Textile treatments for imparting oil repellency include the use of silicone-(meth)acrylate copolymers and urethanes

Abstract

A textile treatment emulsion that can be prepared by mixing an aqueous emulsion of a silicone-(meth)acrylate copolymer and an aqueous emulsion of an alkyl carbamate. The textile treatment emulsion can be applied to a fabric and heated, thereby increasing the oil repellency of the fabric.

Description

Cross-references to related applications

[0001] This application claims priority to U.S. Provisional Patent Application No. 63 / 593716, filed October 27, 2023; U.S. Provisional Patent Application No. 63 / 674322, filed July 23, 2024; U.S. Provisional Patent Application No. 63 / 674323, filed July 23, 2024; U.S. Provisional Patent Application No. 63 / 674325, filed July 23, 2024; and U.S. Provisional Patent Application No. 63 / 593716, 63 / 674322, 63 / 674323, 63 / 674325, and 63 / 674328, filed July 23, 2024, pursuant to 35 USC §119(e). Technical Field

[0002] Textile treatment emulsions contain silicone-(meth)acrylate copolymers and urethane compounds. These emulsions can be used to impart oil-repellent properties to textiles. Background Technology

[0003] Per- and polyfluoroalkyl substances (PFAS) have dominated the textile coatings market for many years; however, due to environmental regulations, customers and regulators want to eliminate PFAS. There has been a persistent need in the textile industry to find an alternative to PFAS that imparts oil repellency to textiles and is compatible with current capital infrastructure, as plasma treatments and engineered surface structures cannot typically be performed in the factory using existing equipment.

[0004] WO2023019044 discloses an organosilicon-(meth)acrylate copolymer emulsion that can impart water repellency to textiles. However, this disclosure does not address the issue of oil repellency. Summary of the Invention

[0005] A method for preparing a textile treatment emulsion includes: I) mixing starting materials comprising i) an aqueous copolymer emulsion comprising a silicone-(meth)acrylate copolymer, a surfactant, and water; and ii) an aqueous composition comprising an alkyl carbamate, a surfactant, and water; wherein the starting material i) the aqueous copolymer emulsion and the starting material ii) the aqueous composition are used in an amount sufficient to provide a weight ratio of silicone-(meth)acrylate copolymer:alkyl carbamate of 1:<9. Detailed Implementation

[0006] The starting material i) an aqueous copolymer emulsion comprising a silicone-(meth)acrylate copolymer, a surfactant, and water can be prepared as described in U.S. Provisional Patent Application 63 / 593716, which is hereby incorporated by reference. In the starting material i) aqueous copolymer emulsion described above, the silicone-(meth)acrylate copolymer comprises the following unit formula:

[0007] , where 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 selected; and 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; where each R 4 is independently selected from the group consisting of R and DSi(R 5 )3, where each R is a monovalent hydrocarbon group having 1 to 12 carbon atoms independently selected, 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; each R 5 is independently selected from the group consisting of R and DSi(R 6 )3; where 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 copolymer macromonomer unit having subscript b2 has at least 5 silicon atoms; subscripts a, b1, and b2 represent the weight fractions of the units in the copolymer, and the values of subscripts a, b1, and b2 are such that 0.25 < a ≤ 1; and 0 ≤ (b1 + b2) < 0.75. As described below, based on the combined weight of the macromonomers used to prepare the copolymer, (a + b1 + b2) = 1.

[0008] The organosilicon-(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 organosilicon-(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 organosilicon-(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.

[0009] Those skilled in the art will recognize that the above-described organosilicon-(meth)acrylate copolymer (copolymer) can be prepared by free radical polymerization via the method described below, and that this method will form the end portion of the copolymer. The copolymer having the above-described unit formula also contains end portions that can be derived from an initiator, a chain transfer agent, or both, such as, for example, Odian, George (2004). "Principles of Polymerization (… Principles of PolymerizationAs described in (4th edition). New York: Wiley-Interscience, ISBN 978-0-471-27400-1.

[0010] The copolymer can be prepared by methods including the following:

[0011] 1) Copolymerize the starting materials, which include: (A) Organosilicon-(meth)acrylate macromonomers, wherein 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 Selected from the group consisting of H and methyl; optionally (B) organosilicon-(meth)acrylate copolymer macromonomer, wherein the organosilicon-(meth)acrylate copolymer 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 , 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 Selected from the group consisting of H and methyl groups; formula (B-2) is , where R 2 Select from the group consisting of H and methyl groups; D 2 It 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 6The organosilicon-(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% to 100% by weight based on the combined weight of starting materials (A) and (B); and wherein starting material (B) is present in an amount of 0% to <75% by weight based on the combined weight of starting materials (A) and (B); and wherein starting materials (A) and (B) are copolymerized in the presence of an additional starting material, wherein the additional starting material comprises 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.

[0012] Step 1) of the method for preparing the copolymer may include an emulsion polymerization reaction. Additional starting materials used in this emulsion polymerization method 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 (when 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 (when present), (D) surfactants and (E) water, and (H) chain transfer agents (when present), the starting materials (I) manganese ion source and / or (J) phenolic compounds can inhibit the formation of acrylic acid radicals, which can affect copolymer formation during copolymerization in step 1). These starting materials can be mixed under shear to form i) an aqueous copolymer emulsion. Shear mixing can be carried out by any convenient means for forming an aqueous emulsion, such as ultrasonication and subsequent microfluidization. Equipment for shear mixing (such as rotor-stator, acoustic spectrometer, ultrasonicator, homogenizer, microfluidizer, and high-speed mixer) is known in the art and commercially available. Without being bound by theory, it is believed that shear mixing can be used to obtain submicron particle sizes in the emulsion. In step 1), a starting material comprising (A) a silicone-(meth)acrylate macromonomer, (B) a silicone-(meth)acrylate copolymer macromonomer (if present), (C) an initiator (and (H) a chain transfer agent (if present)) is copolymerized to form (F) a silicone-(meth)acrylate copolymer, thereby forming a starting material i) an aqueous copolymer emulsion comprising (F) the silicone-(meth)acrylate copolymer, (D) a surfactant and (E) water, and optionally (I) a manganese ion source and (J) a phenolic compound (if used).

[0013] The method described herein may optionally include one or more additional steps. For example, prior to step 1), the starting material comprising (A) a silicone-(meth)acrylate macromonomer and (if present) (B) a silicone-(meth)acrylate copolymer macromonomer and / or (H) a chain transfer agent may be combined under aerobic or anaerobic conditions, optionally with prolonged heating time. For example, prior to the addition of the initiator in step 1) and copolymerization, the starting material comprising one or more of (A) a silicone-(meth)acrylate macromonomer and (B) a silicone-(meth)acrylate copolymer macromonomer and (if 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 starting materials and copolymerization in the above method can be carried out on a commercial scale under anaerobic or aerobic conditions, optionally at elevated temperatures (e.g., up to 100°C, alternatively 25°C to 60°C, alternatively 40°C to 80°C, and alternatively 45°C to 50°C). Copolymerization can be carried out batchwise, with residence times ranging from 15 minutes to 48 hours, alternatively 30 minutes to 12 hours, alternatively 40 minutes to 8 hours, and alternatively 40 minutes to 2 hours. For the purposes of this application, aerobic or anaerobic conditions mean that oxygen is not required to be present in the gas in the headspace of the reactor 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. Anaerobic conditions mean that the gas in the headspace contains no more than 2% oxygen.

[0014] Alternatively, the above-mentioned organosilicon-(meth)acrylate copolymer 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): (A) organosilicon-(meth)acrylate macromonomers and optionally one or more of the following: (B) organosilicon-(meth)acrylate comonomers, (H) chain transfer agents, (I) manganese ion sources, and (J) phenolic compounds; 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) organosilicon-(meth)acrylate macromonomers and (when present) (B) organosilicon-(meth)acrylate comonomers and (H) chain transfer agents. The resulting copolymer can be solvent-based. All or part of the solvent can be removed by any convenient means, such as by stripping or heated distillation and optionally by reduced pressure. The resulting copolymer can be emulsified using (D) surfactants and (E) water.

[0015] Regardless of the method used to prepare the copolymer, such as via emulsion polymerization or by emulsification of a copolymer prepared in a solvent (after solvent removal), the product prepared in step 1) is a starting material i) an aqueous copolymer emulsion comprising (F) an organosilicon-(meth)acrylate copolymer, (D) a surfactant, and (E) water. The starting material i) aqueous copolymer emulsion may optionally also comprise (I) a manganese ion source and / or (J) a phenolic compound. The starting materials used in the method for preparing the i) aqueous copolymer emulsion are further described below.

[0016] The starting material (A) used in this paper is an organosilicon-(meth)acrylate macromonomer. The organosilicon-(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.

[0017] 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.

[0018] 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.

[0019] 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 WO2020 / 142388 and U.S. Patent 6,420,504.

[0020] 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).

[0021] Alternatively, in addition to or instead of formula (B-1) shown above, the starting material (B) comonomer may comprise an organosilicon-(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 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 6This 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.

[0022] 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.

[0023] 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.

[0024] Examples of divalent hydrocarbon groups of D can be alkylene groups, such as ethylene, propylene, or butylene; arylene groups such as phenylene; or alkylarylene groups such as: 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.

[0025] 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.

[0026] 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.

[0027] Alternatively, equation (B-2) may include equation (B-2-1): , where R2 R 4 and R 5 As stated above.

[0028] Alternatively, equation (B-2) may include equation (B-2-2): , where R 2 D and R are as described above.

[0029] Alternatively, equation (B-2) may include equation (B-2-3): , where R 2 D and R are as described above.

[0030] Alternatively, formula (B-2) may comprise a copolymeric macromonomer 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 of the following formula: (Si10); 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 U.S. Patent Application Publication US20220112322 and U.S. Patent 6420504, both of which are hereby incorporated by reference.

[0031] When preparing the copolymer, the starting material (A) organosilicon-(meth)acrylate macromonomer and the starting material (B) organosilicon-(meth)acrylate comonomer are used in the following amounts: based on the combined weight of the starting materials (A) and (B), the starting material (A) is used in an amount of >25% to 100% by weight; and based on the combined weight of the starting materials (A) and (B), the starting material (B) is used in an amount of 0% to <75% by weight. Alternatively, based on the combined weight of the starting materials (A) and (B), the 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, on the same basis, the amount of the starting material (A) may be up to 100%, alternatively up to 99%, alternatively up to 95%, alternatively up to 75%, alternatively up to 63%, alternatively up to 50%, and alternatively up to 40%. 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%.

[0032] 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 exemplified by (2-acetylacetoxy)ethyl methacrylate, hydroxybutyl methacrylate, hydroxyethyl methacrylate, hydroxyethylcaprolactone methacrylate, hydroxypropyl methacrylate, urea methacrylate, and glycidyl methacrylate (GMA). 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).

[0033] 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.

[0034] In step 1) of the method for preparing the above copolymer, a starting material (C), i.e., an 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-methylpropionamide) 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., St. Louis, Missouri, USA. Alternatively, the initiator may include isoascorbic acid.

[0035] 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.

[0036] Alternatively, the initiator may optionally also include ferrous sulfate heptahydrate (II), potassium persulfate, or combinations thereof. Based on the weight of the organosilicon-(meth)acrylate copolymer (F), the initiator (C) may be sufficient to provide an amount of 0.01% to 3%, or alternatively 0.1% to 1.5%.

[0037] 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.

[0038] 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.

[0039] 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.

[0040] Based on the weight of the organosilicon-(meth)acrylate copolymer in the i) aqueous copolymer 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%.

[0041] 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: (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; and (vii) alkyl polyethylene glycol ethers based on C10 Guerbert alcohol and ethylene oxides such as LUTENSOLS. ™ XP 79.

[0042] 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.

[0043] 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-nonoxyethylene oxyethanol (6EO) and (10EO); under the trademark TERGITOL ™ 15-S-7, TERGITOL ™ 15-S-9, TERGITOL ™ 15-S-15 sold alkoxylated polyethylene oxyethanol (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 ™ X-405 sells octylphenoxy polyethoxyethanol (40EO); and products marketed under the name ECOSURF. ™ EH alcohol ethoxylates, such as ECOSURF ™ EH-40. All of these surfactants are sold by Dow Chemical Company.

[0044] Other useful commercial nonionic surfactants are produced by Stepan Corporation under the trademark MAKON.™ 10 nonylphenoxy polyethoxyethanol (10EO) sold by Sigma-Aldrich; polyoxyethylene 23 lauryl ether (Lauryl ether-23) commercially sold by Sigma-Aldrich; and RENEX ™ 30, a polyoxyethylene ether alcohol available from Fisher Scientific.

[0045] 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 Chemical Company. ™ 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 copolymer 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.

[0046] 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 silicone-(meth)acrylate copolymer in the aqueous copolymer 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 silicone-(meth)acrylate copolymer in the aqueous copolymer emulsion, the starting materials (D-1) cationic surfactant and (D-2) nonionic surfactant may be present in a combined amount of ≤10%.

[0047] 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 for preparing the copolymer. Additional water may be added after step 1). For example, the aqueous copolymer emulsion prepared as described above may be diluted with additional water to obtain the desired amount of starting material. Based on the combined weight of all the starting materials in step 1), water may be added in amounts of 10% to 97%, alternatively 30% to 90%, alternatively 40% to 80%, alternatively 50% to 97%, alternatively 50% to 90%, and alternatively 60% to 80%. 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%.

[0048] The silicone-(meth)acrylate copolymer (F) can be prepared by emulsion polymerization of a starting material comprising the aforementioned (A) macromonomer and (C) initiator (and optionally (B) copolymer macromonomer). Alternatively, the silicone-(meth)acrylate copolymer is a reaction product of a starting material consisting essentially of the starting material (A) macromonomer and (C) initiator (and, when present, (B) copolymer macromonomer and / or (H) 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 materials (D) surfactant, (E) water, (I) manganese ion source, and (J) phenolic compound do not copolymerize with the starting materials (A) and (C) (and, when present, (B) and / or (H)), but 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 (e.g., starting materials (B) and / or (H)) (if present) should not be excluded in this document.

[0049] The method described above may optionally include step 2) adding additional starting materials. The additional starting materials 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), (R) catalysts (such as condensation reaction catalysts), and combinations of two or more of these. Step 2) of the method may optionally also include adding additional (D) surfactants.

[0050] 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, BASF Schweiz AG, Basel, Switzerland, and the Encyclopedia of Radicals in Chemistry, Biology and Materials, Online © 2012 John Wiley & Sons, Ltd. Starting material (H) is optional and may be added in an amount of 0 to 1% based on the combined weight of starting material (A) and (if present) starting material (B). Alternatively, chain transfer agent (H) may be used in an amount of 0.5% to 0.6% on the same basis.

[0051] The starting material (I) is optionally a manganese ion source, which may be a manganese (III) compound or a manganese (II) compound. Alternatively, the starting material (I) may be a manganese (II) compound. Suitable manganese (II) compounds include manganese acetate (II), manganese nitrite (II), manganese propionate (II), manganese oxide (II), manganese hydroxide (II), manganese chloride (II), manganese phosphate (II), manganese perchlorate (II), their hydrates (e.g., manganese acetate (II) tetrahydrate), and combinations thereof. Alternatively, the manganese ion source may comprise manganese acetate (II) or manganese acetate (II) tetrahydrate, or combinations thereof. Suitable manganese ion sources are commercially available from Millipore Sigma of St. Louis, Missouri, USA; Feischel Technologies Inc. of Waltham, Massachusetts, USA; and CityChemical LLC of Connecticut, USA. The amount of manganese ion source depends on various factors, including the selection and amount of other starting materials used; however, 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, 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, based on the combined weight of all starting materials in the aqueous copolymer emulsion of starting material i), the amount of manganese ion source can be up to 10 ppm, alternatively up to 5 ppm, alternatively up to 4 ppm, and alternatively up to 3 ppm, and alternatively up to 2 ppm.

[0052] 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 available, for example, from Millipore Signature. 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 aqueous copolymer emulsion of starting material i), 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.

[0053] 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.

[0054] 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 i) aqueous copolymer emulsion, the amount of biocide when used can be >0% to 5%. 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.

[0055] The aqueous copolymer emulsion 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, MethylCARBITOL ™ and Butyl CARBITOL ™ .

[0056] The aqueous copolymer emulsion may optionally further comprise an amount of (Q) softening additive sufficient to impart softness to the textile without significantly reducing its water and / or oil repellency, the softening additive being selected from (Q-1) unit formula (R 19 3SiO)2(R 19 2SiO 2 / 2 ) aa Alkyl polysiloxanes, wherein 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 K6249:2003, 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 K6249:2003. The measurement using method 2283:2000 at 25°C is 10 mm. 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%.

[0057] In the (Q-1) alkyl polysiloxane shown below, 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... 19 It 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 purchased commercially from Dow Chemical Company.

[0058] 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) combination of the (Q-2) combination of the (Q-2) combination of the (Q-2) combination of the (Q-2) combination of the (Q-2) combination of the (Q-2) combination of the (Q-2) combination of the (Q-1 ... 2 / s to 100,000mm 2 kinematic viscosity / s.

[0059] The starting material (Q) softening additive can be delivered in an additional 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 additional aqueous emulsion can be prepared by known methods, such as those described in U.S. Patent Application Publication 20200332148, by varying the type and amount of the starting material as described herein.

[0060] The starting material (R) is optionally a catalyst. The catalyst comprises a metal complex, which may be a metal carboxylate (e.g., a metal acetate or a metal acetylacetonate), wherein the metal is selected from the group consisting of manganese (Mn), zinc (Zn), and zirconium (Zr). Alternatively, the metal may be Zn or Zr, and alternatively, Zn. Suitable catalysts include manganese(II) acetate (CAS No. 638-38-0), manganese(II) acetate tetrahydrate (CAS No. 6156-78-1), manganese(II) acetylacetonate (CAS No. 14024-58-9), manganese(III) acetylacetonate (CAS No. 14284-89-0), zinc acetate hydrate (CAS No. 16788-43-5), zinc(II) acetate (CAS No. 557-34-6), zinc(II) acetate dihydrate (CAS No. 5970-45-6), zinc(II) acetylacetonate (CAS No. 14024-63-6), zinc(II) acetylacetonate hydrate (CAS No. 108503-47-5), zirconium acetate (CAS No. 7585-20-8), and zirconium(IV) acetylacetonate (CAS No. 17501-44-9), all of which are commercially available from Sigma-Aldrich. The amount of starting material (R) depends on various factors, including the type and amount of the silicone-(meth)acrylate copolymer, whether or not a capped isocyanate is used, and the type and amount of other optional additional starting materials. However, based on the weight of the metal complex and the amount of capped isocyanate (solid content) (when used), the amount of catalyst can be >0 to 10%, alternatively 0.5% to 7.5%, alternatively >0.5% to <7.5%, and alternatively 1% to 5%. Alternatively, based on the combined weight of all starting materials used, the aqueous copolymer emulsion prepared as described above or the textile treatment emulsion prepared as described below may contain 0.001% to 0.1% of the (R) catalyst.

[0061] When selecting starting materials to add to the i) aqueous copolymer emulsions prepared as described in steps 1) and (if present) 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. For example, manganese acetylacetonate (II) can be an inhibitor or a condensation reaction catalyst. The starting materials used for the aqueous copolymer emulsions (prepared as described above) and the textile treatment emulsions (prepared as described below) can be different from each other.

[0062] Step 2) of the above-described method for preparing the aqueous copolymer emulsion 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 equipment. Step 2) can be carried out at room temperature or 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 room temperature. Alternatively, step 2) can be carried out at lower temperatures and elevated pressures (e.g., up to 5 atmospheres). Alternatively, step 2) may be absent, and any additional starting materials may be combined with the aqueous copolymer emulsion prepared later in step 1).

[0063] Method for preparing a textile treatment emulsion

[0064] The aqueous copolymer emulsion prepared as described above is used to prepare the textile treatment emulsion described herein. The method for preparing the textile treatment emulsion includes: step I) mixing starting materials comprising starting material i) and starting material ii), wherein starting material i) is an aqueous copolymer emulsion comprising (F) a silicone-(meth)acrylate copolymer, (D) a surfactant, and (E) water as described above; and starting material ii) is an aqueous composition comprising an alkyl carbamate, a surfactant, and water; and wherein starting material i) and starting material ii) are used in amounts sufficient to provide a silicone-(meth)acrylate copolymer:alkyl carbamate weight ratio of 1:<9. Alternatively, the weight ratio may be from 1:3 to 1:1 (copolymer:alkyl carbamate weight ratio). The weight ratio represents the relative amount of solids delivered by the emulsion, i.e., the weight of the silicone-(meth)acrylate copolymer delivered in starting material i) : the weight of the alkyl carbamate delivered in starting material ii).

[0065] The aqueous copolymer emulsion used for starting material i) is as described above. The aqueous composition comprising alkyl carbamate, surfactant, and water is known in the art and can be prepared by known methods, such as those disclosed in EP 3 198072 B1 (corresponding to U.S. Patent 10246608, which is incorporated herein by reference). For example, the aqueous composition may comprise a hydrophobic compound (e.g., an alkyl carbamate compound) having at least one bond of formula (I): -NHC(O)-X- (I), wherein the bond of formula (I) accounts for 30 mol% to 100 mol% of the total carbamate bonds in the hydrophobic compound; X is a residue of a cyclic or acyclic sugar alcohol substituted with at least two of the following groups: -R'; -C(O)R'; -(CH2CH2O). n (CH(CH3)CH2O)m C(O)R'; or mixtures thereof; wherein the cyclic or acyclic sugar alcohol is selected from glucose, glyceraldehyde, erythrose, arabinose, ribose, allose, azoose, mannose, xylose, lysose, gulose, galactose, tarose, fructose, ribulose, mannoketose, sedoheptulose, threose, erythritol, threitol, glucopyranose, mannoketose, tarose, allose, azoose, idooketose, gulose, glucol, mannitol, sorbitol, arabinose, xylitol, ribitol, and semi-cyclic sugar alcohols. Lactitol, fucitol, idutitol, inositol, dipentaerythritol, volemitol, gluconic acid, glyceric acid, xylanic acid, galactobionic acid, ascorbic acid, gluconolactone, glycerolactone, xylanolactone, glucosamine, galactosamine, or mixtures thereof; wherein each subscript n is independently 0 to 20; each subscript m is independently 0 to 20; the amount (m+n) is greater than 0; each R' is independently a straight-chain or branched alkyl group having 5 to 29 carbons, optionally containing at least one unsaturated bond. Starting material ii) is commercially available. For example, Zalan R3 from Chemours Company PC, LLC, Wilmington, Delaware, USA, is used herein as starting material ii).

[0066] The method may optionally include one or more additional steps. For example, the method may also include step II) adding starting materials iii) to the textile treatment emulsion containing capped isocyanates and water. Alternatively, the method may also include step III) adding additional starting materials selected from the group consisting of biocides, additional water, flame retardants, wrinkle reducers, antistatic agents, penetrants, softeners, catalysts (each as described above), and combinations of two or more of these to the textile treatment emulsion; wherein each of these additional starting materials is as described above and may be added in step III) of the method for preparing the textile treatment emulsion, for example, if not in step 2) of the method for preparing the above-described starting material i) aqueous copolymer emulsion. In the method for preparing the textile treatment emulsion herein, the order of addition of the starting materials is not critical. Steps I), II), and III) may be performed in any order. For example, step I) may be performed before steps II) and III). Alternatively, one or more additional starting materials from step III) may be combined with i) the aqueous copolymer emulsion or ii) the aqueous composition before mixing the starting materials i) and ii).

[0067] An aqueous additive comprising a capped isocyanate and water is optional and is added (when used) in step III as described herein. The term "capped isocyanate" encompasses monoisocyanates, diisocyanates, and polyisocyanates in which the isocyanate group has reacted with a capping agent, releasing the isocyanate and capping agent upon heating. Suitable capping agents are known in the art, such as amines, amides, compounds having an active hydrogen atom, alcohols, N-heterocyclic compounds, or oximes. Capped isocyanates are commercially available, such as ARKOPHOB from Archroma, Pratteln, Switzerland. ™ DAN and ARKOPHOB ™ SR; RUCO, from the Rudolf Group (Rudolf GmbH, Geretsreid, Bayern, Germany). ™ -GUARD WEB and RUCO ™ -LINK XCR, and PHOBOL from Angco ™ EXTENDER UXN and PHOBOL ™ EXTENDER XAN extender. Alternatively, the capped isocyanate can be an oxime-capped isocyanate, such as PHOBOL. ™ EXTENDER XAN. Alternatively, the capped isocyanate may comprise a nitrogen-containing heterocyclic (N-heterocyclic) capped isocyanate. The N-heterocyclic capped isocyanate comprises an isocyanate compound and an N-heterocyclic capping 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 end-capping agent may be 2,6-dimethylpyrazine or dimethylpyrazole, such as 3,5-dimethylpyrazole. Alternatively, the aqueous additives used herein may be free of oxime compounds. It is not intended to be theoretically construed that the end-capped isocyanates may be free of substances that may interfere with the performance of isocyanates in textile treatment emulsions, such as organosilicones and amines (which are not within the end-capping group). Furthermore, it is not intended to be theoretically construed that the end-capped 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 1 below.

[0068] Table 1 - Commercially available aqueous additives

[0069] The exact amount of the capped isocyanate compound depends on various factors, including (F) the type and amount of the silicone-(meth)acrylate copolymer, the alkyl carbamate, and the type and amount of the textile to be treated. However, on the same basis, the weight of the capped isocyanate may be sufficient to provide a solid content of 0.1% to 3.75%, alternatively 0.1% to 0.75%, alternatively 0.25% to 1%, and alternatively 0.25% to 0.5% by fabric weight; wherein the solid content refers to the amount of capped isocyanate that can be delivered in an aqueous dispersion together with other components (e.g., water and optional surfactants). Alternatively, the amount of starting material iii) that can be mixed with starting materials i) and ii) may be sufficient to provide a combination of silicone-(meth)acrylate copolymer and alkyl carbamate:capped isocyanate weight ratio of 16:1 to 1:1; alternatively 16:1 to 2:1; and alternatively 16:1 to 4:1. Alternatively, when using capped isocyanates, the catalysts described above as starting materials (R) can also be used in textile treatment emulsions.

[0070] Step III) of the method for preparing a textile treatment emulsion may be performed during or after step I). For example, the additional starting material may be mixed with the aqueous copolymer emulsion i) before step II). Alternatively, the additional starting material may be added during or after mixing the starting materials i) and ii).

[0071] Steps II) and III) of the above-described method for preparing textile treatment emulsions can be carried out in any convenient manner, such as by mixing using a jacketed container equipped with a stirrer. Steps II) and III) can be carried out simultaneously or sequentially in the same container. Alternatively, steps II) and III) can be carried out in different devices. Step II) can be carried out at room temperature or elevated temperatures (e.g., up to 100°C, alternatively room temperature to 80°C, alternatively room temperature).

[0072] Method of use

[0073] The textile treatment emulsion prepared as described above can be used to treat textiles. For example, methods for treating textiles include: 1) contacting the textile with the textile treatment emulsion described above, and 2) heating the textile. Step 1) can be carried out by any convenient method, such as padding, dipping, impregnating, or spraying the textile with the textile treatment emulsion. However, according to the method described herein, the method should be sufficient to deliver a sufficient amount of silicone-(meth)acrylate copolymer and alkyl carbamate to impart durable oil-resistant properties to the textile. Based on the weight of the textile, the method is sufficient to deliver a combination of silicone-(meth)acrylate copolymer and alkyl carbamate at 0.25% to 10% by weight of the fabric.

[0074] Step 2) 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 optionally cure the silicone-(meth)acrylate copolymer. 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, deseal the end-capped isocyanate (when end-capped isocyanate is used), and / or cure the silicone-(meth)acrylate copolymer.

[0075] 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 textile treatment emulsions described herein are suitable for any form of textile, such as woven, knitted, or nonwoven fabrics.

[0076] Examples

[0077] The following examples are provided to illustrate the invention to those skilled in the art, and these examples should not be construed as limiting the invention as set forth in the claims. The starting materials used in these examples are summarized in Table 2 below.

[0078] Table 2 - Starting materials

[0079] In this synthetic example 1, organosilicon-(meth)acrylate copolymer emulsions were prepared as follows. All monomers, water, and surfactants were added to a wide-mouth flask (approximately 400 mL) in the selections and amounts shown in Table 3 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 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 (emulsions 1, 2, and 5) prepared as described above are summarized in Table 3 below. The amounts of each starting material in Table 3 are in grams.

[0080] In this synthetic example 2, an organosilicon-(meth)acrylate copolymer emulsion was prepared as follows: The following monomers, water, surfactants, and inhibitors were added to a wide-mouth flask (approximately 400 mL): 3.38 g EH40, 85.13 g water, 9.06 g 3MT-ALMA, 27.19 g Si16, 0.36 g 4-methoxyphenol solution (2.5% aqueous solution), 0.0046 g hydroquinone, and 0.10 g manganese(II) acetate tetrahydrate solution (0.7% aqueous solution). The resulting material was sonicated at an amplitude of 50 for two minutes using a Fisher sonic 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. This material is emulsion 3 as summarized in Table 3 below.

[0081] In this synthetic example 3, the aqueous composition was prepared as follows. First, solutions A, B, and C were prepared. Solution A preparation: 0.0566 g of tert-butyl hydroperoxide (70% aqueous solution) was added, followed by the addition of sufficient water to prepare a 10 g solution. Solution B preparation: 0.0773 g of isoascorbic acid was added, followed by the addition of sufficient water to prepare a 10 g solution. Solution C preparation: 6 mg of ferrous sulfate heptahydrate (II) was added, followed by the addition of sufficient water to prepare a 10 g solution.

[0082] Next, the following macromonomers, water, surfactants, and inhibitors were added to a wide-mouth flask (approximately 400 mL): 1.76 g EH40, 67.06 g water, 3.63 g 3MT-ALMA, 32.79 g SA, 0.42 g 4-methoxyphenol solution (2.5% aqueous solution), 0.0034 g hydroquinone, and 0.08 g manganese(II) acetate tetrahydrate solution (0.7% aqueous solution). The SA monomer was first melted and added as a liquid. An emulsion was prepared using an ultrasonic sonicator (Fisherbrand sonic breaker, amplitude 50, duration 2 minutes). The resulting crude emulsion was then passed through a microfluidizer (Microfluidics Microfluidizer 110Y) at 5,000 psi twice. The resulting emulsion was then transferred to a 1 L four-necked flask equipped with a reflux condenser, nitrogen inlet, top stirrer (IKARW20), and thermocouple probe. The emulsion was stirred at 250 RPM using a Teflon blade and heated to 60 °C. Once the temperature was reached, solution C (1.74 g of prepared solution C) was added, followed by the addition of the redox initiator (solutions A + B, prepared as described in separate feeds) to the flask at 0.25 mL / min. The reaction was run for 45 minutes. The resulting material was then cooled to 30-40 °C with slow stirring and poured off. This material is emulsion 4, as summarized in Table 3 below.

[0083] Table 3 - Preparation of aqueous copolymer emulsions via emulsion polymerization

[0084] * indicates the use of 0.4 g of a 2.5% aqueous solution of 4-methoxyphenol, 0.006 g of hydroquinone, and 0.12 g of a 0.7% aqueous solution of manganese(II) acetate tetrahydrate.

[0085] In this Reference Example 1, the textile treatment emulsion was prepared by mixing the starting materials in the amounts shown in Table 4 below as follows: each starting material was added to a 125g Nalgene plastic bottle, and the bottle was inverted twice to mix.

[0086] Table 4 - Textile treatment emulsions

[0087] In Table 4, the weight ratio refers to the weight of the copolymer delivered in the aqueous copolymer emulsion (from Table 3): the weight of the alkyl urethane in Zelan R3 (solid content).

[0088] In this Reference Example 2, PES fabrics were treated with the textile treatment emulsion prepared as described above and shown in Table 4. The treatment was performed as follows: all fabrics were washed / dried prior to coating. The textile treatment emulsion was then poured into beakers, dip-coated, and coated using a Werner Mathis AG Textilmaschinen rolling mill (tension set to 70). After one pass, the sample was placed in a forced-ventilation Mathis LTF oven at 160°C for 3 minutes.

[0089] In this Reference Example 3, oil repellency was tested using a modified version of AATCC 118, i.e., using surface ratings of A, B, C, and D, as described in AATCC 118 (and as shown in Figure 3 of "Fluorine-free low surface energy organic coating for anti-stain applications" in Lei et al., Progress in Organic Coatings 103 (2017) 182-192, 184). A surface rating of A indicates a clear, rounded oil droplet; B indicates a partially dark, rounded droplet; C indicates significant wicking and / or complete wetting; and D indicates complete wetting. The modification to this test method is that the oil used is olive oil, and the time is extended from 10 seconds to 5 minutes. Relatively large olive oil drops are used for this test, i.e., at least 250 μL / drop. For the purposes of this application, if a sample has a rating of A or B after 5 minutes, it is considered to have durable oil repellency. A surface rating of C or D indicates an unacceptably high oil absorption rate for the fabric. The results are shown in Table 5 below.

[0090] Table 5 - PES textile treatment results

[0091] Examples 1-7 show that, under the tested conditions, mixing Zelan R3 with an aqueous copolymer emulsion of a silicone-(meth)acrylate copolymer prepared with 3MT-ALMA yields a textile treatment emulsion that imparts durable oil repellency to textiles. Examples 1 and 4 show that, under the tested conditions, the end-capped isocyanate additive is not necessary for imparting oil repellency to textiles. Examples 2, 3, and 5-7 show that end-capped isocyanates can be added to the textile treatment emulsion, and the resulting treated textiles exhibit durable oil repellency under the tested conditions. Comparative Example 1 shows that, without the silicone-(meth)acrylate copolymer, Zelan R3 cannot provide durable oil repellency to textiles. Comparative Example 2 shows that, under the tested conditions, a silicone-(meth)acrylate copolymer:alkyl carbamate weight ratio of 1:<9 provides durable oil repellency. Comparative Example 4 shows that the prepared emulsion containing a copolymer of 3MT-ALMA and stearyl acrylate did not impart oil repellency under the tested conditions.

[0092] 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 at room temperature to a round-bottom flask containing 47.95 g of anhydrous xylene. 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.

[0093] 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.

[0094] The procedures for Comparative Examples 5 and 6 included fabric pretreatment followed by treatment with PDMS resin 1, as follows: A 1cm × 1cm 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 (2.08g, 10mmol) in 60mL ethanol / 15mL deionized water in the presence of ammonium hydroxide (2.75mL). 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 (5g of a 40% solution of Ludox HS-40 colloidal silica and 35g of deionized water) until saturated (approximately 4 seconds) and then dried overnight at 80°C. The pretreated 1cm × 1cm PES or nylon fabric sample was dipped into PDMS resin 1 three times. The sample was cured at 200°C for 1 hour.

[0095] The procedures for comparative examples 7 and 8 are as follows: 1 cm × 1 cm PES or nylon fabric samples were dipped into synthetic PDMS resin 1 three times. The samples were then cured at 200°C for 1 hour.

[0096] The procedures for these comparative examples 9 and 10 are as follows:

[0097] 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 deionized 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 deionized water) until saturated (approximately 4 seconds) and then dry overnight at 80°C.

[0098] Table 6 - Results of Comparative Examples 18 to 23

[0099] Comparative Examples 5 and 6 correspond to Example 2 disclosed in U.S. 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 to 7 in Table 5 above) exhibits excellent oil repellency using the modified AATCC method 118 described herein. Comparative Examples 7 and 8 underwent sol-gel and nanoparticle removal treatment and were tested on 3MT-ALMA / vinyltrimethoxysilane copolymer; these examples also failed the modified AATCC method 118 after 5 minutes.

[0100] In Comparative Example 11, the PES fabric was treated with two separate emulsions in two separate steps. First, PHOBOL was used. ™ The fabric was coated with EXTENDER XAN (0.69 g XAN + 74.31 g deionized water) as described in the coating / curing method in Reference Example 2 above. In the second step, the fabric was treated with an aqueous copolymer emulsion, wherein 5.75 g of emulsion 1 from Table 3 was combined with 69.25 g of deionized water using the same coating and curing method as described in Reference Examples 2 and 3 above.

[0101] Comparative Example 11 illustrates a pretreatment method for a terminated isocyanate (XAN) additive similar to that described in Example 2 of U.S. Patent Publication US20230038369 (Comparative Examples 5 and 6 above). Comparative Example 11 failed the modified AATCC method 118 after 10 seconds and exhibited worse oil repellency than Comparative Examples 5 and 6 at 10 seconds.

[0102] In Comparative Example 12, 3.83g of Emulsion 1 described in Table 3 above and 1.59g of DOWSIL were used. ™ IE-8749 (a 70% solids silicone-based 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 above in Reference Example 3, and the oil repellency was measured. The fabric had a C rating after 10 seconds and a D rating after 30 seconds. Comparative Example 12 showed 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.

[0103] In Comparative Example 13, 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 according to the method in Reference Example 2 and evaluated by a modified AATCC 118 test as described in Reference Example 3. The treated fabric failed the oil repellency test at 30 seconds.

[0104] Industrial applicability

[0105] The above embodiments demonstrate that the textile treatment emulsion and method of the present invention impart durable oil repellency to textiles. It is not intended to be theoretically restrictive, but rather to suggest that the textile treatment emulsion of the present invention can impart both water and oil repellency to textiles. The method for imparting oil repellency to textiles includes: step 1) applying the textile treatment emulsion prepared as described above to the textile; and step 2) drying the textile to remove all or part of the water. However, the method may consist essentially of steps 1) and 2) or be composed of them, because the present invention provides the additional benefit of requiring only one application of the textile treatment emulsion; for example, to impart oil repellency, it is not necessary to repeat step 1) to reapply the textile treatment emulsion.

[0106] Definitions and use of terms

[0107] 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, revised January 2018, 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 7.

[0108] Table 7 - Abbreviations

Claims

1. A method for preparing a textile treatment emulsion, wherein the method comprises: I) Mixing starting materials, the starting materials comprising i) an aqueous copolymer emulsion, the aqueous copolymer emulsion comprising a silicone-(meth)acrylate copolymer, a surfactant, and water, wherein the silicone-(meth)acrylate copolymer comprises the following unit formula: ,in Each R 1 It is a monovalent hydrocarbon group consisting of 1 to 12 carbon atoms, chosen independently; Each D 2 It is a divalent hydrocarbon group consisting of 2 to 12 carbon atoms, chosen independently; 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 Groups consisting of 3, among which 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 of 2 to 4 carbon atoms; 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; The condition is to choose R. 4 R 5 and R 6 This ensures that the organosilicon-(meth)acrylate copolymer macromonomer unit with 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; ii) an aqueous composition, the aqueous composition comprising an alkyl carbamate, a surfactant, and water; And wherein starting materials i) and ii) are used in amounts sufficient to provide a weight ratio of the silicone-(meth)acrylate copolymer: the alkyl carbamate of 1: <9.

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

1.

3. The method according to claim 1 or claim 2, further comprising: II) Adding starting material iii) an aqueous additive comprising a blocked isocyanate and water.

4. The method according to claim 3, wherein starting material iii) the aqueous additive is added in an amount sufficient to provide a weight ratio of the combined silicone-(meth)acrylate copolymer and alkyl carbamate: the blocked isocyanate of 16:1 to 1:

1.

5. The method according to claim 3 or claim 4, wherein the blocked isocyanate comprises an oxime-blocked isocyanate or an N-heterocyclic-blocked isocyanate.

6. The method according to any one of claims 1 to 5, wherein starting material ii) comprises Zelan R3 from Chemours.

7. The method according to any one of claims 1 to 6, wherein starting material i) is prepared by a method comprising the following steps: 1) Copolymerizing starting materials, the starting materials comprising (A) a silicone-(meth)acrylate macromonomer of the following formula: , 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; Optionally (B) a silicone-(meth)acrylate copolymer macromonomer, wherein (B) the silicone-(meth)acrylate copolymer macromonomer 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 Equation (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; Equation (B-2) is , where R 2 Select the group consisting of H and methyl groups; D 2 It 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 results in the organosilicon-(meth)acrylate copolymer macromonomer of formula (B-2) having at least 5 silicon atoms per molecule; wherein based on the combined weight of starting materials (A) and (B), starting material (A) is present in an amount of >25% by weight to 100% by weight; and wherein based on the combined weight of starting materials (A) and (B), starting material (B) is present in an amount of 0% by weight to <75% by weight; 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 manganese ion source; and Optionally (J) a phenolic compound; and where one of the conditions (i) or (ii) is satisfied, where condition (i) is that step 1) further includes adding a solvent before or during step 1), removing the solvent after forming the organosilicon-(meth)acrylate copolymer of (F), and forming i) the aqueous copolymer emulsion containing the organosilicon-(meth)acrylate copolymer, the surfactant, and the water; and where condition (ii) is that step 1) includes an emulsion polymerization reaction; the additional starting materials further include (D) a surfactant and (E) water; and where the product of step 1) includes i) the aqueous copolymer emulsion, and the aqueous copolymer emulsion contains (F) the organosilicon-(meth)acrylate copolymer, the surfactant, and the water.

8. The method according to any one of claims 1 to 7, the method further comprising: III) adding additional starting materials selected from the group consisting of biocides, additional water, flame retardants, wrinkle reducers, antistatic agents, penetrants, softeners, condensation reaction catalysts, and combinations of two or more of them.

9. A textile treatment emulsion, the textile treatment emulsion comprising: an organosilicon-(meth)acrylate copolymer, the organosilicon-(meth)acrylate copolymer comprising the following unit formula: ,in Each R 1 It is a monovalent hydrocarbon group consisting of 1 to 12 carbon atoms, chosen independently; Each D 2 It is a divalent hydrocarbon group consisting of 2 to 12 carbon atoms, chosen independently; 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 Groups consisting of 3, among which 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 having 1 to 12 units, and a divalent hydrocarbon group having 2 to 4 carbon atoms; 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; The condition is to choose R. 4 R 5 and R 6 This ensures that the organosilicon-(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; and an alkyl carbamate; where the copolymer and the alkyl carbamate are present in an amount such that the weight ratio of copolymer:alkyl carbamate is 1:<9 to 1:1; a surfactant; and water.

10. The textile treatment emulsion according to claim 9, the textile treatment emulsion further comprising a blocked isocyanate.

11. The textile treatment emulsion according to claim 9 or claim 10, wherein the blocked isocyanate includes an oxime-blocked isocyanate or an N-heterocyclic-blocked isocyanate.

12. The textile treatment emulsion according to any one of claims 9 to 11, wherein the copolymer and the alkyl carbamate are present in an amount such that the weight ratio of copolymer:alkyl carbamate is 1:1 to 1:

3.

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

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

15. An oil-repellent textile fabric prepared by the method according to claim 13 or claim 14.

16. The method according to any one of claims 1 to 8, wherein the organosilicon-(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 from 212,000 g / mol to 2,000,000 g / mol.

18. The textile treatment emulsion according to any one of claims 9 to 12, wherein the organosilicon-(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 from 212,000 g / mol to 2,000,000 g / mol.

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