicone-(meth)acrylate copolymer, a surfactant, water, and a blocked isocyanate. Also provided are methods for preparing and using the silicone-(meth)acrylate copolymer and the emulsion formulation. Detailed Description

[0005] Those skilled in the art will recognize that the silicone-(meth)acrylate copolymer (copolymer) introduced above can be prepared by free radical polymerization via the method described below, and this method will form the end portions of the copolymer. The copolymer having the above unit formula also contains end portions that can be derived from an initiator, a chain transfer agent, or both, as described, for example, in Odian, George (2004). Principles of Polymerization ( Principles of Polymerization ), 4th Edition. New York: Wiley-Interscience. ISBN 978-0-471-27400-1.

[0006] The copolymer can be prepared via a method including the following: 1) Copolymerize starting materials that include (A) a silicone-(meth)acrylate macromonomer of the formula where each R 1 is an independently selected monovalent hydrocarbon group of 1 to 12 carbon atoms; D 2 is a divalent hydrocarbon group of 2 to 12 carbon atoms; and R 2 is selected from the group consisting of H and methyl; (B) optionally, a silicone-(meth)acrylate copolymer macromonomer, where (B) the silicone-(meth)acrylate copolymer macromonomer has a formula selected from the group consisting of formula (B-1), formula (B-2), and the combination of both formula (B-1) and formula (B-2), where formula (B-1) is where each R 1 is an independently selected monovalent hydrocarbon group of 1 to 12 carbon atoms; D 2 is a divalent hydrocarbon group of 2 to 12 carbon atoms; and R 2 is selected from the group consisting of H and methyl; formula (B-2) is where R 2 is selected from the group consisting of H and methyl; D 2It is a divalent hydrocarbon group with 2 to 12 carbon atoms, and each R 3 It is the formula OSi(R) 4 )3 groups; wherein each R 4 Independently select R and DSi(R) 5 The group consists of 3 groups, 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)oxyolefin group of 1 to 12 units, and a divalent hydrocarbon group of 2 to 4 carbon atoms; each R 5 Independently select R and DSi(R) 6 A group consisting of 3 groups; where each R 6 Independently select the group consisting of R and DSiR3; the condition is that R is selected. 4 R 5 and R 6 This ensures that each molecule of the silicone-(meth)acrylate copolymer macromonomer of formula (B-2) has at least 5 silicon atoms; The starting material (A) is present in an amount >25% to 100% by weight, based on the combined weight of starting materials (A) and (B); and the starting material (B) is present in an amount from 0% to <75% by weight, based on the combined weight of starting materials (A) and (B); and the starting materials (A) and (B) are copolymerized in the presence of an additional starting material, wherein the additional starting material comprises an initiator (C). The additional starting material used in step 1) may optionally also comprise one or more of the following: (H) a chain transfer agent; (I) a manganese ion source; (J) a phenolic compound; and a chelating agent.

[0007] Step 1) of the method may include an emulsion polymerization reaction. Additional starting materials also include (D) a surfactant and (E) water. In step 1), the emulsion polymerization may include forming an emulsion, followed by the addition of (C) an initiator and copolymerization, the emulsion comprising starting materials (A) a silicone-(meth)acrylate macromonomer, (B) a silicone-(meth)acrylate comonomer (if present), (D) a surfactant, (E) water, and optionally one or more of (H) a chain transfer agent, (I) a manganese ion source, and (J) a phenolic compound. Without being bound by theory, it is believed that during the processing of combining and emulsifying (A) silicone-(meth)acrylate macromonomers, (B) silicone-(meth)acrylate copolymer macromonomers, (D) surfactants and (E) water and (when present) (H) chain transfer agents, the starting materials (I) manganese ion source and / or (J) phenolic compounds can inhibit the formation of acrylic acid radicals, which can affect the formation of copolymers during copolymerization in step 1).

[0008] Step 1) of the above method may include forming an emulsion comprising starting materials (A) a silicone-(meth)acrylate macromonomer, (B) a silicone-(meth)acrylate comonomer, (C) an initiator, (D) a surfactant, and (E) water, and optional additional starting materials selected from the group consisting of: (H) a chain transfer agent, (I) a manganese ion source, (J) phenolic compounds, and combinations of two or more thereof. These starting materials may be mixed under shear to form an aqueous emulsion. Shear mixing can be performed by any convenient means for forming an aqueous emulsion, such as ultrasonication and subsequent microfluidization. Equipment for shear mixing (such as ultrasonicators, homogenizers, microfluidizers, and high-speed mixers) is known in the art and commercially available. It is not intended to be theoretically construed that shear mixing can be used to obtain submicron particle sizes in emulsions. In step 1), a starting material comprising (A) a silicone-(meth)acrylate macromonomer, (B) a silicone-(meth)acrylate copolymer macromonomer, (C) an initiator (and (when present) (H) a chain transfer agent) is copolymerized with a starting material (D) a surfactant and (E) water, and optionally (I) a manganese ion source and (J) a phenolic compound to form (F) a silicone-(meth)acrylate copolymer in an aqueous emulsion.

[0009] The method described herein may optionally include one or more additional steps. For example, prior to step 1), a starting material comprising (A) a silicone-(meth)acrylate macromonomer and (B) a silicone-(meth)acrylate copolymer macromonomer and (when present) (H) a chain transfer agent may be combined under aerobic or anaerobic conditions, optionally with prolonged heating. For example, prior to the addition of (C) the initiator and copolymerization in step 1), a starting material comprising one or more of (A) a silicone-(meth)acrylate macromonomer and (B) a silicone-(meth)acrylate copolymer macromonomer and (when present) (H) a chain transfer agent, (I) a manganese ion source and / or (J) a phenolic compound may be emulsified with (D) a surfactant and (E) water. In step 1), the combination of the starting material and copolymerization in the above method may be carried out on a commercial scale under anaerobic or aerobic conditions, optionally at elevated temperatures (e.g., up to 100°C, alternatively 40°C to 80°C, and alternatively 45°C to 50°C). Copolymerization can be carried out in a batch process, with residence times ranging from 15 minutes to 24 hours, alternatively from 30 minutes to 12 hours, alternatively from 40 minutes to 8 hours, and alternatively from 40 minutes to 2 hours. For the purposes of this application, aerobic or anaerobic conditions mean that oxygen is not required to be present in the gas at the headspace of the reactor where copolymerization occurs, or dissolved in the liquid where copolymerization occurs. The remaining gas in the headspace can be an inert gas, such as nitrogen or argon.

[0010] Alternatively, the copolymer described above can be prepared by a method comprising dissolving one or more of the following starting materials in an organic solvent (such as a monohydric alcohol): such as (A) a silicone-(meth)acrylate macromonomer, (B) a silicone-(meth)acrylate comonomer, and optionally one or more of (H) a chain transfer agent, (I) a manganese ion source, and (J) a phenolic compound; and in a method such as that disclosed in U.S. Patent 10,047,199 to Iimura et al., by varying the appropriate starting materials and their amounts, copolymerizing the starting materials (A) the silicone-(meth)acrylate macromonomer and (B) the silicone-(meth)acrylate comonomer, and (H) a chain transfer agent (if present). The resulting copolymer may be solvent-based. All or part of the solvent may be removed by any convenient means, such as by stripping or heated distillation and optionally by reduced pressure. The resulting copolymer may be emulsified using (D) a surfactant and (E) water.

[0011] Regardless of the method used to manufacture the copolymer, such as via emulsion polymerization or by emulsifying a solvent-based copolymer (after solvent removal), the product prepared in step 1) is an aqueous emulsion comprising (F) a silicone-(meth)acrylate copolymer, (D) a surfactant, and (E) water. This aqueous emulsion may optionally also comprise (I) a manganese ion source and / or (J) a phenolic compound. This aqueous emulsion can be used to prepare emulsion formulations suitable for treating textiles. A method for preparing an emulsion formulation suitable for treating textiles includes performing step 1) as described above to prepare the aqueous emulsion, and 2) combining the aqueous emulsion prepared in step 1) with an additional starting material comprising (G) a blocked isocyanate. Step 2) may optionally also include the addition of additional starting materials, which may be selected from the group consisting of: (K) biocides, (L) additional water (which may be the same as starting material (E)), (M) flame retardants, (N) wrinkle reducers, (O) antistatic agents, (P) penetrants, (Q) additives (such as softeners), and combinations of two or more of these. Step 2) of the method may optionally also include the addition of additional (D) surfactants.

[0012] Step 2) of the above-described method for manufacturing emulsion formulations can be carried out in any convenient manner, such as mixing using a jacketed container equipped with a stirrer. Steps 1) and 2) and any optional and / or additional steps as described above can be carried out sequentially in the same container. Alternatively, steps 1) and 2) can be carried out in different devices. Step 2) can be carried out at RT or at elevated temperatures (e.g., up to 100°C, alternatively 40°C to 80°C). Alternatively, heating can be carried out in step 1), and step 2) can be carried out at RT. Alternatively, step 2) can be carried out at lower temperatures and elevated pressures (e.g., up to 5 atmospheres). The starting materials used in the above-described methods are further described below.

[0013] The starting material (A) used in this paper is a silicone-(meth)acrylate macromonomer. The silicone-(meth)acrylate macromonomer has the formula (A-1): , where each R 1 It is a monovalent hydrocarbon group consisting of 1 to 12 independently selected carbon atoms; D 2 It is a divalent hydrocarbon group with 2 to 12 carbon atoms; and R 2 Choose the group consisting of H and methyl groups.

[0014] In equation (A-1), each R 1 It is a monovalent hydrocarbon group consisting of 1 to 12 independently selected carbon atoms. R 1 The monovalent hydrocarbon group can be an alkyl group, such as an alkyl group with 1 to 6 carbon atoms. Alternatively, the alkyl group may have 1 to 3 carbon atoms, or alternatively 1 to 2 carbon atoms. Alternatively, each R 1 The group can be methyl.

[0015] In equation (A-1), D 2 It is a divalent hydrocarbon group with 2 to 12 carbon atoms. Alternatively, D 2 It may have 2 to 10, alternatively 3 to 5, and alternatively 3 carbon atoms. D 2 Examples of divalent hydrocarbon groups can be alkylene groups (such as ethylene, propylene, or butylene). Alternatively, D 2 The divalent hydrocarbon group can be propylene. Alternatively, D 2 It can be a linear chain, such as -(CH2)2- or -(CH2)3-. Alternatively, D 2 It can be -(CH2)3-. Alternatively, when D 2 When -(CH2)3- is included, the starting material (A) includes formula (A-2): , where R 1 As stated above.

[0016] Starting material (A) may comprise 3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxane-3-yl)propyl methacrylate of the following formula: (3MT-ALMA). The starting material (A) can be prepared by known methods, such as those disclosed in PCT Publication WO2020142388 and U.S. Patent 6420504.

[0017] Starting material (B) is optionally a silicone-(meth)acrylate comonomer (copolymer macromonomer) copolymerizable with the silicone-(meth)acrylate macromonomer described above (A). The starting material (B) copolymer macromonomer may comprise formula (B-1), wherein formula (B-1) is... , where each R 1 It is a monovalent hydrocarbon group consisting of 1 to 12 independently selected carbon atoms; D 2 It is a divalent hydrocarbon group with 2 to 12 carbon atoms; and R 2 Choose from the group consisting of H and methyl groups, each as described and exemplified above with respect to formula (A-1). Alternatively, when D 2 When -(CH2)3- is included, equation (B-1) may include: , where R 1 and R 2 As described above. Alternatively, formula (B-2) may comprise 3-(1,1,1,3,5,5,5-heptamethyltrisiloxane-3-yl)propyl methacrylate of the following formula: (MDM-ALMA).

[0018] Alternatively, in addition to or instead of formula (B-1) shown above, the starting material (B) comonomer may comprise a silicone-(meth)acrylate comonomer of formula (B-2): D 2 It is a divalent hydrocarbon group with 2 to 12 carbon atoms; and R 2 The groups consisting of H and methyl groups are selected, each as described above for formula (A-1). In formula (B-2), each R 3 It is the formula OSi(R) 4 )3 groups; each R 4 Independently select R and DSi(R) 5 The group consists of 3 groups, where each R is an independently selected monovalent hydrocarbon group of 1 to 12 carbon atoms; each D is independently selected from a group consisting of an oxygen atom, a (poly)oxyolefin group of 1 to 12 units, and a divalent hydrocarbon group of 2 to 4 carbon atoms; each R 5 Independently select R and DSi(R) 6 A group consisting of 3 R groups, where each R 6Independently select the group consisting of R and DSiR3; the condition is that R is selected. 4 R 5 and R 6 This results in each molecule of the copolymer macromonomer of formula (B-2) having at least 6 silicon atoms; alternatively, R is selected. 4 R 5 and R 6 Each molecule of 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.

[0019] In formula (B-2), each R is a monovalent hydrocarbon group with 1 to 12 carbon atoms. The monovalent hydrocarbon group of R can be an alkyl group, such as an alkyl group with 1 to 6 carbon atoms. Alternatively, the alkyl group can have 1 to 3 carbon atoms, or alternatively 1 to 2 carbon atoms. Alternatively, each R group can be a methyl group.

[0020] In formula (B-2), each D is independently selected from the group consisting of an oxygen atom, a (poly)oxyolefin group of 1 to 12 units, and a divalent hydrocarbon group of 2 to 4 carbon atoms; Examples of divalent hydrocarbon groups in D can be alkylene groups (such as ethylene, propylene, or butylene). Aromatic groups include phenylene, or alkylarylene groups include: or Each subscript u is independently 1 to 6, or alternatively 1 to 2. Alternatively, the divalent hydrocarbon group of D may be alkylene, and alternatively, the divalent hydrocarbon group of D may be ethylene.

[0021] Each unit of the (poly)oxyolefin group of D can have 2 to 4 carbon atoms, for example, having the formula D 5 (OD 6 ) v' -OR, where D 5 It is an alkylene group with 2 to 4 carbon atoms, D 6 It is an alkylene group with 2 to 4 carbon atoms, R as described above, and subscript v' from 0 to 12. Alternatively, subscript v' can be 0 or 1. Alternatively, subscript v' can be 0. Examples of (poly)oxyalkylene groups include ethylene oxide and propylene oxide.

[0022] Alternatively, each D may be selected from an oxygen atom and a divalent hydrocarbon group. Alternatively, each divalent hydrocarbon group of D may be an alkylene group, such as ethylene. Alternatively, each D may be oxygen. Alternatively, in the same unit, some instances of D may be oxygen, and other instances of D may be alkylene, such as ethylene.

[0023] Alternatively, equation (B-2) may include equation (B-2-1): , where R 2 R 4 and R 5 As stated above.

[0024] Alternatively, equation (B-2) may include equation (B-2-2): , where R 2 D and R are as described above.

[0025] Alternatively, equation (B-2) may include equation (B-2-3): , where R 2 D and R are as described above.

[0026] Alternatively, formula (B-2) may contain copolymer macromonomers selected from the group consisting of: The following formula is 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: (Si10); The following formula is 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. Copolymer macromonomers of formula (B-2) as described and illustrated above can be prepared by known methods, such as those disclosed in PCT Publication WO2020142388 and U.S. Patent 6420504.

[0027] When manufacturing copolymers, starting material (A) silicone-(meth)acrylate macromonomer and starting material (B) silicone-(meth)acrylate comonomer are used in the following amounts: based on the combined weight of starting materials (A) and (B), starting material (A) is used in an amount of >25% to 100% by weight; and based on the combined weight of starting materials (A) and (B), starting material (B) is used in an amount of 0% to <75% by weight. Alternatively, based on the combined weight of starting materials (A) and (B), starting material (A) may be used in an amount of >25%, alternatively at least 40%, alternatively at least 50%, alternatively at least 63%, and alternatively at least 75%; while the amount of starting material (A) may be up to 100%, alternatively up to 99%. On the same basis, alternatively up to 95%, alternatively up to 75%, alternatively up to 63%, alternatively up to 50%, and alternatively up to 40%. 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 on the same basis, the amount of starting material (B) may be >0%, alternatively at least 1%, alternatively at most 5%, alternatively at most 10%, alternatively at most 15%, alternatively at most 20%, and alternatively at least 25%; while the amount of starting material (B) may be at most 60%, alternatively at most 50%, alternatively at most 37%, and alternatively at most 25%. The starting material used to manufacture the copolymer may optionally be free of crosslinkable groups; for example, the starting material for copolymerization 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 material used in step 1) may be free of crosslinkable (meth)acrylate monomers, such as organic (meth)acrylate monomers having crosslinkable groups, such as ethyl methacrylate (2-acetylacetoxy)methacrylate, hydroxybutyl methacrylate, hydroxyethyl methacrylate, hydroxyethylcaprolactone (meth)acrylate, hydroxypropyl methacrylate, urea methacrylate, glycidyl methacrylate (GMA), and poly(alkylene glycol) (meth)acrylate macromonomers, such as poly(ethylene glycol) mono(meth)acrylate (PEGMA) and poly(ethylene glycol) di(meth)acrylate. The starting material used in step 1) may be free of organic silyl monomers having crosslinkable groups, such as alkenyltrialkoxysilanes (e.g., 3-(trimethoxysilyl)propyl methacrylate, vinyltriethoxysilane, and vinyltrimethoxysilane). Alternatively, the starting material for the co-polymerization in step 1) may consist essentially of starting materials (A), (B), and (C) and (when present) (H).

[0028] Starting material (A) and (if present) starting material (B) are copolymerized in the presence of an additional starting material. The additional starting material includes (C) an initiator. Alternatively, the starting material copolymerized in step 1) may consist of starting material (A) a macromonomer, (B) a copolymer macromonomer, and (C) an initiator, and (if present) (H) a chain transfer agent. Alternatively, the starting material used in step 1) may consist substantially of or may consist of: (A) a macromonomer, (B) a copolymer macromonomer, (C) an initiator, (D) a surfactant, and (E) water, and (if present) (H) a chain transfer agent, (I) a manganese ion source, and (J) a phenolic compound, and these starting materials are further described below.

[0029] In step 1) above, the starting material (C) initiator is also added. Suitable initiators include azo compounds and peroxide compounds. For example, the azo compound can be an aliphatic azo compound, such as 1-tert-pentylazo-1-cyanocyclohexane, azo-bis-isobutyronitrile and 1-tert-butylazo-cyanocyclohexane, 2,2'-azo-bis-(2-methyl)butyronitrile, 2,2'-azobis(2-methylpropionitrile), 2,2'-azobis(2-methylpropanediamine) dihydrochloride, 2,2'-azobis(cyanopentanoic acid), or combinations of two or more thereof. Azo compounds are known in the art and are available from Chemours Company, Wilmington, Delaware, USA, for example, under the trademark VAZO. ™ WSP is commercially available. The peroxide compound can be a peroxide or hydroperoxide, such as tert-butyl peroctanoate, tert-butyl perbenzoate, dicumyl peroxide, di-tert-butyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, di-tert-pentyl peroxide, and combinations of two or more of these. Alternatively, the dieperoxide initiator can be used alone or in combination with other initiators. Such dieperoxide initiators include, but are not limited to, 1,4-bis-(tert-butylperoxycarbonyl)cyclohexane, 1,2-bis(tert-butylperoxy)cyclohexane, and 2,5-bis(tert-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 initiator may contain isoascorbic acid.

[0030] The initiator may be used alone as the starting material (C). Alternatively, the starting material (C) may be a redox pair comprising the initiator as an oxidizing component and a reducing component. Alternatively, a redox pair comprising isoascorbic acid and an organic hydroperoxide (such as tert-amyl hydroperoxide or tert-butyl hydroperoxide) may be used as the starting material (C). Examples of suitable initiators and / or redox pairs for the starting material (C) are disclosed in U.S. Patent 6,576,051 to Bardman et al. (starting from column 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 over time.

[0031] Alternatively, the initiator may optionally also comprise ferric(II) heptahydrate, potassium persulfate, or a combination thereof. Based on the weight of the silicone-(meth)acrylate copolymer, the initiator (C) may be used in an amount sufficient to provide 0.01% to 3%, or alternatively 0.1% to 1.5%.

[0032] The starting material (D) is a surfactant. The surfactant can be selected from the group consisting of (D-1) cationic surfactants, (D-2) nonionic surfactants, and (D-3) combinations of both cationic and nonionic surfactants. Cationic surfactants that can be used in this paper include compounds containing a positively charged quaternary ammonium hydrophilic moiety in their molecules, such as quaternary ammonium salts represented by formula (D-1-1): R 12 R 13 R 14 R 15 N + X' - , where R 12 To R 15 It is an alkyl group containing 1 to 30 carbon atoms, or an alkyl group derived from tallow, coconut oil, or soybean; and X' is a halogen, such as chlorine or bromine. Alternatively, the quaternary ammonium compound can be an alkyltrimethylammonium and dialkyldimethylammonium halide or acetate having at least 8 carbon atoms in each alkyl substituent. Dialkyldimethylammonium salts can be used, represented by formula (D-1-2): R 16 R 17 N + (CH3)2X' - , where R 16 and R 17 It is an alkyl group containing 12 to 30 carbon atoms, or an alkyl group derived from tallow, coconut oil, or soybean; and X' is a halogen. A monoalkyltrimethylammonium salt, represented by formula (D-1-3), can be used: R18 N + (CH3)3X'' - , where R 18 It is an alkyl group containing 12 to 30 carbon atoms, or an alkyl group derived from tallow, coconut oil or soybean; and X'' is a halogen or an acetate.

[0033] Representative quaternary ammonium halide salts are dodecyltrimethylammonium chloride / lauryltrimethylammonium chloride (LTAC), hexadecyltrimethylammonium chloride (CTAC), hexadecyltrimethylammonium chloride, didodecyldimethylammonium bromide, dihexadecyldimethylammonium chloride, dihexadecyldimethylammonium bromide, dioctadecyldimethylammonium chloride, dieicoyldimethylammonium chloride, and didocosyldimethylammonium chloride. These quaternary ammonium salts can be branded as ADOGEN. ™ ARQUAD ™ TOMAH ™ and VARIQUAT ™ Acquired through commercial purchase.

[0034] Other suitable cationic surfactants that can be used include fatty acid amines and amides, as well as their salts and derivatives, such as aliphatic fatty amines and their derivatives. Commercially available cationic surfactants of this type include compositions produced by Akzo Nobel Chemicals Inc., Chicago, Illinois under the name ARQUAD. ™ T27 W, ARQUAD ™ 16-29 for sale; and sold by Stepan Company, Northfield, Illinois, USA, for Ammonyx Cetac-30.

[0035] Based on the weight of the starting material (F) silicone-(meth)acrylate copolymer in the aqueous emulsion, the amount of (D-1) cationic surfactant may be from 0.1% to 5%. Alternatively, on the same basis, the amount of cationic surfactant may be at least 0.1%, alternatively at least 0.2%, alternatively at least 0.3%, alternatively at least 0.4%, alternatively at least 0.5%; while the amount of cationic surfactant may be at most 5%, alternatively at most 4%, alternatively at most 3%, alternatively at most 2%, alternatively at most 1%. Alternatively, on the same basis, the amount of cationic surfactant may be from 0.2% to 4%, alternatively 0.3% to 3%, alternatively 0.4% to 2.5%, and alternatively 0.5% to 2%.

[0036] The starting material (D-2) is a nonionic surfactant. Some suitable nonionic surfactants that can be used include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, alkyl glucosides, polyoxyethylene fatty acid esters, sorbitol fatty acid esters, and polyoxyethylene sorbitol fatty acid esters. Commercially available nonionic surfactants include compositions such as those listed below: (i) those under the name TERGITOL ™ TMN-6 and TERGITOL ™ (ii) 2,6,8-trimethyl-4-nonyl polyoxyethylene ether sold by TMN-10; and (ii) TERGITOL manufactured by Dow Chemical Company, Midland, Michigan, USA. ™ 15-S-7, TERGITOL ™ 15-S-9, TERGITOL ™ 15-S-15, TERGITOL ™ 15-S-30 and TERGITOL ™ C11-15 secondary alkyl polyoxyethylene ether sold under the name TRITON by Dow Chemical Company, 15-S-40. ™ (iii) Octylphenyl polyoxyethylene (40) ether sold by X405; and (iii) MAKON by Stepan Company. ™ 10. Nonylphenyl polyoxyethylene (10) ether sold; (iv) Ethoxylated alcohol sold by Henkel Corp. / Emery Group, Cincinnati, Ohio, USA under the name Trycol 5953; (v) Croda Inc., Edison, New Jersey, USA under the name BRIJ ™ L23 and BRIJ ™ L4 sells ethoxylated alcohols; (vi) alkyl-oxo alcohol polyethylene glycol ethers, such as GENAPOL. ™ UD 050 and GENAPOL ™ UD110; (vii) Alkyl polyethylene glycol ethers based on C10 Guerbert alcohol and ethylene oxides such as LUTENSOLS ™ XP 79.

[0037] Suitable nonionic 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. Poloxamers are nonionic triblock copolymers composed of a central hydrophobic poly(propylene oxide) chain and two flanking hydrophilic poly(ethylene oxide) chains. Poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) triblock copolymers are commercially available from BASF, Florham Park, New Jersey, USA, under the trademark PLURONIC. ™ Such as PLURONIC ™ L61, L62, L64, L81, and P84 are for sale.

[0038] Other suitable nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenol ethers, polyoxyethylene lauryl ethers, polyoxyethylene sorbitan monooleate, polyoxyethylene alkyl esters, polyoxyethylene sorbitan alkyl esters, polyethylene glycol (such as polyethylene glycol having 23 ethylene oxide units), polypropylene glycol, diethylene glycol, ethoxylated trimethylnonanol, and polyoxyethylene glycol-modified polysiloxane surfactants. Commercially available nonionic surfactants that can be used include compositions such as those marketed under the trademark TERGITOL. ™ TMN-6 and TERGITOL ™ TMN-10 is sold as 2,6,8-trimethyl-4-nonyloxyethylene glycol (6EO) and (10EO); under the trademark TERGITOL ™ 15-S-7, TERGITOL ™ 15-S-9, TERGITOL ™ 15-S-15 sells alkylene oxide polyvinyl alcohol (C 11-15 Secondary alcohol ethoxylates 7EO, 9EO and 15EO); under the trademark TERGITOL ™ Other C products sold under 15-S-12, 15-S-20, 15-S-30, and 15-S-40 11-15 Secondary alcohol ethoxylates; under the trademark TRITON ™ Octylphenoxy polyethoxyethanol (40EO) sold under the trademark X-405; and ECOSURF. ™ EH such as ECOSURF ™ EH-40 is an alcohol ethoxylated product. All of these surfactants are sold by Dow Chemical Company.

[0039] Other useful commercial nonionic surfactants are produced by Stepan Corporation under the trademark MAKON.™ 10. Nonylphenoxy polyethoxyethanol (10EO) for sale; polyoxyethylene 23 lauryl ether (Laureth-23), commercially sold by Sigma Aldrich, Inc. of St. Louis, Missouri, USA; and RENEX. ™ 30, a polyoxyethylene ether alcohol available from Fisher Scientific.

[0040] Nonionic surfactants can also be silicone polyethers (SPEs). Silicone polyethers, as emulsifiers, can have a rake-like structure, in which polyoxyethylene or polyoxyethylene-polyoxypropylene copolymer units are grafted onto the siloxane backbone, or the SPE can have an ABA block copolymer structure, where A represents the polyether moiety and B represents the ABA-structured siloxane moiety. Suitable SPEs include DOWSIL from Dow Silicones Corporation, Midland, Michigan, USA. ™ OFX-5329 fluid. Alternatively, the nonionic surfactant may be selected from polyoxyethylene-substituted silicones, silicone alkanolamides, silicone esters, and silicone glycosides. Such silicone-based surfactants can be used to form such aqueous emulsions and are known in the art, and have been described, for example, in U.S. Patent 4,122,029 to Gee et al., U.S. Patent 5,387,417 to Rentsch, and U.S. Patent 5,811,487 to Schulz et al.

[0041] The starting material (D-2) nonionic surfactant can be delivered in the diluent, and the amount used is sufficient to provide 0.1% to 10% surfactant based on the weight of the starting material (F) silicone-(meth)acrylate copolymer in the aqueous emulsion. Alternatively, on the same basis, 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 the amount of nonionic surfactant may be at most 10%, alternatively at most 9%, alternatively at most 8%, alternatively at most 7%, alternatively at most 5%, alternatively at most 4%, alternatively at most 3%, alternatively at most 2%, alternatively at most 1%. Alternatively, on the same basis, 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%. Alternatively, based on the weight of the starting material (F) silicone-(meth)acrylate copolymer in the aqueous emulsion, the starting materials (D-1) cationic surfactant and (D-2) nonionic surfactant may be present in a combined amount of ≤10%.

[0042] The starting material (E) is water. Water is generally not limited; for example, it can be treated or untreated. Examples of processes that can be used to purify water include distillation, filtration, deionization, and combinations of two or more of these, such that the water can be deionized, distilled, and / or filtered. Alternatively, the water can be untreated (e.g., tap water, i.e., supplied by a municipal water supply 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 described above. Additional water may be added after step 1). For example, the aqueous emulsion prepared as described above may be diluted with additional water to obtain the desired amount of starting material before treating textiles with the emulsion formulation. Based on the combined weight of all the starting materials in step 1), water may be added in amounts of 20% to 97%, alternatively 30% to 90%, alternatively 40% to 80%, alternatively 50% to 97%, alternatively 50% to 90%, and alternatively 60% to 80%. Alternatively, on the same basis, water may be added in amounts of at least 20%, at least 30%, at least 40%, at least 50%, and at least 60%; while the amount of water may be at most 97%, at most 96%, at most 95%, and at most 80%.

[0043] The silicone-(meth)acrylate copolymer (F) can be prepared by emulsion polymerization of a starting material comprising the macromonomer (A) and initiator (C) as described above (and optionally comonomer (B)). Alternatively, the silicone-(meth)acrylate copolymer is a reaction product of a starting material consisting essentially of the macromonomer (A) and initiator (C) (and, when present, comonomer (B) and / or chain transfer agent). Alternatively, the silicone-(meth)acrylate copolymer is a reaction product of a starting material consisting of starting materials (A) and (C) (and, when present, (B) and / or (H)). Without being bound by theory, it is assumed that the starting material (D) surfactant and (E) water do not copolymerize with the starting materials (A) and (C) (and, when present, (B) and / or (H)), but that the starting materials (D) and (E) merely act as mediators for copolymerization. However, the possibility that one or more of the starting materials (D) and / or (E) or any other starting material added during the method may participate in the copolymerization of the starting materials including (A) and (C) and any optional starting materials (i.e. (B) and / or (H)) (if present) should not be excluded in this document.

[0044] Silicone-(meth)acrylate copolymers contain the unit formula (F-1): , where each R 1 It is an independently chosen monovalent hydrocarbon group consisting of 1 to 12 carbon atoms; each D 2 Independently, it is a divalent hydrocarbon group with 2 to 12 carbon atoms; and each R 2 Independently selected from the group consisting of H and methyl groups; each R 3 It is the formula OSi(R) 4 )3 groups; wherein each R 4 Independently select R and DSi(R) 5 The group consists of 3 groups, 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)oxyolefin group of 1 to 12 units, and a divalent hydrocarbon group of 2 to 4 carbon atoms; each R 5 Independently select R and DSi(R) 6 A group consisting of 3 groups; where each R 6 Independently select the group consisting of R and DSiR3; the condition is that R is selected. 4 R 5 and R 6The silicone-(meth)acrylate copolymer macromonomer unit having the subscript b2 has at least 5 silicon atoms; the subscripts a, b1, and b2 represent the weight fractions of the units in the copolymer, and the values of the subscripts a, b1, and b2 are such that 0.25 < a ≤ 1 and 0 ≤ (b1 + b2) < 0.75; and the silicone-(meth)acrylate copolymer further comprises a terminal portion. In the unit formula (F-1), R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R, D and D 2 are as described and illustrated above for formulas (A-1), (B-1) and (B-2). Alternatively, in the unit formula (F-1) of the silicone-(meth)acrylate copolymer, each R 1 may be methyl, each R 2 may be methyl, each D 2 may be propylene, each R 3 may be a group of the formula OSi(R 4 )3; wherein each R 4 is independently selected from the group consisting of R and OSi(R 5 )3, wherein each R is methyl; each R 5 is independently selected from the group consisting of R and OSi(R 6 )3; wherein each R 6 is independently selected from the group consisting of R and OSiR3; provided that R 4 , R 5 and R 6 are selected such that the silicone-(meth)acrylate copolymer macromonomer has 10 to 16 silicon atoms per molecule. Alternatively, the subscript a may have a value such that 0.50 ≤ a ≤ 1, alternatively 0.63 ≤ a ≤ 1, alternatively 0.75 ≤ a ≤ 1, and alternatively a = 1. Alternatively, the subscript b1 may have a value such that 0 ≤ b1 < 0.75, alternatively 0 ≤ b1 ≤ 0.5, alternatively 0 ≤ b1 < 0.25, and alternatively b1 = 0. Alternatively, the subscript b2 may have a value such that 0 ≤ b2 < 0.75, alternatively 0.01 ≤ b2 ≤ 0.5, alternatively 0.05 ≤ b1 < 0.25, and alternatively b1 = 0.25.

[0045] The silicone-(meth)acrylate copolymer prepared as described above may have a weight-average molecular weight of >181,000 g / mol as measured by GPC. Alternatively, the weight-average molecular weight of the silicone-(meth)acrylate copolymer as measured by GPC may be 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 the weight-average molecular weight may be at most 2,000,000 g / mol. Alternatively, up to 1,000,000 g / mol; alternatively up to 950,000 g / mol; alternatively up to 925,000 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 silicone-(meth)acrylate copolymer has a weight-average molecular weight of 212,000 g / mol to 912,000 g / mol as measured by GPC. Samples for GPC analysis are prepared in THF eluent at a concentration of 10 mg / mL copolymer. The solution can be shaken on a plate shaker at ambient temperature for 2 hours. The solution was then filtered through a 0.45m PTFE syringe filter before injection. Samples were analyzed using a Waters e2695 LC pump and autosampler equipped with two 5µM Agilent PLG gel mixing C-columns in series and a Shodex RI501 differential refractive index detector. The instrument was equilibrated at 1 mL / min for 30 minutes, and samples were run at 1 mL / min. Data collection and reduction were performed using Agilent GPC software Cirrus version 3.3. Molecular weight calibration was performed using a total of 16 linear narrow molecular weight polystyrene standards from Agilent Technologies, ranging from 3750 kg / mol to 0.58 kg / mol. Calibration curve fitting was performed using a third-order polynomial. Therefore, all molecular weight averages, distributions, and molecular weight references provided in this report are polystyrene equivalents.

[0046] The starting material (G) is a blocked isocyanate, which is added to an emulsion formulation suitable for treating textiles. The term "blocked isocyanate" encompasses monoisocyanates, diisocyanates, and polyisocyanates in which the isocyanate groups have reacted with a blocking agent, releasing the isocyanate and blocking agent upon heating. Suitable blocking agents are known in the art, such as amines, amides, compounds having active hydrogen atoms, alcohols, or oximes. Blocked isocyanates are commercially available, such as ARKOPHOB from Archroma of Pratteln, Switzerland. ™ DAN and ARKOPHOB ™ SRR; RUCO, from Rudolf GmbH of Geretsreid, Bayern, Germany. ™ -GUARD WEB and RUCO ™ -LINK XCR, and PHOBOL from Angco ™ EXTENDER XAN. Alternatively, the blocked isocyanate can be an oxime-blocked isocyanate, such as PHOBOL. ™ EXTENDER XAN. Alternatively, the blocked isocyanate may comprise a nitrogen-containing heterocyclic (N-heterocyclic) blocked isocyanate. The N-heterocyclic blocked isocyanate comprises an isocyanate compound and an N-heterocyclic blocking agent. The isocyanate compound may be monomeric or polymeric. The isocyanate compound may comprise or may be selected from IPDI, H... 12 Units comprising the group consisting of MDI, TMXDI, TMI, XDI, H6XDI, MDI, and HDI. Alternatively, the polyisocyanate may be an aliphatic isocyanate in which the NCO group is not directly attached to an aromatic ring. Alternatively, the polyisocyanate may be HDI or MDI. The N-heterocyclic blocking agent may be 2,6-dimethylpyrazine or dimethylpyrazole, such as 3,5-dimethylpyrazole. It is not desired to be theoretically constrained that blocked isocyanates may be free of substances that could interfere with the performance of isocyanates in emulsion formulations, such as silicones and amines (which are not within the blocking group). Furthermore, it is not desired to be theoretically constrained that blocked isocyanates may be delivered in emulsions or dispersions free of anionic surfactants. Suitable aqueous additives are commercially available and can be delivered in aqueous dispersions, and examples of such additives are shown in Table 0 below.

[0047] Table 0 - Commercially Available Aqueous Additives The exact amount of (G) blocked isocyanate compound depends on various factors, including the (F) silicone-(meth)acrylate copolymer formed in step 1) and the type and amount of textiles to be treated; however, on the same basis, the weight of (G) blocked isocyanate may be sufficient to provide 0.25% to 3.75% by fabric weight, alternatively 0.25% to 1% and alternatively 0.25% to 0.5%.

[0048] Additional starting materials that may be added in step 1) of the above method include (H) chain transfer agents. Suitable chain transfer agents include thiols, such as alkyl thiols, for example n-octyl thiol, n-dodecyl thiol, dodecyl thiol (dodecane thiol), and / or 2,2-dimethyldecyl thiol. 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 Peter Nesvadba's "Radical Polymerization in Industry," *Performance Chemical Research*, GASF Schweiz AG, Basel, Switzerland, and *Encyclopedia of Radicals in Chemistry, Biology and Materials*, Online. © 2012 John Wiley & Sons, Ltd.

[0049] The starting material (H) is optional and can be added in an amount of 0% to 1% based on the combined weight of the starting material (A) and (if present) the starting material (B). Alternatively, on the same basis, the chain transfer agent (H) can be used in an amount of 0.5% to 0.6%.

[0050] The starting material (I) is optionally 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, their hydrates (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 combinations thereof. Suitable manganese ion sources are commercially available from Millipore Sigma of St. Louis, Missouri, USA; Feischel Technologies, Waltham, Massachusetts, USA; and City Chemical LLC, Connecticut, USA. The amount of manganese ion source depends on various factors, including the selection and amount of other starting materials used; however, based on the combined weight of starting material (A) and (if present) starting material (B), the amount can be from 0.1 ppm to 5,000 ppm. Alternatively, based on the combined weight of all starting materials in the emulsion formulation used to treat textiles, the amount of manganese ion source can be >0 ppm, alternatively at least 0.5 ppm, alternatively at least 1 ppm, alternatively at least 1.5 ppm; while the amount of manganese ion source can be up to 10 ppm, alternatively up to 5 ppm, alternatively up to 4 ppm, alternatively up to 3 ppm, and alternatively up to 2 ppm.

[0051] The starting material (J) is optionally a phenolic compound. Suitable phenolic compounds include hydroquinone (HQ), 2-methylhydroquinone, 2-tert-butylhydroquinone, dihydroxybenzene (catechol), 4-di-tert-butyldihydroxybenzene (4-di-tert-butylcatechol), resorcinol, dihydroxyxylene, methoxyphenol (such as guaiacol, p-methoxyphenol (also known as the methyl ether of hydroquinone or MeHQ)), tert-butylhydroquinone (tBuHQ), pyrogallol, methylpyrogallol, cresol, phenol, xylenol, butylhydroxytoluene, N-nitrosophenylhydroxylamine, butylhydroxyanisole, and combinations thereof. Alternatively, the phenolic compound may be selected from the group consisting of HQ, MeHQ, tBuHQ, and combinations of two or more of them. Suitable phenolic compounds are commercially available, for example, from Millibor Sigma, Inc., St. Louis, Missouri, USA. The amount of phenolic compound source depends on various factors, including the selection and amount of other starting materials used; however, based on the combined weight of starting material (A) and (if present) starting material (B), the amount can be from 5 ppm to 5,000 ppm. Alternatively, based on the combined weight of all starting materials in the emulsion formulation used to treat textiles, the amount of phenolic compound can be at least 5 ppm, alternatively at least 50 ppm, alternatively at least 100 ppm, alternatively at least 150 ppm; while the amount of phenolic compound can be at most 500 ppm, alternatively at most 400 ppm, alternatively at most 350 ppm, and alternatively at most 320 ppm.

[0052] Alternatively, in addition to or in place of the manganese ion source (I) and the phenolic compound (J) described above, another inhibitor may be used. For example, the inhibitor may contain or may be nitrobenzene; 2,2-diphenyl-1-picrylhydrazyl (DPPH); phenothiazine; N,N-diethylhydroxylamine; (2,2,6,6-tetramethylpiperidin-1-yl)oxoalkyl (TEMPO); 4-hydroxy-(2,2,6,6-tetramethylpiperidin-1-yl)oxoalkyl (4-hydroxyTEMPO); or a combination of two or more of these.

[0053] The starting material (K) is an optional biocide. The amount of biocide will depend on factors including the type of biocide selected and the desired beneficial effect. However, based on the combined weight of all starting materials in the emulsion formulation, the amount of biocide may be >0% to 5% when used. Examples of starting materials (K) include (K-1) fungicides, (K-2) herbicides, (K-3) insecticides, (K-4) antimicrobials, or combinations thereof. Suitable biocides are disclosed, for example, in U.S. Patent 9,480,977.

[0054] Emulsion formulations suitable for treating textiles may optionally also include a starting material (P) penetrant. Examples of suitable penetrants include glycol ethers, commercially available from Dow Chemical Company, and include DOWANOL. ™ DPM, TPM, PPh, EPh, Methyl CARBITOL ™ and Butyl CARBITOL ™ .

[0055] Emulsion formulations suitable for treating textiles may optionally further comprise an amount of (Q) softening additive sufficient to impart softness to the textiles without significantly reducing their water and / or oil repellency, the softening additive being selected from alkyl polysiloxanes of formula (Q-1): , where each R 19 It is an independently selected monovalent saturated hydrocarbon group having 1 to 18 carbon atoms, and the subscript aa has an average value of 20 to 300; or a combination (Q-2) comprising 60% to 70% by weight of (Q-1) alkyl polysiloxane based on the combined weight of all starting materials in the (Q-2) combination, 29% to 39% by weight of (Q-2-1) silicone resin based on the combined weight of all starting materials in the (Q-2) combination, and 0% to 2% by weight of (Q-2-2) amino-functionalized polysiloxane based on the combined weight of all starting materials in the (Q-2) combination, wherein the silicone resin has a hardness of ≥20 as measured by a type A hardness tester according to JIS K 6249:2003, and the amino-functionalized polysiloxane has a functional group equivalent of 100 g / mol to 20,000 g / mol, wherein the equivalent means the molecular weight of the amino-functionalized polysiloxane per mole of nitrogen atoms, and has a functional group equivalent as measured by a type A hardness tester according to JIS K 6249:2003. The measurement using method 2283:2000 at 25℃ is 10mm. 2 / s to 100,000mm 2 / s kinematic viscosity. Alternatively, on the same basis, (Q-2-2)amino-functionalized polyorganosiloxane may be present in amounts of 1% to 2%.

[0056] (Q-1) Alkyl polysiloxanes have the following formula: , where each R 19 It is an independently chosen monovalent saturated hydrocarbon group with 1 to 18 carbon atoms, and the subscript aa has an average value of 20 to 300. R 19 The monovalent saturated hydrocarbon group can be an alkyl group, alternatively an alkyl group with 1 to 6 carbon atoms. Alternatively, the alkyl group may have 1 to 3 carbon atoms, alternatively 1 to 2 carbon atoms. Alternatively, each R... 19It can be methyl. Suitable alkyl polysiloxanes (e.g., bis-trimethylsiloxy-terminated polydimethylsiloxanes) are known in the art and can be used, for example, as XIAMETER. ™ The 200 fluid was commercially available from The Dow Chemical Company of Midland, Michigan, USA.

[0057] Alternatively, the (Q) softening additive may comprise a (Q-2) combination comprising: 60% to 70% by weight of the combined weight of all the starting materials in the (Q-2) combination of the (Q-1) alkyl polysiloxane as described above, 29% to 39% by weight of the combined weight of all the starting materials in the (Q-2) combination of the (Q-1) silicone resin, and 1% to 2% by weight of the combined weight of all the starting materials in the (Q-2) combination of the (Q-2) combination of the (Q-2) amino-functionalized polysiloxane, wherein the silicone resin has a hardness of ≥20 as measured by a type A hardness tester according to JIS K 6249:2003, and the amino-functionalized polysiloxane has a functional group equivalent of 100 g / mol to 20,000 g / mol, wherein the equivalent means the molecular weight of the amino-functionalized polysiloxane per mole of nitrogen atoms, and has a functional group equivalent of 10 mm at 25°C as measured by the method of JIS K 2283:2000. 2 / s to 100,000mm 2 kinematic viscosity / s.

[0058] The starting material (Q) softening additive can be delivered in a second aqueous emulsion comprising the (Q) softening additive, (D') a surfactant (which may be as described above for the starting material (D) surfactant), and (E') water (which may be as described above for the starting material (E)). The second aqueous emulsion can be prepared by known methods, such as those described in U.S. Patent Application Publication 2020 / 0332148, by varying the type and amount of the starting material as described herein.

[0059] When selecting starting materials to add to the aqueous emulsion prepared as described in step 1) above and the emulsion formulation formed in step 2) above, 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 aqueous emulsion and / or emulsion formulation may be different from each other.

[0060] Emulsion formulations suitable for treating textiles comprise: (F) a silicone-(meth)acrylate copolymer, (D) a surfactant, (E) water, and (G) a blocked isocyanate, as described above. The emulsion formulation may optionally also comprise additional starting materials selected from the group consisting of: (I) a manganese ion source, (J) phenolic compounds, (K) biocides, (L) additional water (as described above with respect to starting material (E)), (M) flame retardants, (N) wrinkle reducers, (O) antistatic agents, (P) penetrants, (Q) softening additives, and combinations of two or more of the starting materials (K), (L), (M), (N), (O), (P), and (Q). These additional starting materials and their amounts are as described above. Furthermore, the emulsion formulations 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.

[0061] The emulsion formulation prepared as described above can be used to treat textiles. For example, methods for treating textiles include: I) coating the textiles with the emulsion formulation described above, and II) heating the textiles. Step I) can be carried out by any convenient method, such as padding, impregnating, or spraying the textiles with the emulsion formulation. However, the method should be sufficient to deliver a sufficient amount of (F) silicone-(meth)acrylate copolymer and (G) blocked isocyanate, sufficient to impart durable water-repellent properties to the textiles according to the method described below. The method is sufficient to deliver 0.25% to 10% by weight of (F) silicone-(meth)acrylate copolymer and 0.1% to 3.75% by weight, or alternatively 0.25% to 1% by weight of (G) blocked isocyanate, both based on the weight of the textiles.

[0062] Step II) can be performed 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 type of textile selected and the required drying time. However, heating can be performed at temperatures >100°C to remove water. Alternatively, the temperature can be >100°C to 200°C for a duration sufficient to remove all or part of the water, unblock the blocked isocyanate, and / or cure the (F) silicone-(meth)acrylate copolymer.

[0063] There are no particular limitations on the textiles to be treated. 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, polyester, polyamides (such as nylon), polyacrylonitrile, and polyolefins (such as polyethylene and / or polypropylene), and combinations of two or more of these (e.g., blends such as polyester / cotton blends). There are also no particular limitations on the form of the textiles. The emulsion formulations described herein are suitable for any form of textile, such as woven, knitted, or nonwoven fabrics.

[0064] Example The following embodiments are provided to illustrate the invention to those skilled in the art, and these embodiments should not be construed as limiting the scope of the invention as set forth in the claims.

[0065] Table 1 - Starting Materials (3MT-1C) In Reference Example 1, a silicone-(meth)acrylate copolymer emulsion was prepared as follows. All macromonomers, water, and surfactants were added to a wide-mouth bottle (approximately 400 mL) in the selections and amounts shown in Table 2 below. The emulsion was prepared using an ultrasonic apparatus (Fisherbrand Model 705 sonic disruptor, amplitude 50, power approximately 62 W, ​​duration 2 minutes). The aqueous emulsion was then transferred to a reactor and heated to 65°C. After the aqueous emulsion reached the desired temperature, initiator 1 (0.26 g) was added, and the reactor contents were stirred for 6 hours. The reactor contents were then cooled to room temperature, and the resulting copolymer emulsions were poured into individual bottles.

[0066] Table 2. Preparation of copolymers via emulsion polymerization *0.4 g of 2.5 wt% aqueous solution of 4-methoxyphenol, 0.006 g of hydroquinone, and 0.12 g of 0.7 wt% aqueous solution of manganese(II) acetate tetrahydrate.

[0067] In Reference Example 2, an emulsion formulation was prepared, the fabric was treated, and the oil repellency was evaluated as follows: All fabrics were washed / dried prior to coating. The absorbency of each fabric was measured, and the emulsion formulation was then prepared based on this absorbent weight by adding a blocked isocyanate additive. Table 3 provides the exact emulsion formulation formulations. Each emulsion formulation was then poured into a Mathis HVF roller (2 m / min at 60 psi) for coating. The fabric was passed through the coating machine until no dry spots were observed (usually twice), and then placed in a forced-ventilation Mathis LTF oven at 160°C for 3 minutes. The fabric was weighed before and after coating to obtain the actual coated weight. Each sample was approximately 2% by weight on the fabric.

[0068] In Example 7, 90% of the washing machine used was a Whirlpool model WTW4855HW1. ° Wash F, then use a cold rinse cycle (approximately 70 seconds). ° F) Wash the sheet (Settings: Normal cycle, hot wash temperature, deep wash, automatic sensor rinse). Use Tide Free and Gentle Liquid Laundry Detergent as detergent, 39g for a 6-pound load of fabric. For smaller loads, adjust the detergent amount proportionally. Hot water for washing the sample was passed through the building-wide water softening system. Cold water was also softened and passed through a PDIMX-60 water softener system from Franklin Electric using standard settings (default hardness set to 20). The sample was dried using a Whirlpool model WED4850HW0 dryer (at a height of approximately 140°C). o Automatic drying cycle under F).

[0069] Table 3. Results of Emulsion Formulation and Oil Repellency Oil repellency (surface rating) was determined using a modified version of the American Association of Textile Chemists and Dyers (AATCC) standard test method 118. Face ratings of A, B, C, and D were used, as described in AATCC 118 (and as in Lei et al., Progress in Organic Coatings). Progress in Organic CoatingsAs shown in Figure 3 of "Fluorine-free low surface energy organic coating for anti-stain applications" in 103 (2017) 182-192, 184, surface rating A indicates clear, rounded oil droplets; B indicates rounded droplets indicating localized darkening; C indicates significant wicking and / or complete wetting; and D indicates complete wetting. A modification to this test method is that olive oil is used, and the time is extended from 10 seconds to 5 minutes. A rating of A or B is required after 5 minutes. A surface rating of C or D indicates unacceptably high oil absorption of the fabric. Relatively large olive oil droplets are used for this test, i.e., at least 500 μL / drop.

[0070] In Table 3, * indicates that the sample was washed 5 times before the oil repellency test, ** indicates the value obtained after 10 seconds instead of 1 minute, and *** indicates that the sample also has an A face rating when the value is obtained again after 15 minutes. The data in Table 3 show that the presence of blocked isocyanate additives significantly improves oil repellency. For example, Example 1 and Comparative Example 2 (Comp 2) contain the same starting material (i.e., an emulsion of a copolymer of 3MT-ALMA), the difference being that Example 1 contains blocked isocyanate, while Comp 2 does not. Example 1 showed significantly improved oil repellency under all test conditions. Similarly, Example 4 showed significantly improved oil repellency relative to Comparative Example 5 after 1 minute and 5 minutes. Comparative Example 6 showed that the use of stearyl acrylate in the copolymer unexpectedly failed to provide passability. Example 7 showed unexpected washability without any added crosslinking points in the copolymer backbone. Examples 1, 2, 5, and 6 demonstrate that oil repellency can be achieved on a variety of fabric types using the emulsion formulations described herein. In addition, Examples 1 and 2 show that oil repellency is improved when isocyanate additives are used.

[0071] Additional samples were prepared and evaluated as follows: method A In this synthetic example 1, a silicone-(meth)acrylate copolymer emulsion was prepared as follows. All starting materials (except the initiator) were added to a wide-mouth flask (approximately 400 mL) according to the selections and amounts shown in Table 4 below. The emulsion was prepared using an ultrasonic apparatus (Fisherbrand Model 705 sonic disruptor, amplitude 50, power approximately 62 W, ​​duration 2 minutes). The aqueous emulsion was then transferred to a reactor and heated to 65°C. After the aqueous emulsion reached the desired temperature, 0.26 g of 2,2'-azobis(2-methylpropanediamine) dihydrochloride (AIBN) was added, and the reactor contents were stirred for 6 hours. The reactor contents were then cooled to room temperature, and the resulting aqueous copolymer emulsions were poured into individual flasks. The aqueous copolymer emulsions prepared as described above are summarized in Table 4 below. The amounts of each starting material in Table 4 are in grams.

[0072] method B In this synthetic example 2, a silicone-(meth)acrylate copolymer emulsion was prepared as follows. All starting materials (except the initiator) were added to a wide-mouth flask (approximately 400 mL) according to the selections and amounts shown in Table 4 below. First, the stearyl acrylate monomer was melted and added as a liquid. Furthermore, the emulsion was suppressed with hydroquinone (based on 50 ppm of monomer), manganese(II) acetate*4H2O (based on 1.5 ppm of monomer), and methyl ether hydroquinone (based on 150 ppm of monomer). The resulting material was sonicated at an amplitude of 50 for two minutes using a Fisher sonicator to produce an emulsion. The resulting emulsion was then transferred to a 500 mL four-necked flask equipped with a reflux condenser, nitrogen inlet, top stirrer (IKA RW20), and thermocouple probe. The emulsion was stirred at 250 RPM using a Teflon blade and heated to 65°C. After reaching the desired temperature, 0.25 g of 2,2'-azobis(2-methylpropanediamine) dichloride was added, and the reaction was allowed to proceed for 6 hours. The resulting material was then cooled to 30°C to 40°C with slow stirring and poured off. The aqueous copolymer emulsions prepared as described above are summarized in Table 4 below. The amounts of each starting material in Table 4 are in grams.

[0073] In the preparation of method C, several solutions are prepared as follows: Solution A preparation: Add 0.0566 g of tert-butyl hydroperoxide (70% in water), and then add sufficient water to prepare 10 g of solution. Solution B preparation: Add 0.0773 g of isoascorbic acid, and then add sufficient water to prepare 10 g of solution. Solution C preparation: Add 6 mg of ferric(II) sulfate heptahydrate, and then add sufficient water to prepare 10 g of solution.

[0074] method C In this synthetic example 3, the emulsion was prepared as follows. The starting materials, selected and weighed according to the amounts shown in Table 4, were placed into a 400 mL wide-mouth flask. First, stearyl acrylate and benzyl acrylate monomers were melted and added as a liquid. Furthermore, the emulsion was suppressed with hydroquinone (based on 50 ppm of monomer), manganese(II) acetate*4H2O (based on 1.5 ppm of monomer), and methyl ether hydroquinone (based on 150 ppm of monomer). The resulting material was ultrasonicated at an amplitude of 50 for two minutes using a Fisher sonicator to produce an emulsion. The crude emulsion was then passed through a microfluidizer (Microfluidics Microfluidizer 110Y) set to 1,000 psi, twice. The aqueous emulsion was then transferred to a reactor and heated to 65°C. After the aqueous emulsion reached the desired temperature, 2,2'-azobis(2-methylpropanediamine) dihydrochloride (AIBN) (0.26 g) was added, and the reactor contents were stirred for 6 hours. The reactor contents were then cooled to room temperature, and the resulting aqueous copolymer emulsions were poured into individual bottles. The aqueous copolymer emulsions prepared as described above are summarized in Table 4 below. The amounts of each starting material in Table 4 are in grams.

[0075] Table 4 - Methods used according to Synthesis Examples 1 to 3 A To method C Starting materials for synthesis In Reference Example 3, the weight-average molecular weights of some silicone-(meth)acrylate copolymers in Table 4 were measured by GPC as follows: Samples for GPC were prepared by dissolving 174.41 mg of the 29% emulsion copolymer sample described in Table 4 above in 10 mL of THF (5 mg / mL) in a 20 mL vial. The sample was placed on a shaker for 2 hours. The sample was then filtered through a 0.45 μm PTFE filter and injected into the GPC instrument. The sample was analyzed using a Waters e2695 LC pump and an autosampler equipped with two 5 μM Agilent PLG gel mixing C-columns in series and a Shodex RI-501 differential refractive index detector. The molecular weight range was calibrated using a polystyrene 1683 broad molecular weight standard. The instrument was equilibrated at 1 mL / min for 30 minutes, and the sample was also run at 1 mL / min. The results for the copolymers tested are shown in Table 5 below.

[0076] Table 5 – GPC Dataset: In this Reference Example 5, an emulsion formulation was prepared using the aqueous copolymer emulsion described in Table 4, the fabric was treated, and the oil repellency was evaluated using the same method as described in Reference Example 2 above. The emulsion formulation and oil repellency results are shown in Table 6 below.

[0077] Table 6 - Results of Emulsion Formulations and Oil Repellency Examples 9 to 13 and Comparative Examples 8 to 10 show that the Mw of the silicone-(meth)acrylate copolymer can affect the oil-repellent properties. Although it is shown that various methods can be used (e.g., the methods in Synthetic Examples 1 to 3),... A To method C The silicone-(meth)acrylate copolymer was manufactured using [a specific method / methcoat], however, when the Mw of the silicone-(meth)acrylate copolymer was >181,000 g / mol, the oil repellency improved under the tested conditions. These results contradict the disclosure in *Progress in Organic Coatings*, Lei, H. et al., 2016, which discloses an oil repellency test with a molecular weight of 80,000 g / mol. Examples 14 through 17 demonstrate the breadth of use of blocked isocyanate additives in (16:1–2:1, copolymer:additive, in these cases additive = XAN).

[0078] In this synthetic example 4, PDMS resin 1 was prepared as follows (as described in Example 1 of US Patent Publication 20230038369): 0.88 g (10 mmol) of 3MT-ALMA, 0.31 g (1 mmol) of vinyltrimethoxysilane, and 0.033 g (0.1 mmol) of azobisisobutyronitrile were added to a round-bottom flask containing 47.95 g of anhydrous xylene at room temperature. The round-bottom flask was equipped with a condenser, a nitrogen inlet, a top stirrer, and a thermocouple probe. The system was purged with nitrogen for 5 minutes, and then the solution was heated to 65°C and then maintained for 24 hours.

[0079] In this synthetic example 5, PDMS resin 2 was prepared as follows: 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 hours to obtain a pale yellow solution. After removing the solvent under vacuum, the residue was dissolved in 75 mL of dichloromethane. The material was washed with a saturated NaHCO3 solution (75 mL × 5). The water was then distilled off, leaving a pale yellow liquid product. PDMS resin 2 gelled by the next day, therefore this resin cannot be coated onto textiles.

[0080] The procedures for Comparative Examples 18 and 19 included fabric pretreatment followed by treatment with PDMS resin 1, as follows: 1 cm × 1 cm PES or nylon fabric was washed with 200% standard strength ethanol and then dried in an oven at 80°C for 10 minutes. A silica sol was then prepared by hydrolyzing tetraethoxysilane (2.08 g, 10 mmol) in 60 mL ethanol / 15 mL DI water in the presence of ammonium hydroxide (2.75 mL). The fabric was immersed in the sol for 5 minutes and dried at room temperature (approximately 30 minutes). This process was repeated twice. The fabric was then immersed 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 (approximately 4 seconds) and then dried overnight at 80°C. The pretreated 1 cm × 1 cm PES or nylon fabric sample was dipped into PDMS resin 1 three times. The sample was cured at 200°C for 1 hour.

[0081] The procedures for Comparative Examples 20 and 21 are as follows: A 1cm × 1cm PES or nylon fabric sample was dipped into synthetic PDMS resin 1 three times. The sample was then cured at 200°C for 1 hour.

[0082] The procedures for Comparative Example 22 and Comparative Example 23 are as follows: Wash 1cm × 1cm PES or nylon fabric with 200% standard strength ethanol and then dry in an oven at 80°C for 10 minutes. Prepare a silica sol by hydrolyzing tetraethoxysilane (2.08g, 10mmol) in 60mL ethanol / 15mL DI water in the presence of ammonium hydroxide (2.75mL). Immerse the fabric in the sol for 5 minutes and dry at room temperature (approximately 30 minutes). Repeat this process twice more. Then, immerse the fabric in a 5% suspension of Ludox HS silica (5g of a 40% solution of Ludox HS-40 colloidal silica and 35g of DI water) until saturated (approximately 4 seconds) and then dry overnight at 80°C.

[0083] Table 7 - Results of Comparative Examples 18 to 23 Comp 18 and Comp 19 correspond to Example 2 disclosed in US Patent Publication US20230038369. In the modified AATCC method 118, these yielded unacceptable oil repellency ratings after 5 minutes. In contrast, the present invention (e.g., as shown in Examples 1 and 5 in Table 3 above) exhibits excellent oil repellency using AATCC method 118. Comp 20 and Comp 21 removed the sol-gel and nanoparticle treatments and tested the 3MT-ALMA / vinyltrimethoxysilane copolymer; these examples also failed the modified AATCC method 118 after 5 minutes.

[0084] In Comparative Example 24, the PES fabric was treated with two separate emulsions in two separate steps. First, the fabric was coated with a Phobol-XAN emulsion (0.69 g XAN + 74.31 g DI water) as described in the coating / curing method in Reference Example 2 above. In the second step, the fabric was treated with an emulsion of copolymer 1 from Table 2 above, wherein 5.75 g of copolymer emulsion 1 from Table 2 was combined with 69.25 g of DI water using the same coating and curing method as described in Reference Example 2 above.

[0085] Comparative Example 24 illustrates a pretreatment method for a blocked isocyanate (XAN) additive similar to that described in Example 2 (Comp 18 and Comp 19 above) of U.S. Patent Publication US20230038369. Comparative Example 24 failed the modified AATCC method 118 after 10 seconds and exhibited worse oil repellency than Comparative Examples 18 and 19 at 10 seconds.

[0086] In Comparative Example 25, 3.83 g of the copolymer emulsion 1 described in Table 2 above and 1.59 g of DOWSIL were used. ™ IE-8749 (a 70% solid silicone durable water repellent commercially available from Dow Chemical Company) was added to a 125g Nalgene plastic bottle. The bottle was then inverted twice to mix the contents. The mixture was applied to a fabric as described in Reference Example 2 above, and the oil repellency was measured. The fabric had a C rating after 10 seconds and a D rating after 30 seconds. Comparative Example 25 shows that the silicone material blended with the copolymer of 3MT-ALMA (the active ingredient in IE-8749) failed the oil repellency test described herein after 30 seconds.

[0087] In Reference Example 6, the study of the blocked isocyanate as described in Table 8 was conducted as follows. The textile treatment emulsion was prepared as follows. The amounts of each starting material listed in Table 9 were added to a 125g Nalgene plastic bottle. After addition, the bottle was inverted twice to mix the contents. The order of addition is not important. In Reference Example 6, the fabric was treated with the textile treatment emulsion prepared as described above. All fabrics were washed and dried before coating. The textile treatment emulsion as described in Table 9 was then poured into a beaker, and then dip-coated and coated using a Werner Mathis AG Textilmaschinen rolling mill (tension set to 70). After one pass, the sample was held in a forced-ventilation Mathis LTF oven at 160°C for 3 minutes. The oil repellency of the sample was evaluated using the method described in Reference Example 2 above. The results are shown in Table 10 below.

[0088] Table 8 - Commercially available blocked isocyanate dispersions (additives) Table 9 - Emulsion Formulations Prepared According to Reference Example 6 AATCC test results of samples in Tables 10-9 We do not wish to be bound by theory, assuming that additives can be free of substances that may interfere with the performance of isocyanates in emulsion formulations, such as silicones and amines (not within the blocked group). Furthermore, we do not wish to be bound by theory, assuming that blocked isocyanates can be delivered in emulsions or dispersions without anionic surfactants.

[0089] In Comparative Example 26, 2.25 g Daikin XF-5100 (available in the US, replacing XF-5003, 3%), 4.5 g RUCODRY Eco Plus (6%), and 1.875 g RUCO-LINK XCR (2.5%) (both from the Rudolf Group) were mixed with 66.125 g water. The resulting sample was coated onto PES and evaluated using a modified AATCC 118 test as described in Reference Example 2. The treated fabric failed the oil repellency test at 30 seconds.

[0090] Industrial applicability The above embodiments demonstrate that the emulsion formulations and methods described herein can produce fabrics with durable oil repellency. As used herein, "oil repellency" means an A or B side rating after 5 minutes of contact with a large oil droplet, as measured by the modified AATCC 118 test described above. As used herein, "durable" means that the fabric can be washed at least 5 times after treatment with the emulsion formulation described herein, and the fabric will still have the oil repellency as described above (as shown in Example 7 above).

[0091] The inventors have surprisingly discovered that the inclusion of blocked isocyanates in the emulsion formulation improves the oil repellency of textiles treated with the emulsion formulation compared to fabrics treated with comparative compositions that do not contain blocked isocyanates (see Examples 1 and 2 above; and Examples 2 and 3 above). This finding is particularly unexpected when the starting materials copolymerized in the above method and the resulting silicone-(meth)acrylate copolymer do not contain crosslinkable groups. Furthermore, the inventors have surprisingly discovered that the emulsion formulation imparts durable oil repellency to textiles even when the fabric is not pretreated, for example, by plasma treatment or washing, before being coated with the emulsion formulation.

[0092] Definition and use of terms Unless otherwise specified, all quantities, ratios, and percentages herein are by weight. The summary of the invention and the abstract of the specification are incorporated herein by reference. Unless the context otherwise indicates, the articles “a,” “an,” and “the” refer to one (a kind) or more (a plurality of kinds). The transitional phrases “comprising,” “substantially consisting of,” and “consisting of” are used as described in Chapters §2111.03 I, II, and III of the Patent Examining Procedure Ninth Edition, last revised January 2018, Amendment 08.2017. The use of “for example,” “for instance,” “such as,” and “including” to list exemplary examples does not imply limitation to the listed examples. Thus, “for example” or “such as” means “for example, but not limited to” or “such as, but not limited to” and covers other similar or equivalent examples. The symbol “<” means “less than,” the symbol ">” means “greater than,” the symbol “≤” means “less than or equal to,” and the symbol “≥” means “greater than or equal to.” The abbreviations used in this article have the definitions in Table 11.

[0093] Table 11—Abbreviations

Claims

1. A method for preparing an emulsion formulation suitable for treating a textile, wherein the method comprises: 1) copolymerizing starting materials comprising (A) a silicone-(meth)acrylate macromonomer of the formula: wherein each R 1 is an independently selected monovalent hydrocarbon group of 1 to 12 carbon atoms; D 2 is a divalent hydrocarbon group of 2 to 12 carbon atoms; and R 2 is selected from the group consisting of H and methyl; (B) optionally a silicone-(meth)acrylate co-macromonomer, wherein the silicone-(meth)acrylate co-macromonomer of (B) has a formula selected from the group consisting of formula (B-1), formula (B-2), and a combination of both formula (B-1) and formula (B-2), wherein Formula (B-1) is wherein each R 1 is an independently selected monovalent hydrocarbon group of 1 to 12 carbon atoms; D 2 is a divalent hydrocarbon group of 2 to 12 carbon atoms; and R 2 is selected from the group consisting of H and methyl; Formula (B-2) is wherein R 2 is selected from the group consisting of H and methyl; D 2 is a divalent hydrocarbon group of 2 to 12 carbon atoms, and each R 3 is a group of the 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)oxyalkylene 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 DSiR3; with the proviso that R 4 , R 5 , and R 6 are selected such that the silicone-(meth)acrylate copolymer macromonomer of Formula (B-2) has at least 5 silicon atoms per molecule; wherein starting material (A) is present in an amount of > 25 wt% to 100 wt% based on the combined weight of starting materials (A) and (B); and wherein starting material (B) is present in an amount of 0 wt% to < 75 wt% based on the combined weight of starting materials (A) and (B); and wherein starting materials (A) and (B) are copolymerized in the presence of additional starting materials, wherein the additional starting materials comprise: (C) an initiator; optionally (H) a chain transfer agent; optionally (I) a source of manganese ions; and optionally (J) a phenolic compound; and wherein one of conditions (i) or (ii) is met, wherein condition (i) is that step 1) further comprises adding a solvent prior to or during step 1), removing the solvent after formation of (F) the silicone-(meth)acrylate copolymer, and forming an aqueous emulsion comprising (F) the silicone-(meth)acrylate copolymer, (D) the surfactant, and (E) the water; and wherein condition (ii) is that step 1) comprises an emulsion polymerization reaction; the additional starting materials further comprise (D) the surfactant and (E) the water; and wherein the product of step 1) comprises an aqueous emulsion containing (F) the silicone-(meth)acrylate copolymer, (D) the surfactant, and (E) the water; 2) combining materials comprising the aqueous emulsion and (G) a blocked isocyanate, and optionally additional starting materials, wherein the additional starting materials, when present, are selected from the group consisting of (K) a biocide, (L) additional water, (M) a flame retardant, (N) a wrinkle reduction agent, (O) an anti-static agent, (P) a penetrating agent, (Q) a softening agent, and a combination of two or more thereof.

2. The method of claim 1, wherein Each R 1 It is methyl. Each R 2 It is methyl. each D 2 is propylene, each R is independently a group of formula OSi(R)3; wherein 3 each R is independently a group of formula OSi(R)3; wherein 4 each R is independently a group of formula OSi(R)3; Each R 4 Independently select free R and OSi(R) 5 Groups consisting of 3, among which each R is methyl; Each R 5 Independently select free R and OSi(R) 6 Groups consisting of 3; among which Each R 6 Independently select the group composed of free R and OSiR3; with the proviso that R is selected 4 R 5 and R 6 such that said silicone-(meth)acrylate copolymer macromonomer of formula (B-2) has from 10 to 16 silicon atoms per molecule.

3. The method of claim 1 or claim 2, wherein starting material (A) is 3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxane-3-yl)propyl methacrylate.

4. The method of any one of claims 1 to 3, wherein the silicone-(meth)acrylate co- macromonomer of (B) of formula (B-1) is present in an amount of 1 wt% to 50 wt% based on the combined weight of starting materials (A) and (B), and formula (B-1) is 3-(1,1,1,3,5,5,5-heptamethyltrisiloxane-3-yl)propyl methacrylate.

5. The method of any one of claims 1 to 3, wherein the silicone-(meth)acrylate copolymer macromonomer of (B) Formula (B-2) is present in an amount of 1 wt% to 50 wt% based on the combined weight of starting materials (A) and (B), and Formula (B-2) 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; 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; and combinations thereof.

6. The method of any one of claims 1 to 5, wherein (C) the initiator comprises: 2,2'-azobis(2-methylpropionamidine) dihydrochloride.

7. The method of any one of claims 1 to 6, wherein (D) the surfactant is selected from the group consisting of cationic surfactants, nonionic surfactants, and combinations thereof.

8. The method of any one of claims 1 to 5, wherein (H) the chain transfer agent is present, and the chain transfer agent comprises dodecanethiol.

9. The method of any one of claims 1 to 8, wherein (I) the manganese ion source is present, and the manganese ion source comprises manganese (II) acetate, manganese (II) acetate tetrahydrate, or combinations thereof.

10. The method of any one of claims 1 to 9, wherein the phenolic compound is present, and the phenolic compound is selected from the group consisting of hydroquinone, monomethyl ether of hydroquinone, t-butyl hydroquinone, and combinations of two or more thereof.

11. The method of any one of claims 1 to 10, wherein (G) the blocked isocyanate comprises an oxime blocked isocyanate.

12. A textile treatment emulsion prepared by the method of any one of claims 1 to 11, wherein the textile treatment emulsion comprises: (F) a silicone-(meth)acrylate copolymer, wherein the silicone-(meth)acrylate copolymer comprises units of the formula: wherein each D is independently selected from the group consisting of an oxygen atom, a (poly)oxyalkylene group of 1 to 12 units, and a divalent hydrocarbon group of 2 to 4 carbon atoms; subscript a, b1, and b2 represent the weight fraction of units in the copolymer, and subscripts a, b1, and b2 have values such that 0.25 < a < 1; and 0 < (b1 + b2) < 0.75; and the silicone-(meth)acrylate copolymer further comprises a terminal moiety; (D) a surfactant; wherein each R is an independently selected monovalent hydrocarbon group of 1 to 12 carbon atoms; 1 each R is an independently selected monovalent hydrocarbon group of 1 to 12 carbon atoms; each D is independently -CH2-, -CH2CH2-, or -CH2CH2CH2-; 2 independently a divalent hydrocarbon group of 2 to 12 carbon atoms; and Each R 2 Independently selected from the group consisting of H and methyl groups; each R is independently a group of formula OSi(R 3 )3; wherein 4 each R is independently a group of formula OSi(R 3 )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 (E) water; and Each R 5 Independently select R and DSi(R) 6 Groups consisting of 3; among which Each R 6 Independently select the group composed of R and DSiR3; with the proviso that R is selected 4 R 5 and R 6 such that the silicone-(meth)acrylate copolymer macromonomer units having subscript b2 have at least 5 silicon atoms; (G) a blocked isocyanate. ​ ​ ​ ​ ​ ​ 13. The textile treatment emulsion of claim 12, wherein the textile treatment emulsion is free of fluorocarbons.

14. A method for treating a textile, wherein the method comprises: I) coating the textile with the emulsion formulation of claim 12 or claim 13; and II) heating the textile.

15. A composition comprising: (F) a silicone-(meth)acrylate copolymer comprising the following unit formula: wherein each R is an independently selected monovalent hydrocarbon group of 1 to 12 carbon atoms; 1 each R is an independently selected monovalent hydrocarbon group of 1 to 12 carbon atoms; each D is independently -CH2-, -CH2CH2-, or -CH2CH2CH2-; 2 independently a divalent hydrocarbon group of 2 to 12 carbon atoms; Each R 2 Independently selected from the group consisting of H and methyl groups; each R is independently a group of formula OSi(R)3; wherein 3 each R is independently a group of formula OSi(R)3; wherein 4 each R is independently a group of formula OSi(R)3; each R is independently selected from the group consisting of R and DSi(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)oxyalkylene group of 1 to 12 units, and a divalent hydrocarbon group of 2 to 4 carbon atoms; Each R 5 Independently select R and DSi(R) 6 Groups consisting of 3; among which Each R 6 Independently select the group composed of R and DSiR3; with the proviso that R is selected 4 R 5 and R 6 such that the silicone-(meth)acrylate copolymer macromonomer units having subscript b2 have at least 5 silicon atoms; subscript a, b1, and b2 represent the weight fraction of units in the copolymer, and subscript a, b1, and b2 have values such that 0.25 < a < 1 ; and 0 < (b1 + b2) < 0.75; (I) a source of manganese ions; and (J) a phenolic compound.

16. The method of any one of claims 1 to 11, wherein the silicone-(meth)acrylate copolymer has a weight average molecular weight of > 181,000 g / mol as 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 claim 12 or claim 13, wherein the silicone-(meth)acrylate copolymer has a weight average molecular weight of > 181,000 g / mol as 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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