Silicone-(meth)acrylate copolymer emulsion and its preparation, and use of emulsion to impart oil repellency to textiles.

Abstract

Disclosed are a fabric treatment emulsion formulation comprising a silicone-(meth)acrylate copolymer, a surfactant, water, and a blocked isocyanate, as well as a method for preparing the same. The fabric treatment emulsion may be used in a method comprising coating a fabric with the emulsion formulation and heating the fabric to dry the emulsion formulation. This method makes the fabric oil-repellent.

Description

[Technical Field]

[0001] (Cross-reference of related applications) This application claims priority under 119(e) of the United States Patent Act to U.S. Provisional Patent Application No. 63 / 593716, filed on 27 October 2023, and U.S. Provisional Patent Application No. 63 / 674322, filed on 23 July 2024. U.S. Provisional Patent Applications No. 63 / 593716 and No. 63 / 674322 are incorporated herein by reference.

[0002] (Field of invention) An emulsion formulation suitable for treating textiles, as well as a method for preparing and using the same, is provided. More specifically, the emulsion formulation comprises a silicone-(meth)acrylate copolymer. The emulsion formulation is useful for treating textiles to impart durable oil repellency. [Background technology]

[0003] Introduction Fluorinated materials have dominated the water- and oil-repellent fabric coating market for many years. However, regulatory and customer pressures are contributing to the industrial need for non-fluorocarbon fabric treatments. [Overview of the project]

[0004] Silicone-(meth)acrylate copolymer has the following unit formula:

[0005] [ka] The formula includes, and in the formula, each R 1 This is a monovalent hydrocarbon group consisting of 1 to 12 independently selected carbon atoms, each D 2 R is a divalent hydrocarbon group of 2 to 12 carbon atoms, which are independently selected. 2 Each R is independently selected from the group consisting of H and methyl, and each R 3 is the formula OSi(R 4 ) is the basis of 3, and in the formula, each R4 independently selected from the group consisting of R and DSi(R 5 )3, wherein each R is an independently selected monovalent hydrocarbon group having 1 to 12 carbon atoms, and each D is independently selected from the group consisting of an oxygen atom, a (poly)alkylene oxide group of 1 to 12 units, and a divalent hydrocarbon group having 2 to 4 carbon atoms, and 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, provided that R 4 , R 5 , and R 6 are selected such that the silicone-(meth)acrylate comonomer unit having a subscript b2 has at least 5 silicon atoms, and the subscripts a, b1, and b2 represent the weight fractions of the units in the copolymer, and the subscripts a, b1, and b2 have values such that 0.25 < a ≤ 1 and 0 ≤ (b1 + b2) < 0.75. An emulsion formulation suitable for treating fabrics comprises 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. <000017​​​​​​​​​​​1) It can be prepared by a method comprising copolymerizing the starting materials, the starting materials being Formula (A)

[0008] [ka] A silicone-(meth)acrylate macromonomer, in which each R 1 D is a monovalent hydrocarbon group consisting of 1 to 12 independently selected carbon atoms. 2 R is a divalent hydrocarbon group consisting of 2 to 12 carbon atoms. 2 (A) a silicone-(meth)acrylate macromonomer selected from the group consisting of H and methyl, The material optionally comprises (B) a silicone-(meth)acrylate commuromonomer, wherein (B) the silicone-(meth)acrylate commuromonomer has a formula selected from the group consisting of formula (B-1), formula (B-2), and combinations of both formula (B-1) and formula (B-2). Equation (B-1) is,

[0009] [ka] And in the formula, each R 1 D is a monovalent hydrocarbon group consisting of 1 to 12 independently selected carbon atoms. 2 R is a divalent hydrocarbon group consisting of 2 to 12 carbon atoms. 2 It is selected from the group consisting of H and methyl, Equation (B-2) is,

[0010] [ka] And in the formula, R 2 D is selected from the group consisting of H and methyl. 2 It is a divalent hydrocarbon group with 2 to 12 carbon atoms, and each R 3 is the formula OSi(R 4 ) is the basis of 3, and in the formula, each R4 These are independently R and DSi(R 5 ) Selected from the group consisting of 3, where each R is an independently selected monovalent hydrocarbon group of 1 to 12 carbon atoms, and each D is independently selected from the group consisting of an oxygen atom, 1 to 12 units of (poly)alkylene oxide group, and 2 to 4 carbon atoms of divalent hydrocarbon group, and each R 5 These are independently R and DSi(R 6 ) Selected from the group consisting of 3, in the formula each R 6 It is independently selected from the group consisting of R and DSiR3, however, R 4 , R 5 , and R 6 The silicone-(meth)acrylate comacromonomer of formula (B-2) is selected such that it has at least 5 silicon atoms per molecule. Starting material (A) is present in an amount greater than 25% to 100% by weight based on the total weight of starting material (A) and starting material (B), and starting material (B) is present in an amount of 0 to less than 75% by weight based on the total weight of starting material (A) and starting material (B), and starting material (A) and starting material (B) are copolymerized in the presence of additional starting material, the additional starting material comprising (C) initiator. The additional starting material used in step 1) optionally further comprises one or more of the following: (H) chain transfer agent, (I) manganese ion source, (J) phenol compound, and chelating agent.

[0011] Step 1) of this method may include an emulsion polymerization reaction. Additional starting materials further include (D) a surfactant and (E) water. In Step 1), the emulsion polymerization described above may include forming an emulsion containing the starting materials (A) silicone-(meth)acrylate macromonomer, (B) silicone-(meth)acrylate comacromonomer (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 phenol compound, and then adding (C) an initiator and copolymerizing. While we do not wish to be bound by theory, it is thought that during the emulsification process of combining (A) silicone-(meth)acrylate macromonomers, (B) silicone-(meth)acrylate comacromonomers, (D) surfactants, and (E) water, and (H) chain transfer agents, if present, the starting materials (I) manganese ion source and / or (J) phenolic compounds may suppress the formation of acrylic radicals that may affect copolymer formation during copolymerization in step 1).

[0012] Step 1) of the above method may include forming an emulsion comprising starting materials (A) silicone-(meth)acrylate macromonomer, (B) silicone-(meth)acrylate comacromonomer, (C) initiator, (D) surfactant, and (E) water, and optionally additional starting materials selected from the group consisting of (H) chain transfer agent, (I) manganese ion source, (J) phenol compound, and two or more combinations thereof. These starting materials can be mixed under shear to form an aqueous emulsion. Mixing under shear can be carried out by any convenient means for forming an aqueous emulsion, e.g., sonication and subsequent microfluidization. Equipment for mixing under shear, e.g., sonicators, homogenizers, microfluidizers, and speed mixers are known in the art and commercially available. While not wishing to be bound by theory, it is conceivable that submicron particle sizes can be obtained in the emulsion using mixing under shear. In step 1), the starting material comprising (A) silicone-(meth)acrylate macromonomer, (B) silicone-(meth)acrylate comacromonomer, and (C) initiator (and, if present, (H) chain transfer agent) is copolymerized with the starting material (D) surfactant and (E) water, and optionally with (I) manganese ion source and (J) phenol compound to form (F) silicone-(meth)acrylate copolymer in an aqueous emulsion.

[0013] The methods described herein may optionally further include one or more additional steps. For example, prior to step 1), the starting materials comprising (A) silicone-(meth)acrylate macromonomers and (B) silicone-(meth)acrylate comacromonomers, and if present, (H) a chain transfer agent, may be combined under aerobic or anaerobic conditions with optional long heating. For example, the starting materials comprising (A) silicone-(meth)acrylate macromonomers and (B) silicone-(meth)acrylate comacromonomers, and if present, one or more of (H) a chain transfer agent, (I) a manganese ion source, and / or (J) a phenol compound may be emulsified with (D) a surfactant and (E) water before adding (C) an initiator and copolymerizing in step 1). In step 1), the combination of starting materials and copolymerization in the above method may be carried out on a commercial scale under anaerobic or aerobic conditions, at optionally high temperatures, e.g., up to 100°C, or 40°C to 80°C, or 45°C to 50°C. Copolymerization may be carried out in a batch process with residence times 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 purposes of this application, aerobic or anaerobic conditions mean that oxygen does not need to be present in the gas in the upper space of the reactor where copolymerization occurs, or is dissolved in the liquid in which copolymerization occurs. The remainder of the gas in the upper space may be an inert gas such as nitrogen or argon.

[0014] Alternatively, the copolymer may be prepared by a method comprising dissolving one or more of the following starting materials in an organic solvent (such as a monohydric alcohol): (A) silicone-(meth)acrylate macromonomer, (B) silicone-(meth)acrylate comacromonomer, and optionally one or more of (H) a chain transfer agent, (I) a manganese ion source, and (J) a phenol compound; and copolymerizing the starting materials (A) silicone-(meth)acrylate macromonomer and (B) silicone-(meth)acrylate comacromonomer, and (H) a chain transfer agent, if present, by varying the appropriate starting materials and their amounts, as disclosed in U.S. Patent No. 1,0047,199 by Iimura et al. The resulting copolymer may be solvent-free. All or part of the solvent can be removed by any convenient means, such as stripping or distillation using heat and optionally reduced pressure. The resulting copolymer can be emulsified with (D) a surfactant and (E) water.

[0015] Regardless of the method used to produce the copolymer, e.g., by emulsion polymerization or by emulsifying a solvent 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. The aqueous emulsion may optionally further comprise (I) a manganese ion source and / or (J) a phenol compound. This aqueous emulsion can be used to prepare an emulsion formulation useful for processing textiles. A method for preparing an emulsion formulation suitable for processing textiles comprises carrying out step 1) as described above to prepare an 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 further include adding additional starting materials, which may be selected from the group consisting of additives such as (K) biocides, (L) additional water (which may be the same as the starting material (E)), (M) flame retardants, (N) wrinkle reducers, (O) antistatic agents, (P) penetrating agents, (Q) softeners, and two or more combinations thereof. Step 2) of this method may optionally further include adding additional (D) surfactants.

[0016] Step 2) of the above process for preparing an emulsion formulation may be carried out by any convenient means, such as mixing in a jacketed container equipped with a stirrer. Steps 1) and 2), and any optional and / or additional steps described above, may be carried out sequentially in the same container. Alternatively, steps 1) and 2) may be carried out in different equipment. Step 2) may be carried out at room temperature or high temperature, for example, up to 100°C or 40°C to 80°C. Alternatively, heating may be performed in step 1) and step 2) may be carried out at room temperature. Alternatively, step 2) may be carried out at low temperature and high pressure, for example, up to 5 atmospheres. The starting materials used in the above method will be described further below.

[0017] The starting material (A) used in this invention is a silicone-(meth)acrylate macromonomer. The silicone-(meth)acrylate macromonomer is of formula (A-1):

[0018] [ka] It has, in the formula, each R 1 D is a monovalent hydrocarbon group consisting of 1 to 12 independently selected carbon atoms. 2 R is a divalent hydrocarbon group consisting of 2 to 12 carbon atoms. 2 This is selected from the group consisting of H and methyl.

[0019] In equation (A-1), each R 1 R is a monovalent hydrocarbon group consisting of 1 to 12 independently selected carbon atoms. 1 The monovalent hydrocarbon group may be an alkyl group, for example, an alkyl group with 1 to 6 carbon atoms. Alternatively, the alkyl group may have 1 to 3 carbon atoms, or 1 to 2 carbon atoms. Alternatively, each R 1 The group can be methyl.

[0020] In equation (A-1), D 2 It is a divalent hydrocarbon group consisting of 2 to 12 carbon atoms. Alternatively, D 2 It may have 2 to 10 carbon atoms, or 3 to 5 carbon atoms, or 3 carbon atoms. 2 The divalent hydrocarbon group can be exemplified by alkylene groups such as ethylene, propylene, or butylene. Alternatively, D 2 The divalent hydrocarbon group may be propylene. Alternatively, D 2 It may be linear, for example, -(CH2)2- or -(CH2)3-. Or, D 2 It may also be -(CH2)3-. Or, D 2 If the material contains -(CH2)3-, the starting material (A) is formula (A-2):

[0021] [ka] Includes, in the formula, R 1 The above is true.

[0022] Starting material (A) is, formula

[0023] [ka] The starting material (A) may include 3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxane-3-yl)propyl methacrylate (3MT-ALMA). The starting material (A) can be prepared by known methods, such as those disclosed in PCT Published International Patent No. 2020142388 and U.S. Patent No. 6420504.

[0024] Starting material (B) is a silicone-(meth)acrylate comacromonomer (comocromonomer) that can be optionally copolymerized with the above (A) silicone-(meth)acrylate macromonomer. Starting material (B), the comacromonomer may include formula (B-1), where formula (B-1) is

[0025] [ka] And in the formula, each R 1 D is a monovalent hydrocarbon group consisting of 1 to 12 carbon atoms, which are independently selected. 2 R is a divalent hydrocarbon group consisting of 2 to 12 carbon atoms. 2 These are selected from the group consisting of H and methyl, and are described and illustrated above for formula (A-1), respectively. Alternatively, D 2 If it contains -(CH2)3-, then formula (B-1) is

[0026] [ka] It may include, in the formula, R 1 and R 2As stated above, or equation (B-2) is equation

[0027] [ka] It may contain 3-(1,1,1,3,5,5,5-heptamethyltrisiloxane-3-yl)propyl methacrylate (MDM-ALMA).

[0028] Alternatively, in addition to or instead of formula (B-1) shown above, the starting material (B) comochromomer is formula (B-2):

[0029] [ka] It may contain a silicone-(meth)acrylate commuromonomer, in which D 2 R is a divalent hydrocarbon group consisting of 2 to 12 carbon atoms. 2 R is selected from the group consisting of H and methyl, as described above for formula (A-1). In formula (B-2), each R 3 is the formula OSi(R 4 )3 is the basis, and each R 4 These are independently R and DSi(R 5 ) Selected from the group consisting of 3, where each R is an independently selected monovalent hydrocarbon group of 1 to 12 carbon atoms, and each D is independently selected from the group consisting of an oxygen atom, 1 to 12 units of (poly)alkylene oxide group, and 2 to 4 carbon atoms of divalent hydrocarbon group, and each R 5 These are independently R and DSi(R 6 ) Selected from the group consisting of 3, in the formula each R 6 It is independently selected from the group consisting of R and DSiR3, however, R 4 , R 5 and R 6 The commacromonomer of formula (B-2) is selected such that each molecule has at least six silicon atoms. Alternatively, R 4 , R 5 , and R 6The unit is selected such that it has at least 5 silicon atoms per molecule, or at least 6 silicon atoms, 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.

[0030] In formula (B-2), each R is a monovalent hydrocarbon group with 1 to 12 carbon atoms. The monovalent hydrocarbon group R may be an alkyl group, for example, an alkyl group with 1 to 6 carbon atoms. Alternatively, the alkyl group may have 1 to 3 carbon atoms, or 1 to 2 carbon atoms. Alternatively, each R group may be methyl.

[0031] In formula (B-2), each D is independently selected from the group consisting of an oxygen atom, 1 to 12 units of (poly)alkylene oxide groups, and 2 to 4 carbon atoms of a divalent hydrocarbon group.

[0032] The divalent hydrocarbon group of D is an alkylene group such as ethylene, propylene, or butylene, an arylene group such as phenylene, or

[0033] [ka] Examples may include alkylarylene groups such as, where each subscript u is independently 1 to 6 or 1 to 2. Alternatively, the divalent hydrocarbon group of D may be alkylene, or the divalent hydrocarbon group of D may be ethylene.

[0034] The (poly)alkylene oxide group of D may have 2 to 4 carbon atoms per unit, for example, formula D 5 (OD 6 ) v’ -OR is present, in the formula, D 5 It is an alkylene group with 2 to 4 carbon atoms, D 6R is an alkylene group with 2 to 4 carbon atoms, R is as described above, and the subscript v' is 0 to 12. Alternatively, the subscript v' can be 0 or 1. Alternatively, the subscript v' can be 0. An example of a (poly)alkylene oxide group is ethylene oxide-propylene oxide.

[0035] 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, some examples of D in the same unit may be oxygen, and other examples of D may be alkylene, such as ethylene.

[0036] Alternatively, equation (B-2) is equation (B-2-1):

[0037] [ka] It may include, in the formula, R 2 , R 4 , and R 5 This is as stated above.

[0038] Alternatively, equation (B-2) is equation (B-2-2):

[0039] [ka] It may include, in the formula, R 2 D and R are as described above.

[0040] Alternatively, equation (B-2) becomes equation (B-2-3):

[0041] [ka] It may include, in the formula, R 2 D and R are as described above.

[0042] Alternatively, equation (B-2) is, formula

[0043] [ka] 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), formula

[0044] [ka] The compound may also contain a comacromonomer selected from the group consisting of 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 comacromonomer of formula (B-2) described and illustrated above can be prepared by known methods, such as those disclosed in PCT Published International Patent Application No. 2020142388 and U.S. Patent No. 6420504.

[0045] Starting material (A) silicone-(meth)acrylate macromonomer and starting material (B) silicone-(meth)acrylate co-macromonomer are used in the following amounts when preparing the copolymer: Starting material (A) is used in an amount greater than 25% to 100% by weight based on the total weight of starting material (A) and starting material (B), and starting material (B) is used in an amount between 0% and less than 75% by weight based on the total weight of starting material (A) and starting material (B). Alternatively, starting material (A) may be used in an amount greater than 25%, or at least 40%, or at least 50%, or at least 63%, or at least 75%, based on the total weight of starting material (A) and starting material (B), and at the same time, the amount of starting material (A) may be up to 100%, or up to 99%. On the same basis, or up to 95%, or up to 75%, or up to 63%, or up to 50%, or 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 the amount of starting material (B) may be greater than 0%, or at least 1%, or up to 5%, or up to 10%, or up to 15%, or up to 20%, or at least 25%, and at the same time, the amount of starting material (B) may be up to 60%, or up to 50%, or up to 37%, or up to 25%, on the same basis. The starting materials used to produce the copolymer may optionally not contain crosslinking groups, for example, the starting materials copolymerized in step 1) of the method described herein may not contain crosslinking (meth)acrylate monomers such as organic (meth)acrylate monomers having crosslinking groups.For example, the starting materials used in step 1) do not have to include crosslinkable (meth)acrylate monomers such as (2-acetoacetoxy)ethyl methacrylate, hydroxybutyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxyethyl caprolactone (meth)acrylate, hydroxypropyl (meth)acrylate, ureido (meth)acrylate, glycidyl (meth)acrylate (GMA), and poly(alkylene glycol) (meth)acrylate macromonomers, such as poly(ethylene glycol) mono-(meth)acrylate (PEGMA) and poly(ethylene glycol) di(meth)acrylate, which have crosslinkable groups. The starting materials used in step 1) do not have to include organosilyl monomers having crosslinkable groups such as alkenyltrialkskoxysilanes (e.g., 3-(trimethoxysilyl)propyl (meth)acrylate, vinyltriethoxysilane, and vinyltrimethoxysilane). Alternatively, the starting materials copolymerized in step 1) may essentially consist of starting materials (A), (B), and (C), and (H) if present.

[0046] Starting material (A), and if present, starting material (B), are copolymerized in the presence of additional starting material, the additional starting material comprising (C) an initiator. Alternatively, the starting material copolymerized in step 1) may consist of starting material (A) a macromonomer, (B) a comacromonomer, and (C) an initiator, and if present, (H) a chain transfer agent. Alternatively, the starting material used in step 1) may essentially consist of (A) a macromonomer, (B) a comacromonomer, (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 phenol compound, which are further described below.

[0047] The starting material (C), which is an initiator, is also added in step 1) above. Suitable initiators include azo compounds and peroxide compounds. For example, the azo compound may be an aliphatic azo compound such as 1-t-amylazo-l-cyanocyclohexane, azo-bis-isobutyronitrile, and 1-t-butylazo-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 of these. Azo compounds are known in the art and are commercially available, for example, from The Chemours Company (Wilmington, Delaware, USA) under the name VAZO® WSP. The peroxide compound may be a peroxide or hydroperoxide, such as t-butyl peroctoate, t-butyl perbenzoate, dicumyl peroxide, di-t-butyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, di-t-amyl peroxide, or a combination of two or more of these. In addition, di-peroxide initiators may be used alone or in combination with other initiators. Examples of such di-peroxide initiators include, but are not limited to, 1,4-bis-(t-butylperoxycarbo)cyclohexane, 1,2-di(t-butylperoxy)cyclohexane, and 2,5-di(t-butylperoxy)-3-hexine. Suitable peroxide compounds are known in the art and are commercially available from various suppliers such as Sigma-Aldrich, Inc. Alternatively, the initiator may include isoascorbic acid.

[0048] The initiator may be used alone as the starting material (C). Alternatively, the starting material (C) may be a redox pair containing an initiator as an oxidizing component and a reducing component. Alternatively, a redox pair containing isoascorbic acid and an organic hydroperoxide such as t-amyl hydroperoxide or t-butyl hydroperoxide may be used as the starting material (C). Examples of initiators and / or redox pairs suitable for the starting material (C) are disclosed in column 11, line 16 of Bardman et al., U.S. Patent No. 6,576,051. 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, if a thermal initiator is used, all initiators are added at once at the start of step 1). Alternatively, if a redox pair is used, it may be metered and supplied over time.

[0049] Alternatively, the initiator may optionally further contain iron(II) sulfate heptahydrate, potassium persulfate, or a combination thereof. Initiator (C) can be used in an amount sufficient to be 0.01% to 3% or 0.1% to 1.5% based on the weight of the silicone-(meth)acrylate copolymer.

[0050] 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 useful herein include compounds containing a quaternary ammonium hydrophilic moiety within a positively charged molecule, for example, formula (D-1-1):R 12 R 13 R 14 R 15 N + X' - Examples of quaternary ammonium salts that can be represented by the formula are, where R 12 ~R 15is 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 may be an alkyltrimethylammonium and dialkyldimethylammonium halide, or acetate, each having at least 8 carbon atoms in each alkyl substituent. Dialkyldimethylammonium salts can be used, and it is represented by the formula (D-1-2): R 16 R 17 N + (CH3)2X’ - wherein, R 16 and R 17 are 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. Monoalkyltrimethylammonium salts can be used, and it is represented by the formula (D-1-3): R 18 N + (CH3)3X’’ - wherein, R 18 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 acetate.

[0051] Representative quaternary ammonium halide salts are dodecyltrimethylammonium chloride / lauryltrimethylammonium chloride (LTAC), cetyltrimethylammonium chloride (CTAC), hexadecyltrimethylammonium chloride, didodecyldimethylammonium bromide, dihexadecyldimethylammonium chloride, dihexadecyldimethylammonium bromide, dioctadecyldimethylammonium chloride, dieicosyldimethylammonium chloride, and didocosyldimethylammonium chloride. These quaternary ammonium salts are commercially available under trademarks such as ADOGEN™, ARQUAD™, TOMAH™, and VARIQUAT™.

[0052] 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. Examples of such commercially available cationic surfactants include compositions sold by Akzo Nobel Chemicals Inc. (Chicago, Illinois) under trade names ARQUAD® T27 W and ARQUAD® 16-29, and compositions sold by Stepan Company (Northfield, Illinois, USA) under the name Ammonyx Cetac-30.

[0053] (D-1) The amount of cationic surfactant may be 0.1% to 5% based on the weight of the starting material (F) silicone-(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%, and 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%, based on the same criteria. 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%, based on the same criteria.

[0054] 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, sorbitan fatty acid esters, and polyoxyethylene sorbitan fatty acid esters. Examples of commercially available nonionic surfactants include: (i) 2,6,8-trimethyl-4-nonyl polyoxyethylene ether sold under the names TERGITOL™ TMN-6 and TERGITOL™ TMN-10; (ii) C11-15 secondary alkyl polyoxyethylene ethers sold by Dow Chemical Company (Midland, Michigan, USA) under the names TERGITOL™ 15-S-7, TERGITOL™ 15-S-9, TERGITOL™ 15-S-15, TERGITOL™ 15-S-30, and TERGITOL™ 15-S-40; octylphenyl polyoxyethylene (40) ether sold by Dow Chemical Company under the name TRITON™ X405; (iii) nonylphenyl polyoxyethylene (10) ether sold by Stepan Company under the name MAKON™ 10; and (iv) Henkel (v) Ethoxylated alcohols sold by Corp. / Emery Group (Cincinnati, Ohio, USA) under the name Trycol 5953; (v) Ethoxylated alcohols sold by Croda Inc. (Edison, New Jersey, USA) under the names BRIJ® L23 and BRIJ® L4; (vi) Alkyl oxo alcohol polyglycol ethers, such as GENAPOL® UD050 and GENAPOL® UD110; (vii) Alkyl polyethylene glycol ethers based on C10 Guerbet alcohol and ethylene oxide, such as LUTENSOL® XP79.

[0055] Suitable nonionic surfactants also include poly(oxyethylene)-poly(oxypropylene)-poly(oxyethylene) tri-block copolymer. Poly(oxyethylene)-poly(oxypropylene)-poly(oxyethylene) tri-block copolymer is also commonly known as poloxamer. It is a nonionic tri-block copolymer consisting of a central hydrophobic chain of polyoxypropylene (poly(propylene oxide)) and two hydrophilic chains of polyoxyethylene (poly(ethylene oxide)) on either side. Poly(oxyethylene)-poly(oxypropylene)-poly(oxyethylene) tri-block copolymer is commercially available from BASF (Florham Park, New Jersey, USA) and is sold under the trade names PLURONIC®, such as PLURONIC® L61, L62, L64, L81, and P84.

[0056] 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 polyoxyalkylene glycol-modified polysiloxane surfactants. Available commercially available nonionic surfactants include 2,6,8-trimethyl-4-nonyloxypolyethyleneoxyethanol (6EO) and (10EO), sold under the trademark names TERGITOL™ TMN-6 and TERGITOL™ TMN-10; and alkyleneoxypolyethyleneoxyethanol (C), sold under the trademark names TERGITOL™ 15-S-7, TERGITOL™ 15-S-9, and TERGITOL™ 15-S-15. 11~15Secondary alcohol ethoxylates 7EO, 9EO, and 15EO); other C alcohols sold under the trademark names TERGITOL® 15-S-12, 15-S-20, 15-S-30, and 15-S-40. 11~15 Examples of compositions include secondary alcohol ethoxylates; octylphenoxypolyethoxyethanol (40EO) sold under the trademark name TRITON®X-405, and alcohol ethoxylates with the trade name ECOSURF®EH, such as ECOSURF®EH-40. All of these surfactants are sold by Dow Chemical Company.

[0057] Other useful nonionic surfactants available on the market include nonylphenoxypolyethoxyethanol (10EO), sold by Stepan Company under the trademark name MAKON® 10; polyoxyethylene 23-lauryl ether (Laureth-23), commercially available from Sigma Aldrich, Inc. (St. Louis, Missouri, USA); and RENEX® 30, a polyoxyethylene ether alcohol available from Fisher Scientific.

[0058] Nonionic surfactants may also be silicone polyethers (SPEs). Silicone polyethers as emulsifiers may have a rake-shaped structure in which polyoxyethylene or polyoxyethylene-polyoxypropylene copolymer units are grafted onto a siloxane backbone, or SPEs may have an ABA block copolymer structure in which A represents the polyether portion and B represents the siloxane portion of the ABA structure. A preferred SPE is DOWSIL™ OFX-5329 fluid manufactured by Dow Silicones Corporation (Midland, Michigan, USA). Alternatively, nonionic surfactants may be selected from polyoxyalkylene-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, for example, as described in U.S. Patent No. 4,122,029 by Gee et al., U.S. Patent No. 5,387,417 by Rentsch et al., and U.S. Patent No. 5,811,487 by Schulz et al.

[0059] The starting material (D-2) nonionic surfactant may be provided in a diluent, and the amount used may be sufficient to provide 0.1% to 10% of the surfactant based on the weight of the starting material (F) silicone-(meth)acrylate copolymer in the aqueous emulsion. Alternatively, the amount of the nonionic 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%, or at least 1%, or at least 2%, or at least 3%, or at least 4%, and at the same time, the amount of the nonionic surfactant may be up to 10%, or up to 9%, or up to 8%, or up to 7%, or up to 5%, or up to 4%, or up to 3%, or up to 2%, or up to 1%, based on the same criteria. Alternatively, the amount of the nonionic surfactant may be 1% to 10%, or 2% to 10%, or 3% to 10%, or 5% to 9%, or 6% to 8%, or 7%, based on the same criteria. Alternatively, the starting materials (D-1) cationic surfactant and (D-2) nonionic surfactant may be present in a total amount of 10% or less based on the weight of the starting material (F) silicone-(meth)acrylate copolymer in the aqueous emulsion.

[0060] The starting material (E) is water. The water is not limited in general; for example, the water may be treated or untreated. Examples of processes that may be used to purify the water include distillation, filtration, deionization, and combinations of two or more of these, thereby deionizing, distilling, and / or filtering the water. Alternatively, the water may be untreated (for example, tap water, i.e., water supplied from a municipal water system, or well water used without further purification). The amount of water is sufficient to form an aqueous emulsion for emulsion polymerization in step 1) of the process described above. Additional water may be added after step 1). For example, the aqueous emulsion prepared as described above may be diluted with further water to achieve the desired amount of starting material before treating the fabric with the emulsion formulation. Water may be added in amounts of 20% to 97%, 30% to 90%, 40% to 80%, 50% to 97%, 50% to 90%, or 60% to 80%, based on the total weight of all starting materials in step 1. Alternatively, water may be added in amounts of at least 20%, at least 30%, at least 40%, at least 50%, or at least 60%, and at the same time, the amount of water may be up to 97%, at least 96%, at least 95%, or at least 80%, based on the same criteria.

[0061] The silicone-(meth)acrylate copolymer (F) can be prepared by emulsion polymerization of starting materials including the above (A) macromonomer and (C) initiator (and optionally (B) comacromonomer). Alternatively, the silicone-(meth)acrylate copolymer is the reaction product of starting materials consisting essentially of starting material (A) macromonomer and (C) initiator (and (B) comacromonomer and / or (H) chain transfer agent if present). Alternatively, the silicone-(meth)acrylate copolymer is the reaction product of starting materials consisting of starting materials (A) and (C) (and (B) and / or (H) if present). Without wishing to be bound by theory, the starting materials (D) surfactant and (E) water do not copolymerize with the starting materials (A) and (C) (and (B) and / or (H) if present), but the starting materials (D) and (E) are thought to simply act as vehicles for the copolymerization. However, this specification does not exclude the possibility that one or more of the starting materials (D) and / or (E), or a portion of other starting materials added in the course of the method, may participate in the copolymerization reaction of the starting materials containing (A) and (C) with optional starting materials (i.e., (B) and / or (H)) if present.

[0062] The silicone-(meth)acrylate copolymer has the unit formula (F-1):

[0063] [Chemical formula] and includes, wherein each R 1 is a monovalent hydrocarbon group having 1 to 12 carbon atoms independently selected, each D 2 is a divalent hydrocarbon group having 2 to 12 carbon atoms independently, each R 2 is independently selected from the group consisting of H and methyl, each R 3 is a group of the formula OSi(R 4 )3, wherein each R 4 is independently R and DSi(R 5)Selected from the group consisting of 3, wherein each R is an independently selected monovalent hydrocarbon group having 1 to 12 carbon atoms, and each D is independently selected from the group consisting of an oxygen atom, a (poly)alkylene oxide group of 1 to 12 units, and a divalent hydrocarbon group having 2 to 4 carbon atoms, and 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, provided that R 4 , R 5 , and R 6 are selected such that the silicone-(meth)acrylate comonomer unit having at least 5 silicon atoms with the subscript b2, and the subscripts a, b1, and b2 represent the weight fractions of the units in the copolymer, and the 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 includes 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 exemplified above for the formulas (A-1), (B-1), and (B-2). Alternatively, in the unit formula (F-1), for the silicone-(meth)acrylate copolymer, each R 1 can be methyl, each R 2 can be methyl, each D 2 can be propylene, each R 3 can 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, each R is a methyl group, each R 5 is independently selected from the group consisting of R and OSi(R 6 )3, each R 6 is independently selected from the group consisting of R and OSiR3, provided that R 4 , R 5 , and R 6The silicone-(meth)acrylate comacromonomer is selected such that it has 10 to 16 silicon atoms per molecule. Alternatively, the subscript a may have a value such that 0.50 ≤ a ≤ 1, or 0.63 ≤ a ≤ 1, or 0.75 ≤ a ≤ 1, or a = 1. Alternatively, the subscript b1 may have a value such that 0 ≤ b1 < 0.75, or 0 ≤ b1 ≤ 0.5, or 0 ≤ b1 < 0.25, or b1 = 0. Alternatively, the subscript b2 may have a value such that 0 ≤ b2 < 0.75, or 0.01 ≤ b2 ≤ 0.5, or 0.05 ≤ b1 < 0.25, or b1 = 0.25.

[0064] 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 silicone-(meth)acrylate copolymer may have a weight-average molecular weight of at least 200,000 g / mol, or at least 210,000 g / mol, or at least 212,000 g / mol, or at least 225,000 g / mol, or at least 230,000 g / mol, or at least 234,000 g / mol, as measured by GPC, and at the same time, the weight-average molecular weight may be up to 2,000,000 g / mol, or up to 1,000,000 g / mol, or up to 950,000 g / mol, or up to 925,000 g / mol, or up to 912,000 g / mol, or up to 900,000 g / mol, or up to 850,000 g / mol, or up to 800,000 g / mol, or up to 750,000 g / mol, or up to 721,000 g / mol. Alternatively, silicone-(meth)acrylate copolymers may have a weight-average molecular weight of 212,000 g / mol to 912,000 g / mol as measured by GPC. Samples for GPC analysis can be prepared in THF eluent at a copolymer concentration of 10 mg / mL. The solution can be shaken in a flatbed shaker at room temperature for 2 hours. The solution can then be filtered through a 0.45 m PTFE syringe filter before injection. Samples were analyzed using a Waters e2695 LC pump and autosampler equipped with two 5 μM Agilent PLG gel Mixed C columns in series and a Shodex RI501 differential refractive index detector. The instrument was equilibrated at 1 mL / min for 30 minutes, and the sample was flowed at 1 mL / min. Agilent GPC software Cirrus version 3.3 can be used for data acquisition and processing. For molecular weight calibration, all 16 types of linear narrow molecular weight polystyrene standards manufactured by Agilent, with Mp values ​​ranging from 3750 to 0.58 kg / mol, can be used. A cubic polynomial was used for fitting the calibration curve. Therefore, all molecular weight averages, distributions, and molecular weight references provided in this report are polystyrene equivalent values.

[0065] The starting material (G) is a blocked isocyanate added to an emulsion formulation suitable for processing textiles. The term “blocked isocyanate” encompasses mono-, di-, and polyisocyanates in which the isocyanate group reacts 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, including ARKOPHOB® DAN and ARKOPHOB® SR from Archroma (Pratteln, Switzerland), RUCO®-GUARD WEB and RUCO®-LINK XCR from Rudolf GmbH (Geretsreid, Bayern, Germany), and PHOBOL® EXTENDER UXN and PHOBOL® EXTENDER XAN from Archroma. Alternatively, the blocked isocyanate may be an oxime blocked isocyanate such as PHOBOL® EXTENDER XAN. Alternatively, the blocked isocyanate may include a nitrogen-containing heterocyclic (N-heterocyclic) blocked isocyanate. The N-heterocyclic blocked isocyanate includes an isocyanate compound and an N-heterocyclic blocking agent. The isocyanate compound may be a monomer or a polymer. The isocyanate compound may be IPDI, H 12The polyisocyanate may contain, or may contain, units selected from 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 bonded to the aromatic ring. Alternatively, the polyisocyanate may be HDI or MDI. The N-heterocyclic blocking agent may be 2,6-dimethylpyrazine or dimethylpyrazole, for example, 3,5-dimethylpyrazole. Although we do not wish to be bound by theory, it is thought that the blocked isocyanate may not contain species that may interfere with the performance of the isocyanate in the emulsion formulation, such as silicones and amines (not in the blocking group). And, although we do not wish to be bound by theory, it is thought that the blocked isocyanate may be provided in an emulsion or dispersion that does not contain anionic surfactants. Suitable aqueous additives are commercially available and may be provided in aqueous dispersions, examples of which are shown in Table 0 below.

[0066] [Table 1]

[0067] The exact amount of (G) the blocked isocyanate compound will vary depending on various factors including the type and amount of (F) the silicone-(meth)acrylate copolymer formed in step 1), and the fabric being treated, but the weight of (G) the blocked isocyanate may be sufficient to provide 0.25% to 3.75%, or 0.25% to 1%, or 0.25% to 0.5% relative to the weight of the fabric.

[0068] The additional starting materials that may be added in step 1) of the above method include (H) a chain transfer agent. Suitable chain transfer agents include alkyl mercaptans, such as n-octyl mercaptan, n-dodecyl mercaptan, dodecyl mercaptan (dodecanethiol), and / or mercaptans such as 2,2-dimethyldecyl mercaptan. Alternatively, the chain transfer agent may be a water-soluble substance such as mercaptoacetic acid and / or 2-mercaptoethanol. Suitable chain transfer agents are known in the art and are disclosed, for example, in "Radical Polymerization in Industry" by Peter Nesvadba, Performance Chemical Research, GASF Schweiz AG, Basel, Switzerland and in "Encyclopedia of Radicals in Chemistry, Biology and Materials," Online (copyright) 2012 John Wiley & Sons, Ltd.

[0069] Starting material (H) is optional and can be added in an amount of 0-1% based on the total weight of starting material (A) and, if present, starting material (B). Alternatively, (H) chain transfer agent may be used in an amount of 0.5-0.6% based on the same criteria.

[0070] The starting material (I) is an optional 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 include manganese(II) acetate or manganese(II) acetate tetrahydrate, or combinations thereof. Suitable manganese ion sources are commercially available from Millipore Sigma (St. Louis, Missouri, USA), Fisher Scientific (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, but may range from 0.1 ppm to 5,000 ppm based on the total weight of starting material (A) and, if present, starting material (B). Alternatively, the amount of manganese ion source may be greater than 0 ppm, or at least 0.5 ppm, or at least 1 ppm, or at least 1.5 ppm. At the same time, the amount of manganese ion source may 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 total weight of all starting materials in the emulsion formulation for processing the fabric.

[0071] The starting material (J) is an optional phenol compound. Suitable phenol compounds include hydroquinone (HQ), 2-methylhydroquinone, 2-t-butylhydroquinone, dihydroxybenzene (catechol), 4-di-t-butyldihydroxybenzene (4-di-t-butylcatechol), resorcinol, dihydroxyxylene, methoxyphenol (e.g., guaiacol), p-methoxyphenol (also called methyl ether of hydroquinone or MeHQ), tert-butylhydroquinone (tBuHQ), pyrogallol, methylpyrogallol, cresol, phenol, xylenol, butylhydroxytoluene, N-nitrosophenylhydroxylamine, butylhydroxyanisole, and combinations thereof. Alternatively, the phenol compound may be selected from the group consisting of HQ, MeHQ, tBuHQ, and combinations of two or more of these. Suitable phenolic compounds are commercially available, for example, from Millipore Sigma (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, but can range from 5 ppm to 5,000 ppm based on the total weight of starting material (A) and, if present, starting material (B). Alternatively, the amount of the phenolic compound may be at least 5 ppm, or at least 50 ppm, or at least 100 ppm, or at least 150 ppm, and at the same time, the amount of the phenolic compound may be up to 500 ppm, or up to 400 ppm, or up to 350 ppm, or up to 320 ppm based on the total weight of all starting materials in the emulsion formulation for treating the fabric.

[0072] Alternatively, in addition to (I) the manganese ion source and (J) the phenol compound described above, or in place thereof, another inhibitor may be used. For example, the inhibitor may include, or may be, nitrobenzene, 2,2-diphenyl-1-picrylhydrazyl (DPPH), phenothiazine, N,N-diethylhydroxylamine, (2,2,6,6-tetramethylpiperidine-1-yl)oxidanyl (TEMPO), 4-hydroxy-(2,2,6,6-tetramethylpiperidine-1-yl)oxidanyl (4-hydroxyTEMPO), or a combination of two or more of these.

[0073] The starting material (K) is an optional biocide. The amount of biocide varies depending on factors including the type of biocide selected and the desired effect. However, when used, the amount of biocide may be greater than 0% to 5% based on the total weight of all starting materials in the emulsion formulation. Starting material (K) is exemplified by (K-1) fungicides, (K-2) herbicides, (K-3) insecticides, (K-4) antimicrobial agents, or combinations thereof. Suitable biocides are disclosed, for example, in U.S. Patent No. 9,480,977.

[0074] An emulsion formulation suitable for processing textiles may optionally further contain a starting material (P) and a penetrant. Suitable penetrants are exemplified by glycol ethers commercially available from The Dow Chemical Company, including DOWANOL® DPM, TPM, PPh, EPh, Methyl CARBITOL®, and Butyl CARBITOL®.

[0075] An emulsion formulation suitable for treating textiles may optionally further contain a sufficient amount of (Q) softening additive to impart softness to the textile without significantly reducing its water-repellent and / or oil-repellent properties, which is formula

[0076] [ka] (Q-1) alkylpolysiloxane, where each R 19 Q-1 is a monovalent saturated hydrocarbon group having 1 to 18 carbon atoms, where the subscript aa has an average value of 20 to 300, or a combination of (Q-2) containing 60 to 70% by weight based on the total weight of all (Q-2) starting materials, a combination of (Q-1) alkylpolysiloxane containing 29 to 39% by weight based on the total weight of all (Q-2) starting materials, a combination of (Q-2-1) silicone resin having a hardness of 20 or higher as measured with a Type A durometer in accordance with JIS K6249:2003, having 0 to 2% by weight based on the total weight of all (Q-2) starting materials, a functional group equivalent of 100 g / mol to 20,000 g / mol, where equivalent means the molecular weight of amino-functional polyorganosiloxane per mole of nitrogen atoms, and a kinematic viscosity at 25°C measured by the method of JIS K2283:2000 is 10 to 100,000 mm². 2 The combination is selected from (Q-2-2) amino-functional polyorganosiloxanes of the form / s. Alternatively, the (Q-2-2) amino-functional polyorganosiloxane may be present in an amount of 1% to 2% according to the same criteria.

[0077] (Q-1) Alkylpolysiloxane is formula

[0078] [ka] It has, in the formula, each R 19 R is a monovalent saturated hydrocarbon group having 1 to 18 independently selected carbon atoms, where the subscript aa has an average value of 20 to 300. 19 The monovalent saturated hydrocarbon group may be an alkyl group, or an alkyl group with 1 to 6 carbon atoms. Alternatively, the alkyl group may have 1 to 3 carbon atoms, or 1 to 2 carbon atoms. Alternatively, each R 19This can be methyl. Suitable alkylpolysiloxanes, such as bistrimethylsiloxy-terminated polydimethylsiloxanes, are known in the art and are commercially available, for example, from The Dow Chemical Company (Midland, Michigan, USA) as XIAMETER® 200 fluid.

[0079] Alternatively, the (Q) flexible additive may consist of a (Q-2) combination containing 60-70% by weight based on the total weight of all the starting materials of (Q-2), a (Q-1) alkylpolysiloxane combination containing 29-39% by weight based on the total weight of all the starting materials of (Q-2), a (Q-2-1) silicone resin combination containing 1-2% by weight based on the total weight of all the starting materials of (Q-2), having a hardness of 20 or higher as measured on a Type A durometer in accordance with JIS K6249:2003, a functional group equivalent of 100-20,000 g / mol, where equivalent refers to the molecular weight of amino-functional polyorganosiloxane per mole of nitrogen atoms, and a kinematic viscosity at 25°C measured by the method of JIS K2283:2000 of 10-100,000 mm². 2 This may include combinations of (Q-2-2) amino-functional polyorganosiloxanes that are / s.

[0080] The starting material (Q) softening additive may be provided in a second aqueous emulsion comprising (Q) softening additive, (D') surfactant (which may be as described above for starting material (D) surfactant), and (E') water (which may be as described above for starting material (E)). The second aqueous emulsion can be prepared by varying the type and amount of the starting materials described herein by known methods, such as those described in U.S. Patent Application Publication No. 2020 / 0332148.

[0081] When selecting starting materials to be added to the aqueous emulsion prepared in step 1) above and the emulsion formulation formed in step 2) above, the types of starting materials may overlap, as the specific starting materials described herein may have two or more functions. The starting materials used for the aqueous emulsion and / or emulsion formulation may be different from each other.

[0082] An emulsion formulation suitable for processing textiles comprises, as described above, (F) silicone-(meth)acrylate copolymer, (D) surfactant, (E) water, and (G) blocked isocyanate. The emulsion formulation may optionally further contain (I) manganese ion source, (J) phenol compound, (K) biocide, (L) additional water (as described above for starting material (E)), (M) flame retardant, (N) wrinkle reducer, (O) antistatic agent, (P) penetrant, (Q) softening additive, and additional starting materials selected from the group consisting of two or more combinations of 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 using starting materials that do not contain fluorocarbons. For example, the emulsion formulation may not contain any starting materials containing fluorine atoms covalently bonded to carbon atoms.

[0083] The emulsion formulation prepared as described above can be used to treat textiles. For example, a method for treating a textile includes I) coating the textile with the emulsion formulation described above, and II) heating the textile. Step I) can be carried out by any convenient method such as padding, dipping, or spraying the textile with the emulsion formulation. However, this method must be sufficient to yield sufficient amounts of (F) silicone-(meth)acrylate copolymer and (G) blocked isocyanate to impart durable oil resistance to the textile, according to the method described below. This method may be sufficient to yield 0.25% to 10% by weight of (F) silicone-(meth)acrylate copolymer and 0.1% to 3.75% or 0.25% to 1% by weight of (G) blocked isocyanate, based on the weight of the textile.

[0084] Step II) can be carried out by any convenient method, such as placing the fabric in an oven. Heating of the fabric may be carried out to remove all or part of the water and / or to cure the emulsion formulation. The exact temperature depends on various factors, including the temperature sensitivity of the selected fabric type and the desired drying time. However, heating may be carried out at a temperature above 100°C to remove water. Alternatively, the temperature may be above 100°C to 200°C for a sufficient time to remove all or part of the water, deblock the blocked isocyanate, and / or cure the (F) silicone-(meth)acrylate copolymer.

[0085] The fabrics to be treated are not particularly limited. Suitable fabrics include natural fabrics such as cotton, silk, linen, and / or wool; fabrics derived 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 of these (e.g., blends such as polyester / cotton blends). The form of the fabric is also not particularly limited. The emulsion formulations described herein are suitable for use in any form of fabric, such as woven fabrics, knitted fabrics, or nonwoven fabrics. [Examples]

[0086] The following embodiments are provided to those skilled in the art to illustrate the present invention and should not be construed as limiting the scope of the invention as defined in the claims.

[0087] [Table 2]

[0088] [ka]

[0089] In this Reference Example 1, a silicone-(meth)acrylate copolymer emulsion was prepared as follows. All macromonomers, water, and surfactants were added to a wide-mouthed bottle (approximately 400 mL) in the selections and amounts shown in Table 2 below. The emulsion was prepared using an ultrasonic device (Fisherbrand Model 705 ultrasonic dismembraner, amplitude 50, output approximately 62 W, ​​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 was added (0.26 g), 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 bottles.

[0090] [Table 3] * A 2.5 wt% aqueous solution of 0.4 g of 4-methoxyphenol, 0.006 g of hydroquinone, and a 0.7 wt% aqueous solution of 0.12 g of Mn(II) acetate tetrahydrate.

[0091] In this Reference Example 2, emulsion formulations were prepared, fabrics were treated, and oil repellency was evaluated as follows: All fabrics were washed / dried before coating. The water absorption of each fabric was measured, and then emulsion formulations were prepared based on the water absorption weight by adding a blocked isocyanate additive. Table 3 provides the exact emulsion formulations. Each emulsion formulation was then poured into a Mathis HVF padder (roll speed of 2 m / min at 60 psi) for coating. The fabrics were passed through the coater until no drying spots were observed (approximately twice), and then passed through a Mathis LTF oven with forced air at 160°C for 3 minutes. The weight of the fabrics before and after coating was measured to obtain the actual coating weight. Each sample was approximately 2 wt% on the fabric.

[0092] In Example 7, sheets were washed in a Whirlpool Model WTW4855HW1 washing machine using a 90°F wash followed by a low-temperature rinse cycle (approximately 70°F) (settings: normal cycle, high wash temperature, deep wash, auto-sensing rinse). Tide Free and Gentle Liquid Laundry Detergent was used as the detergent, with 39g used for 6 pounds of fabric. For smaller amounts, the amount of detergent was adjusted proportionally. The hot water used to wash the samples passed through the building's water softening system. The cold water was also softened and passed through a Franklin Electric PDIMX-60 water softening system using standard settings (default hardness setting of 20). The samples were dried using a Whirlpool Model WED4850HW0 dryer (automatic drying cycle at approximately 140°F).

[0093] [Table 4]

[0094] To determine the oil repellency (surface ranking), a modified version of the American Association of Textile Chemists and Colorists (AATCC) standard test method 118 was used. Surface rankings A, B, C, and D were used, as described in AATCC 118 and as shown in Figure 3 of Lei et al.'s "Fluorine-free low surface energy organic coating for anti-stain applications," Progress in Organic Coatings 103 (2017) 182-192, 184. A surface ranking indicated clear, well-rounded oil droplets. B indicated partially darkened, rounded droplets. C indicated the wick was visible and / or completely wet, and D indicated completely wet. The modifications to this test method were that olive oil was used and the time was extended from 10 seconds to 5 minutes. Passing required an A or B rating after 5 minutes. A C or D surface rating represented unacceptably high oil absorption by the cloth. This test used relatively large olive oil droplets, i.e., at least 500 μL per drop.

[0095] In Table 3, * This indicates that the sample was washed five times before testing for oil repellency. ** This shows the value measured 10 seconds later, not 1 minute later. ***This indicates that the sample still had a surface ranking of A when the value was measured again after 15 minutes. The data in Table 3 shows that the presence of the blocked isocyanate additive dramatically increased oil repellency. For example, Example 1 and Comparative Example 2 (Comparative 2) contained the same starting material (i.e., emulsion of 3MT-ALMA copolymer), except that the blocked isocyanate was present in Example 1 but not in Comparative Example 2. Example 1 showed a dramatic improvement in oil repellency under all tested conditions. Similarly, Example 4 showed dramatically improved oil repellency compared to Comparative Example 5 after 1 minute and 5 minutes. Comparative Example 6 demonstrates that the use of stearyl acrylate in the copolymer unexpectedly does not result in passing performance. Example 7 demonstrated unexpected cleaning durability without adding crosslinking points to the copolymer main chain. Examples 1, 2, 5 and 6 demonstrate that multiple fabric types can be made oil-repellent using the emulsion formulations described herein. Furthermore, Examples 1 and Comparative Example 2 demonstrate that the use of isocyanate additives improves oil repellency.

[0096] Additional samples were prepared and evaluated as follows.

[0097] Method A In this synthesis example 1, a silicone-(meth)acrylate copolymer emulsion was prepared as follows. All starting materials (excluding the initiator) were added to a wide-mouthed bottle (approximately 400 mL) in the selection and amounts shown in Table 4 below. The emulsion was prepared using an ultrasonic device (Fisherbrand Model 705 ultrasonic dismembraner, amplitude 50, output approximately 62 W, ​​2 minutes). 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-methylpropionamidine) dihydrochloride (AIBN) was added (0.26 g), 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 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.

[0098] Method B In this synthesis example 2, a silicone-(meth)acrylate copolymer emulsion was prepared as follows. All starting materials (except the initiator) were added to a wide-mouthed bottle (approximately 400 mL) in the selection and amounts shown in Table 4 below. The stearyl acrylate monomer was first melted and added as a liquid. Furthermore, the emulsion was mixed with hydroquinone (50 ppm based on the monomer) and Mn(II) acetate. * The mixture was suppressed with 4H2O (1.5 ppm based on monomer) and methyl ether hydroquinone (150 ppm based on monomer). The resulting material was sonicated using a Fisher Brand ultrasonic dismembraner at an amplitude of 50 for 2 minutes to prepare an emulsion. The resulting emulsion was then transferred to a 500 mL four-necked flask equipped with a reflux condenser, nitrogen inlet, overhead 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 temperature, 0.25 g of 2,2'-azobis(2-methylpropionamidine) dichloride was added, and the reaction was carried out for 6 hours. The resulting substance was then slowly cooled to 30-40°C with 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.

[0099] In preparing Method C, several solutions were prepared as follows. Preparation of Solution A: 0.0566 g of t-butyl hydroperoxide (70% in water) was added, followed by the addition of sufficient water to prepare a 10 g solution. Preparation of Solution B: 0.0773 g of isoascorbic acid was added, followed by the addition of sufficient water to prepare a 10 g solution. Preparation of Solution C: 6 mg of iron(II) sulfate heptahydrate was added, followed by the addition of sufficient water to prepare a 10 g solution.

[0100] Method C In this synthesis example 3, the emulsion was prepared as follows: The starting materials were weighed according to the selection and quantities shown in Table 4 below and placed in a 400 mL wide-mouthed bottle. Stearyl and behenyl acrylate monomers were first melted and added as liquids. Furthermore, the emulsion was mixed with hydroquinone (50 ppm based on monomer) and Mn(II) acetate. * The mixture was suppressed with 4H2O (1.5 ppm based on monomer) and methyl etherhydroquinone (150 ppm based on monomer). The resulting material was sonicated using a Fisher Brand ultrasonic dismembraner at an amplitude of 50 for 2 minutes to create an emulsion. The crude emulsion was then passed through a 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-methylpropionamidine) 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 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.

[0101] [Table 5]

[0102] In this Reference Example 3, the weight-average molecular weights of several silicone-(meth)acrylate copolymers listed in Table 4 were measured by GPC as follows: A sample for GPC was prepared by dissolving 174.41 mg of the 29% emulsion copolymer sample listed in Table 4 in 10 mL of THF (5 mg / mL) in a 20 mL vial. The sample was left 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 autosampler equipped with two 5 μM Agilent PLG gel Mixed 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 flowed at 1 mL / min. The results for the copolymers tested are shown in Table 5 below.

[0103] [Table 6]

[0104] In this Reference Example 5, an emulsion formulation was prepared using the aqueous copolymer emulsion described in Table 4, and the cloth was treated using the same method as described above in Reference Example 2, and its oil repellency was evaluated. The emulsion formulation and the results of the oil repellency are shown in Table 6 below.

[0105] [Table 7]

[0106] Examples 9-13 and Comparative Examples 8-10 demonstrate that the Mw of a silicone-(meth)acrylate copolymer can affect its oleophobic properties. While it has been shown that silicone-(meth)acrylate copolymers can be prepared using multiple methods (e.g., methods A-C in Synthesis Examples 1-3), oleophobicity improved under the tested conditions when the Mw of the silicone-(meth)acrylate copolymer was >181,000 g / mol. These results teach a difference from the disclosure in Progress in Organic Coatings, Lei, H. et al. 2016, which discloses a molecular weight of 80,000 g / mol for oleophobicity testing. Examples 14-17 demonstrate the range of applications for blocked isocyanate additives (16:1-2:1 copolymer:additive, in these cases additive=XAN).

[0107] In this synthesis example 4, PDMS resin 1 (described in Example 1 of U.S. Patent Application Publication No. 20230038369) was prepared as follows: 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 at room temperature along with 47.95 g of dry xylene. The round-bottom flask was equipped with a condenser, nitrogen inlet, overhead stirrer, and thermocouple probe. The system was purged with nitrogen for 5 minutes, then the solution was heated to 65°C and held for 24 hours.

[0108] In this synthesis example 5, PDMS resin 2 was prepared as follows: 80DP 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 methylene chloride. The substance was washed with a saturated solution of NaHCO3 (75 mL x 5). Then, the water was removed by distillation, leaving a pale yellow liquid product. PDMS resin 2 gelled by the next day, making it impossible to coat the fabric with this resin.

[0109] The procedures for these comparative examples 18 and 19 included pretreatment of the fabric, followed by treatment with PDMS resin 1, and were as follows: A 1 × 1 cm PES or nylon fabric was washed with 200 proof ethanol and then dried in an oven at 80°C for 10 minutes. A silica sol was then prepared by hydrolysis of tetraethoxysilane (2.08 g, 10 mmol) in 60 mL of ethanol / 15 mL of DI water in the presence of ammonium hydroxide (2.75 mL). The fabric was immersed in the sol for 5 minutes and dried at room temperature (approximately 30 minutes). This process was repeated two more times. 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 × 1 cm PES or nylon fabric sample was coated three times by immersion in PDMS resin 1. The sample was cured at 200°C for 1 hour.

[0110] The procedures for Comparative Examples 20 and 21 were as follows: A 1 x 1 cm PES or nylon cloth sample was coated three times by immersion in synthetic PDMS resin 1. The sample was cured at 200°C for 1 hour.

[0111] The procedures for Comparative Examples 22 and 23 were as follows. A 1 x 1 cm PES or nylon cloth was washed with 200 proof ethanol and then dried in an oven at 80°C for 10 minutes. A silica sol was then prepared by hydrolysis of tetraethoxysilane (2.08 g, 10 mmol) in 60 mL of ethanol / 15 mL of DI water in the presence of ammonium hydroxide (2.75 mL). The cloth was immersed in the sol for 5 minutes and dried at room temperature (approximately 30 minutes). This process was repeated two more times. The cloth 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.

[0112] [Table 8]

[0113] Comparisons 18 and 19 correspond to Example 2 disclosed in U.S. Patent Application Publication No. 20230038369. These received a failing oil repellency rating after 5 minutes using the Modified AATCC Method 118. In contrast, the present invention (e.g., as shown in Examples 1 and 5 in Table 3 above) exhibited excellent oil repellency using the AATCC Method 118. Comparisons 20 and 21 tested the 3MT-ALMA / vinyltrimethoxysilane copolymer after removing the sol-gel and nanoparticle treatments, and these examples also failed the Modified AATCC Method 118 after 5 minutes.

[0114] In this comparative example 24 (comparison 24), the PES cloth was treated with two separate emulsions in two separate steps. First, the cloth was coated with the Phobol-XAN emulsion (0.69 g of XAN + 74.31 g of DI water) described in the coating / curing method of Reference Example 2 above. In the second step, the cloth was treated with the copolymer 1 emulsion from Table 2 above, which was prepared by combining 5.75 g of copolymer emulsion 1 from Table 2 with 69.25 g of DI water, using the same coating and curing method as described above in Reference Example 2.

[0115] Comparative Example 24 shows a pretreatment method for a blocked isocyanate (XAN) additive similarly described in Example 2 of U.S. Patent Application Publication No. 20230038369 (comparisons 18 and 19 above). Comparative Example 24 did not pass the modified AATCC method 118 after 10 seconds and had worse oil repellency than comparative examples 18 and 19 at 10 seconds.

[0116] In this Comparative Example 25, 3.83 g of copolymer emulsion 1, as described in Table 2, and 1.59 g of DOWSIL® IE-8749, a 70% solid silicone durable water repellent commercially available from The Dow Chemical Company, were added to a 125 g Nalgene plastic bottle. The contents were then mixed by inverting the bottle twice. A cloth was covered and its oil repellency was measured as described in Reference Example 2. The cloth received a C rating after 10 seconds and a D rating after 30 seconds. Comparative Example 25 showed that the silicone material (active substance in IE-8749) blended with the 3MT-ALMA copolymer failed the oil repellency test specified herein after 30 seconds.

[0117] In this Reference Example 6, the study of the blocked isocyanates listed in Table 8 below 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 contents were mixed by inverting the bottle twice. The order of addition was not important. In this Reference Example 6, the cloth was treated with the textile treatment emulsion prepared as described above. All cloths were washed, dried, and then coated. Next, the textile treatment emulsion as described in Table 9 below was poured into a beaker, followed by immersion coating, and the cloth was passed through a Werner Mathis AG Textilmaschinen padder (tension setting 70) for coating. After one pass, the sample was placed in a 160°C forced-air Mathis LTF oven for 3 minutes. The sample was evaluated for oil repellency using the method described above in Reference Example 2. The results are shown in Table 10 below.

[0118] [Table 9]

[0119] [Table 10]

[0120] [Table 11]

[0121] While we do not wish to be bound by theory, it is conceivable that additives do not need to contain species that could interfere with the performance of isocyanates in emulsion formulations, such as silicones and amines (not in the blocking group). Furthermore, while we do not wish to be bound by theory, it is conceivable that blocked isocyanates can be provided in emulsions or dispersions that do not contain anionic surfactants.

[0122] In this comparative example 26, 2.25 g of Daikin XF-5100 (available in the US as an alternative to XF-5003, 3%), 4.5 g of RUCODRY Eco Plus (6%), and 1.875 g of RUCO-LINK XCR (2.5%) (both from Rudolf Group) were used with 66.125 g of water. The resulting samples were coated onto PES and evaluated by the modified AATCC 118 test of Reference Example 2. The treated cloth failed the oil repellency test after 30 seconds. [Industrial applicability]

[0123] The above examples demonstrate that the emulsion formulations and processes described herein can produce fabrics with durable oil repellency. As used herein, “oil repellency” means a surface ranking of A or B after a large oil droplet has been in contact with the fabric for 5 minutes, as measured by the modified AATCC 118 test described above. As used herein, “durability” means that after treatment with an emulsion formulation as described herein, the fabric can be washed at least 5 times and the fabric still retains its oil repellency as described above (as shown in Example 7 above).

[0124] The inventors have surprisingly found that including a blocked isocyanate in the emulsion formulation improves the oil repellency of fabrics treated with the emulsion formulation compared to fabrics treated with a comparative composition that does not contain a blocked isocyanate (see Examples 1 and Comparative Example 2, and Examples 2 and Comparative Example 3 above). This finding is particularly unexpected when the starting materials copolymerized by the above method and the resulting silicone-(meth)acrylate copolymer do not contain crosslinking groups. Furthermore, the inventors have surprisingly found that the emulsion formulation imparts durable oil repellency to the fabric even when the fabric is not pretreated, for example, by plasma treatment or washing, before being coated with the emulsion formulation.

[0125] Definitions and Usage of Terms All quantities, ratios, and percentages in this specification are based on weight unless otherwise specified. The "Summary of the Invention" and the "Abstract" are incorporated herein by reference. Unless otherwise specified in the context of the specification, 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 Sections §2111.03 I, II, and III of the "Manual of Patent Examining Procedure Ninth Edition," Revision 08.2017, Last Revised January 2018. The use of "for example," "eg," "such as," and "including" to list examples is not limited to the examples listed. Thus, "for example" or "such as" means "for example, but not limited to these" or "such as, but not limited to these," encompassing other similar or equivalent examples. The symbol "<" represents "less than", the symbol ">" represents "greater than", the symbol "≦" represents "less than or equal to", and the symbol "≧" represents "greater than or equal to". Abbreviations used in this specification have the definitions in Table 11.

[0126] [Table 12]

Claims

1. A method for preparing an emulsion formulation suitable for processing textiles, wherein the method is: 1) comprising copolymerizing the starting materials, wherein the starting materials are (A) Formula 【Chemistry 1】 A silicone-(meth)acrylate macromonomer, wherein each R １ is a monovalent hydrocarbon group consisting of 1 to 12 independently selected carbon atoms, D ２ R is a divalent hydrocarbon group consisting of 2 to 12 carbon atoms. ２ (A) a silicone-(meth)acrylate macromonomer selected from the group consisting of H and methyl, Optionally comprising (B) a silicone-(meth)acrylate comacromonomer, wherein (B) the silicone-(meth)acrylate comacromonomer has a formula selected from the group consisting of formula (B-1), formula (B-2), and combinations of both formula (B-1) and formula (B-2), Equation (B-1) is, 【Chemistry 2】 And in the formula, each R １ is a monovalent hydrocarbon group consisting of 1 to 12 independently selected carbon atoms, D ２ R is a divalent hydrocarbon group consisting of 2 to 12 carbon atoms. ２ It is selected from the group consisting of H and methyl, Equation (B-2) is, 【Transformation 3】 and in the formula, R ２ is selected from the group consisting of H and methyl, D ２ is a divalent hydrocarbon group having 2 to 12 carbon atoms, and each R ３ is a group of the formula OSi(R ４ ) ３ In the formula, each R ４ is independently selected from the group consisting of R and DSi(R ５ ) ３ In the formula, each R is an independently selected monovalent hydrocarbon group having 1 to 12 carbon atoms, each D is independently selected from the group consisting of an oxygen atom, a (poly)alkylene oxide group of 1 to 12 units, and a divalent hydrocarbon group having 2 to 4 carbon atoms, and each R ５ is independently selected from the group consisting of R and DSi(R ６ ) ３ In the formula, each R ６ is independently selected from the group consisting of R and DSiR ３ provided that R ４ , R ５ , and R ６ are selected such that the silicone-(meth)acrylate macromonomer of formula (B-2) has at least 5 silicon atoms per molecule. Starting material (A) is present in an amount of more than 25% to 100% by weight, based on the total weight of starting material (A) and starting material (B). Starting material (B) is present in an amount of 0 to less than 75% by weight, based on the total weight of starting material (A) and starting material (B). Starting material (A) and starting material (B) are copolymerized in the presence of an additional starting material, the additional starting material being (C) Initiator, (H) chain transfer agent, optional (I) manganese ion source, and (J) Optionally includes a phenol compound. If one of condition (i) or condition (ii) is met, Condition (i) is that step 1) further comprises adding a solvent before or during step 1), (F) removing the solvent after forming a silicone-(meth)acrylate copolymer, and (F) forming an aqueous emulsion comprising the silicone-(meth)acrylate copolymer, (D) a surfactant, and (E) water. Condition (ii) is that step 1) includes an emulsion polymerization reaction, and the additional starting materials further include (D) a surfactant and (E) water. The product of step 1) comprises (F) the silicone-(meth)acrylate copolymer, (D) the surfactant, and (E) an aqueous emulsion containing water. 2) A method comprising combining the aqueous emulsion with a material comprising (G) a blocked isocyanate and optionally additional starting material, wherein the additional starting material, if present, is selected from the group consisting of (K) a biocide, (L) additional water, (M) a flame retardant, (N) a wrinkle reducer, (O) an antistatic agent, (P) a penetrating agent, (Q) a softening agent, and two or more combinations thereof.

2. Each R １ However, it is methyl, Each R ２ However, it is methyl, Each D ２ However, it is propylene, Each R ３ However, formula OSi(R ４ ) ３ It is the basis of, and in the formula, Each R ４ These are independently R and OSi(R) ５ ) ３ Selected from the group consisting of, in the formula, Each R is methyl, Each R ５ These are independently R and OSi(R) ６ ) ３ Selected from the group consisting of, in the formula, Each R ６ R and OSIR are independent of each other. ３ Selected from the group consisting of, However, R ４ , R ５ , and R ６ The method according to claim 1, wherein the silicone-(meth)acrylate comacromonomer of formula (B-2) is selected to have 10 to 16 silicon atoms per molecule.

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

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

5. The (B) silicone-(meth)acrylate comacromonomer of formula (B-2) is present in an amount of 1% to 50% by weight based on the total weight of the starting materials (A) and (B), and formula (B-2) 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, The method according to any one of claims 1 to 3, selected from the group consisting of 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. (C) The method according to any one of claims 1 to 5, wherein the initiator comprises 2,2'-azobis(2-methylpropionamidine) dihydroxychloride.

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

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

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

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

11. (G) The method according to any one of claims 1 to 10, wherein 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 is (F) The silicone-(meth)acrylate copolymer, wherein the silicone-(meth)acrylate copolymer has the following unit formula: 【Chemistry 4】 Including, in the formula, Each R １ This is a monovalent hydrocarbon group consisting of 1 to 12 independently selected carbon atoms. Each D ２ These are independently divalent hydrocarbon groups consisting of 2 to 12 carbon atoms. Each R ２ These are independently selected from the group consisting of H and methyl, Each R ３ is the formula OSi(R ４ ) ３ It is the basis of, and in the formula, Each R ４ R and DSi(R) are independent of each other. ５ ) ３ Selected from the group consisting of, where each R is an independently selected monovalent hydrocarbon group of 1 to 12 carbon atoms, Each D is independently selected from the group consisting of an oxygen atom, 1 to 12 units of (poly)alkylene oxide groups, and 2 to 4 carbon atoms of a divalent hydrocarbon group. Each R ５ R and DSi(R) are independent of each other. ６ ) ３ Selected from the group consisting of, in the formula, Each R ６ R and DSiR are independent of each other. ３ Selected from the group consisting of, However, R ４ , R ５ , and R ６ The silicone-(meth)acrylate comacromonomer unit having the subscript b2 is selected to have at least five silicon atoms, The subscripts a, b1, and b2 represent the weight fraction of the unit in the copolymer, and the subscripts a, b1, and b2 are, 0.25 < a ≤ 1, and The value is such that 0 ≤ (b1 + b2) < 0.

75. The silicone-(meth)acrylate copolymer further comprises (F) the silicone-(meth)acrylate copolymer, (D) The surfactant and, (E) The water and, (G) A textile treatment emulsion comprising the block isocyanate.

13. The textile treatment emulsion according to claim 12, wherein the textile treatment emulsion does not contain fluorocarbons.

14. A method for processing textiles, wherein the method is I) The fabric is coated with the emulsion formulation according to claim 12 or claim 13, II) A method comprising heating the fabric.

15. A composition, (F) Silicone-(meth)acrylate copolymer, with unit formula: 【Transformation 5】 Including, in the formula, Each R １ This is a monovalent hydrocarbon group consisting of 1 to 12 independently selected carbon atoms. Each D ２ These are independently divalent hydrocarbon groups consisting of 2 to 12 carbon atoms. Each R ２ These are independently selected from the group consisting of H and methyl, Each R ３ is the formula OSi(R ４ ) ３ It is the basis of, and in the formula, Each R ４ R and DSi(R) are independent of each other. ５ ) ３ Selected from the group consisting of, in the formula, Each R is a monovalent hydrocarbon group consisting of 1 to 12 carbon atoms, selected independently. Each D is independently selected from the group consisting of an oxygen atom, 1 to 12 units of (poly)alkylene oxide groups, and 2 to 4 carbon atoms of a divalent hydrocarbon group. Each R ５ R and DSi(R) are independent of each other. ６ ) ３ Selected from the group consisting of, in the formula, Each R ６ R and DSiR are independent of each other. ３ Selected from the group consisting of, However, R ４ , R ５ , and R ６ The silicone-(meth)acrylate comacromonomer units having the subscript b2 are selected to have at least five silicon atoms, The subscripts a, b1, and b2 represent the weight fraction of the unit in the copolymer, and the subscripts a, b1, and b2 are, 0.25 < a ≤ 1, and (F) Silicone-(meth)acrylate copolymer having a value such as 0 ≤ (b1 + b2) < 0.75, (I) A manganese ion source, (J) A composition comprising a phenol compound.

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

18. The textile treatment emulsion according to claim 12 or 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 according to claim 18, wherein the weight-average molecular weight is 212,000 g / mol to 2,000,000 g / mol.

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