Leather treatment agents containing silicone-(meth)acrylate copolymers and organic binders for imparting water and oil repellency.

Abstract

A leather treatment composition comprising: (I) an organic acrylic binder, (II) an organosilicone-(meth)acrylate copolymer, (III) a surfactant, (IV) water, and (V) an isocyanate. A method for treating leather comprising: (I) applying the leather treatment composition to a surface of a leather substrate, and (II) drying the substrate. The leather treatment composition and method can be used to impart stain-repellent and / or oil-repellent properties to the leather substrate.

Description

Cross-references to related applications

[0001] This application claims priority to U.S. Provisional Patent Application No. 63 / 593716, filed October 27, 2023, and U.S. Provisional Patent Application No. 63 / 674322, filed July 23, 2024, pursuant to 35 USC §119(e); and further claims the benefit of PCT Application Serial No. PCT / US24 / 045245, filed September 5, 2024. U.S. Provisional Patent Application Nos. 63 / 593716 and 63 / 674322, and PCT Application Serial No. PCT / US24 / 045245, are hereby incorporated by reference. Technical Field

[0002] A leather treatment composition and its preparation and use methods are provided. More specifically, the leather treatment composition is an aqueous emulsion or dispersion comprising an organic binder and an organosilicon-(meth)acrylate copolymer. This leather treatment composition can be used to impart stain resistance and oil repellency to a leather substrate. Background Technology

[0003] Fluorinated materials have been used as stain repellents on leather. These fluorinated materials are primarily based on perfluoroalkyl substances (PFAS) diluted in various solvents; however, customer and regulatory pressures are driving the industry to require leather treatments based on non-fluorocarbon compounds. The search for alternatives to these PFAS materials (especially for stain and oil repellency) would be for various industries, such as automotive OEMs, interior decorators, and fashion brands, and these alternatives would be durable and high-performance. Summary of the Invention

[0004] A leather treatment composition comprises: (I) an organic binder comprising an organic acrylic polymer, (II) an organosilicon-(meth)acrylate copolymer, (III) a surfactant, (IV) water, and (V) an isocyanate. A method for treating leather comprises: (I) applying the leather treatment composition described above to a surface of a leather substrate, and (II) drying the substrate. Detailed Implementation

[0005] The leather treatment composition described above can be prepared by a method comprising: (I) mixing a starting material comprising: i) an aqueous composition comprising an organic binder and water; ii) an aqueous emulsion comprising a silicone-(meth)acrylate copolymer, a surfactant, and water; and iii) an isocyanate. Optionally, the method may further include one or more additional steps prior to step (I), such as dispersing the starting material containing the pigment in water prior to step (I) to prepare an aqueous pigment dispersion, and mixing the aqueous pigment dispersion with the starting material in step (I). Optionally, the method may further include one or more additional steps after step (I), such as removing agglomerated particles after step (I) and / or the method may further include (II) adding an additional starting material selected from the group consisting of: biocides, silicone polyethers (different from surfactants), rheology modifiers, matting additives, solvents, softening additives, and combinations of two or more of these. Furthermore, the method may optionally include adding additional water for dilution, for example for use at a remote location to reduce the total solids of the leather treatment composition to a desired range. Therefore, leather treatment compositions can be shipped in any stable, concentrated form.

[0006] The mixing of the starting materials in step (I) (and any optional additional steps) can be carried out in any convenient manner, such as optionally under shear using the equipment and methods described below for manufacturing emulsions comprising silicone-(meth)acrylate copolymers. Alternatively, simple mixing can be performed to mix the starting materials in step (I), for example without shearing. Mixing can be carried out in any convenient manner using equipment such as a jacketed container equipped with a stirrer. Step (I) and any optional and / or additional steps as described above can be carried out sequentially in the same container. Alternatively, step (I) and one or more optional additional steps can be carried out in different equipment. Step (I) can be carried out at RT or at elevated temperatures (e.g., up to 100°C, alternatively 40°C to 80°C). Alternatively, heating can be performed in step (I), and one or more of these optional additional steps can be carried out at RT.

[0007] The starting material i) in the leather treatment compositions described herein comprises an organic polymer binder (dry polymer). This polymer binder comprises an organic acrylic polymer and optionally also comprises an organic polyurethane. The organic acrylic polymer may be a copolymer comprising at least one copolymerized olefinically unsaturated monomer and 0.4% to 10%, alternatively 0.4% to 4% of a copolymerized acetoacetate or acetoacetamide monomer, where % is relative to the total weight of the monomers. Suitable olefinically unsaturated monomers include, for example, (meth)acrylate monomers, including methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, lauryl acrylate, methyl methacrylate, butyl methacrylate, isodecyl methacrylate, lauryl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, aminoalkyl (meth)acrylate; styrene or substituted styrene; butadiene; vinyl acetate or other vinyl esters; vinyl monomers, such as vinyl chloride, vinylidene chloride, N-vinylpyrrolidone; and acrylonitrile or methacrylonitrile. Alternatively, the copolymer monomers may be free of one or more functional groups, such as aldehydes and amines, capable of chemically reacting with acetoacetate or acetamide groups. Alternatively, the acrylic polymer may contain 25% to 65% copolyethyl acrylate based on the weight of the acrylic polymer.

[0008] The organoacrylic polymers used herein are available in the form of aqueous emulsions. The solids content of the organoacrylic polymer emulsions can be from 25% to 40%, or alternatively from 30% to 35%. In addition to the organoacrylic polymers described above, the aqueous emulsions of the organoacrylic polymers also contain water and surfactants as described herein for emulsions containing silicone-(meth)acrylate copolymers. Suitable commercially available organoacrylic polymer emulsions for use in this invention may include, for example, HYDRHOLAC available from Dow. ™ Cl-1 emulsion (HYDRHOLAC is a trademark of ROHM and HAAS Company).

[0009] In addition to organic acrylic binders, leather treatment compositions may optionally also include organic polyurethane binders (polyurethane). The polyurethane may be delivered in the form of an aqueous dispersion. The aqueous polyurethane dispersion used herein to prepare aqueous coating compositions may be an externally stabilized polyurethane dispersion or an internally stabilized polyurethane dispersion. "Internally stabilized polyurethane dispersion" herein refers to a polyurethane dispersion stabilized by incorporating ionic or nonionic hydrophilic side groups into polyurethane particles dispersed in a liquid medium. Examples of nonionic internally stabilized polyurethane dispersions are described in U.S. Patents US3905929 and US3920598. Ionic internally stabilized polyurethane dispersions are known and described in U.S. Patent US6231926. Typically, dihydroxyalkyl carboxylic acids (such as those described in U.S. Patent US3412054) are used to manufacture anionic internally stabilized polyurethane dispersions. A commonly used monomer for manufacturing anionic internally stabilized polyurethane dispersions is dimethylolpropionic acid (DMPA).

[0010] Polyurethanes can be prepared by polymerization of monomers selected from: polyisocyanates having two or more isocyanate functional groups and having 4 to 40 carbon atoms, polyols (such as diols), monomers having at least one isocyanate group or at least one isocyanate reactive group and additionally having at least one hydrophilic group or potentially hydrophilic group, and optionally one or more compounds having reactive groups comprising an alcohol hydroxyl group, a primary or secondary amino group or an isocyanate group.

[0011] Suitable polyisocyanates include conventional aliphatic, alicyclic, aryl-aliphatic, and aromatic isocyanates. Polyisocyanates may be selected from the group consisting of: diphenylmethane diisocyanate (“MDI”), polymeric diphenylmethane diisocyanate (“pMDI”), toluene diisocyanate (“TDI”), hexamethylene diisocyanate (“HDI”), dicyclohexylmethane diisocyanate (“HMDI”), isophorone diisocyanate (“IPDI”), cyclohexyl diisocyanate (“CHDI”), naphthalene diisocyanate (“NDI”), phenyl diisocyanate (“PDI”), tetramethylene diisocyanate (“TMDI”), and combinations thereof. Polyisocyanates may have the formula OCN-R-NCO, where R is an alkyl, aryl, or aralkyl moiety. Alternatively, polyisocyanates may contain any number of carbon atoms as described above, alternatively from 4 to 20 carbon atoms.

[0012] Specific examples of suitable polyisocyanates include: alkylene diisocyanates having 4 to 12 carbons in the alkylene group, such as 1,12-dodecane diisocyanate, 2-ethyl-1,4-tetramethylene diisocyanate, 2-methyl-1,5-pentamethylene diisocyanate, 1,4-tetramethylene diisocyanate, and preferably 1,6-hexamethylene diisocyanate; alicyclic diisocyanates, such as 1,3- and 1,4-cyclohexane diisocyanates and any mixtures of these isomers, 1-isocyano-3,3,5-trimethyl-5-isocyanomethylcyclohexane, 2,4- and 2,6-hexahydrodiisocyanates. Toluene diisocyanate and mixtures of corresponding isomers, 4,4'-, 2,2'- and 2,4'-dicyclohexylmethane diisocyanate and mixtures of corresponding isomers, and aromatic diisocyanates and polyisocyanates, such as 2,4- and 2,6-toluene diisocyanate and mixtures of corresponding isomers, 4,4'-, 2,4'- and 2,2'-diphenylmethane diisocyanate and mixtures of corresponding isomers, mixtures of 4,4'-, 2,4'- and 2,2-diphenylmethane diisocyanate and polyphenylene polymethylene polyisocyanate, and mixtures of MDI and toluene diisocyanate (TDI). Alternatively, the polyisocyanate may contain IPDI. Alternatively, the polyurethane may be made from one or more diisocyanates (such as IPDI or TMDI) and one or more polyols (such as polyether polyols, polycarbonate polyols, or polyester polyols, for example having a molecular weight (Mw) of 5,000 or less, or 2,000 or less). Such polyols may be linear and may have two hydroxyl groups, one at each end.

[0013] Suitable polyols include polyester polyols that react with the isocyanates described above, and include, but are not limited to, polyhydroxy alcohols (such as ethylene glycol, propylene glycol, diethylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, cyclohexanediol, glycerol, trimethylolpropane, pentaerythritol, sucrose, or polyether polyols or mixtures thereof) with polycarboxylic acids, particularly dicarboxylic acids or their ester-forming derivatives (e.g., succinic acid, glutaric acid, and adipic acid or their dimethyl esters, sebacic acid, phthalic anhydride, tetrachlorophthalic anhydride, dimethyl terephthalate, or mixtures thereof) with hydroxyl-functionalized reaction products. Polyester polyols obtained by polymerization of lactones (e.g., caprolactone) with polyols or by polymerization of hydroxycarboxylic acids (e.g., hydroxyhexanoic acid) may also be used. In some embodiments, the polyol comprises a mixture of polyester and polyether polyols.

[0014] The term "externally stabilized polyurethane dispersion" as used herein refers to a polyurethane dispersion that does not have ionic or nonionic hydrophilic side groups and therefore requires the addition of a surfactant to stabilize the polyurethane dispersion. This surfactant may be one of those described in the copolymer emulsions described above. Examples of externally stabilized polyurethane dispersions are described in U.S. Patents 2,968,575; 5,539,021; 5,688,842; and 5,959,027.

[0015] Alternatively, the polyurethane dispersion may be an internally stabilized polyurethane dispersion. Alternatively, the polyurethane dispersion may comprise an aqueous polyurethane dispersion based on isophorone diisocyanate and polyester polyol, stabilized by carboxylic acid ester groups in the polyurethane backbone. The glass transition temperature of the polyurethane may be -44°C. Suitable polyurethane dispersions for preparing aqueous coating compositions are known in the art and are commercially available, such as BAYDERM available from Dow. ™ Polyurethane dispersions, such as BAYDERM ™ 91UD. Alternatively, the polyurethane dispersion may be as described in U.S. Patent 11,518,905 to Lenoble et al.

[0016] Other representative examples of applicable commercial polyurethane dispersions include PERMUTEX from Stahl Polymer. ™ HAUTHANE from CL Hauthaway & Sons Corp. ™ L-3121, and PRIMAL from Dow ™BINDER and polyurethanes from Ableridingk Boley, Inc. Other polyurethane dispersions can be prepared by conventional methods in the art. See, for example, the methods described in P. Pieterich, Aqueous Emulsion, Dispersion and Solutions of Polyurethanes; Synthesis and Properties in Progress in Organic Coatings 9 (1981) 281-340. See also: US7232859, US2004 / 0167252 and US2011 / 0112245. Such polyurethanes are generally prepared by reacting one or more organic polyisocyanates with one or more organic compounds, specifically polyols, containing isocyanate reactive groups. This reaction can be carried out in the presence of a catalyst, such as organotin compounds, organomanganese compounds (such as manganese acetylacetonate), organozinc compounds (such as zinc acetylacetonate), and / or tertiary amines. Polyurethanes are conventionally formulated into aqueous dispersions and can be anionic, nonionic, or anionic polyurethane dispersions. In one embodiment, the polyurethane dispersion can be anionic, prepared by reacting one or more polyols with an organic compound having at least one acid group and at least two active hydrogen functional groups and a polyisocyanate. Suitable organic compounds having at least one acid group and at least two active hydrogen functional groups include, for example, 2,2-dimethylolacetic acid and 2,2-dimethylolpropionic acid. Examples of suitable acid groups for organic compounds include carboxylic acids, sulfonic acids, phosphoric acids, phosphonic acids, etc.

[0017] The emulsions or dispersions of the organic polymer binders described above may be used in amounts sufficient to provide 15% to 70%, alternatively 30% to 70%, alternatively 30% to 60%, alternatively 30% to 40%, and alternatively 40% to 60% of the combined weight of all the starting materials in the leather treatment compositions described herein.

[0018] The leather treatment composition also comprises the silicone-(meth)acrylate copolymer (copolymer) described above. This copolymer can be prepared by a method comprising: 1) copolymerizing starting materials comprising: (A) formula 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 R2 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 6 The 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.

[0019] Step 1) of the method for producing the copolymer may include an emulsion polymerization reaction. Additional starting materials also include (D) a surfactant and (E) water. In step 1), the emulsion polymerization may include forming an emulsion, followed by the addition of (C) an initiator and copolymerization, the emulsion comprising starting materials (A) a silicone-(meth)acrylate macromonomer, (B) a silicone-(meth)acrylate comonomer (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) organosilicon-(meth)acrylate macromonomers, (B) organosilicon-(meth)acrylate copolymer macromonomers, (D) surfactants and (E) water, and when present (H) chain transfer agents, the starting materials (I) manganese ion source and / or (J) phenolic compounds can inhibit the formation of acrylic acid radicals, which can affect the formation of copolymers during copolymerization in step 1).

[0020] Step 1) of the method described above may include forming an emulsion comprising starting materials (A) organosilicon-(meth)acrylate macromonomers, (B) organosilicon-(meth)acrylate copolymer macromonomers, (C) an initiator, (D) a surfactant, and (E) water, and optional additional starting materials selected from the group consisting of: (H) chain transfer agents, (I) manganese ion sources, (J) phenolic compounds, and combinations of two or more thereof. These starting materials may be mixed under shear to form an aqueous emulsion. Shear mixing may be performed by any convenient means for forming an aqueous emulsion, such as ultrasonication and subsequent microfluidization. Equipment for shear mixing (such as ultrasonicators, homogenizers, microfluidizers, and high-speed mixers) is known in the art and commercially available. It is not intended to be theoretically construed that shear mixing can be used to obtain submicron particle sizes in emulsions. In step 1), a starting material comprising (A) a silicone-(meth)acrylate macromonomer, (B) a silicone-(meth)acrylate copolymer macromonomer, (C) an initiator (and, when present, (H) a chain transfer agent) is copolymerized with a starting material (D) a surfactant and (E) water, and optionally (I) a manganese ion source and (J) a phenolic compound to form (F) a silicone-(meth)acrylate copolymer in an aqueous emulsion.

[0021] The method described herein may optionally include one or more additional steps. For example, prior to step 1), a starting material comprising (A) a silicone-(meth)acrylate macromonomer and (B) a silicone-(meth)acrylate copolymer macromonomer and (H) a chain transfer agent, if present, may be combined under aerobic or anaerobic conditions, optionally with prolonged heating. For example, prior to the addition of the initiator and copolymerization in step 1), a starting material comprising one or more of (A) a silicone-(meth)acrylate macromonomer and (B) a silicone-(meth)acrylate copolymer macromonomer and (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 the starting material and copolymerization in the method described above may be carried out on a commercial scale under anaerobic or aerobic conditions, optionally at elevated temperatures (e.g., up to 100°C, alternatively 40°C to 80°C, and alternatively 45°C to 50°C). Copolymerization can be carried out in a batch process, with residence times ranging from 15 minutes to 24 hours, alternatively from 30 minutes to 12 hours, alternatively from 40 minutes to 8 hours, and alternatively from 40 minutes to 2 hours. For the purposes of this application, aerobic or anaerobic conditions mean that oxygen is not required to be present in the gas at the headspace of the reactor where copolymerization occurs, or dissolved in the liquid where copolymerization occurs. The remaining gas in the headspace can be an inert gas, such as nitrogen or argon.

[0022] Alternatively, the copolymers described above can be prepared by a method comprising: dissolving one or more of the following starting materials in an organic solvent (such as a monohydric alcohol): such as (A) a silicone-(meth)acrylate macromonomer, and optionally (B) a silicone-(meth)acrylate comonomer, (H) a chain transfer agent, (I) a manganese ion source, and (J) a phenolic compound; and in a method such as that disclosed in U.S. Patent 10,047,199 to Iimura et al., copolymerizing the starting material (A) the silicone-(meth)acrylate macromonomer and, when present, (B) the silicone-(meth)acrylate comonomer and / or (H) the chain transfer agent by varying the appropriate starting material and its amount. 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) a surfactant and (E) water.

[0023] Regardless of the method used to manufacture the copolymer, such as via emulsion polymerization or by emulsifying a solvent-based copolymer (after solvent removal), the product prepared in step 1) is an aqueous emulsion comprising (F) an organosilicon-(meth)acrylate copolymer, (D) a surfactant, and (E) water. This aqueous emulsion may optionally also comprise (I) a manganese ion source and / or (J) a phenolic compound. This aqueous emulsion is used as the starting material ii) in step (I) described above for preparing the leather treatment composition.

[0024] Step 1) of the method for producing the copolymer described above can be carried out in any convenient manner, such as mixing using a jacketed vessel equipped with a stirrer. Step 1) and any optional and / or additional steps as described above can be carried out sequentially in the same vessel. Alternatively, step 1) and any optional additional steps can be carried out in different equipment. Step 1) can be carried out at RT or at elevated temperatures (e.g., up to 100°C, alternatively 40°C to 80°C). Alternatively, heating can be carried out in step 1), and any optional additional steps can be carried out at RT. The starting materials used in the method for producing the copolymer described above are further described below.

[0025] The starting material (A) 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.

[0026] 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.

[0027] 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 2It 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.

[0028] Starting material (A) may comprise 3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxane-3-yl)propyl methacrylate of the following formula: (3MT-ALMA). The starting material (A) can be prepared by known methods, such as those disclosed in PCT Publication WO2020142388 and US Patent 6420504. The amount of starting material (A) can be 23% to 35% based on the combined weight of the starting materials (A), (B), (C), (D), and (E) used in the emulsion polymerization.

[0029] 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).

[0030] 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 R3 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 6 This results in each molecule of the copolymer macromonomer of formula (B-2) having at least 6 silicon atoms. Alternatively, R is selected. 4 R 5 and R 6 Each molecule of the unit has at least 5 silicon atoms, alternatively at least 6 silicon atoms, alternatively 6 to 20 silicon atoms, alternatively 7 to 19 silicon atoms, alternatively 8 to 18 silicon atoms, alternatively 9 to 17 silicon atoms, and alternatively 10 to 16 silicon atoms.

[0031] 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.

[0032] 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.

[0033] 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.

[0034] 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, D6 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.

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

[0036] Alternatively, equation (B-2) may include equation (B-2-1): , where R 2 R 4 and R 5 As stated above.

[0037] Alternatively, equation (B-2) may include equation (B-2-2): , where R 2 D and R are as described above.

[0038] Alternatively, equation (B-2) may include equation (B-2-3): , where R 2 D and R are as described above.

[0039] Alternatively, formula (B-2) may contain copolymer macromonomers selected from the group consisting of:

[0040] 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);

[0041] 3-(1,5-bis(2-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxane-3-yl)ethyl)-3-(((2-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxane-3-yl)ethyl)dimethylsilyl)oxy)-1,1,5,5-tetramethyltrisiloxane-3-yl)propyl methacrylate: (Si16); and combinations thereof. Copolymer macromonomers of formula (B-2) as described and illustrated above can be prepared by known methods, such as those disclosed in PCT Publication WO2020142388 and US Patent 6420504. Based on the combined weight of the starting materials (A), (B), (C), (D), and (E) used for emulsion polymerization, the amount of starting material (B) can be from 0% to 26%, alternatively from 0% to 17%.

[0042] When manufacturing copolymers, starting material (A) silicone-(meth)acrylate macromonomer and starting material (B) silicone-(meth)acrylate comonomer are used in the following amounts: based on the combined weight of starting materials (A) and (B), starting material (A) is used in an amount of >25% to 100% by weight; and based on the combined weight of starting materials (A) and (B), starting material (B) is used in an amount of 0% to <75% by weight. Alternatively, based on the combined weight of starting materials (A) and (B), starting material (A) may be used in an amount of >25%, alternatively at least 40%, alternatively at least 50%, alternatively at least 63%, and alternatively at least 75%; while the amount of starting material (A) may be up to 100%, alternatively up to 99%. On the same basis, alternatively up to 95%, alternatively up to 75%, alternatively up to 63%, alternatively up to 50%, and alternatively up to 40%. Alternatively, the amount of starting material (A) may be 100%, and the amount of starting material (B) may be 0. Alternatively, starting material (B) may be present, and on the same basis, the amount of starting material (B) may be >0%, alternatively at least 1%, alternatively at most 5%, alternatively at most 10%, alternatively at most 15%, alternatively at most 20%, and alternatively at least 25%; while the amount of starting material (B) may be at most 60%, alternatively at most 50%, alternatively at most 37%, and alternatively at most 25%.

[0043] The starting materials used to manufacture the copolymer (and the copolymers prepared as described herein) may optionally be free of crosslinkable groups. For example, the starting materials used for copolymerization in step 1) of the method for manufacturing the copolymers described herein may be free of crosslinkable (meth)acrylate monomers, such as organic (meth)acrylate monomers having crosslinkable groups. For example, the starting materials used in step 1) may be free of crosslinkable (meth)acrylate monomers, such as organic (meth)acrylate monomers having crosslinkable groups, such as ethyl methacrylate (2-acetylacetoxy)methacrylate, hydroxybutyl methacrylate, hydroxyethyl methacrylate, hydroxyethylcaprolactone (meth)acrylate, hydroxypropyl methacrylate, urea methacrylate, glycidyl methacrylate (GMA), and poly(alkylene glycol) (meth)acrylate macromonomers, such as poly(ethylene glycol) mono(meth)acrylate (PEGMA) and poly(ethylene glycol) di(meth)acrylate. The starting material used in step 1) may be free of organosilicon monomers with crosslinkable groups, such as alkenyltrialkoxysilanes (e.g., 3-(trimethoxysilyl)propyl (meth)acrylate, vinyltriethoxysilane, and vinyltrimethoxysilane).

[0044] The starting material (A) and, when present, the 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 the starting material (A) a macromonomer and (C) an initiator, and, when present, (B) a copolymerizable macromonomer and / or (H) a chain transfer agent. Alternatively, the starting material used in step 1) may consist substantially of or may consist of: (A) a macromonomer, (C) an initiator, (D) a surfactant and (E) water, and, when present, one or more of (B) a copolymerizable macromonomer, (H) a chain transfer agent, (I) a manganese ion source and (J) a phenolic compound, and these starting materials are further described below.

[0045] In step 1) described above, the starting material (C) initiator is also added. Suitable initiators include azo compounds and peroxide compounds. For example, the azo compound can be an aliphatic azo compound, such as 1-tert-pentylazo-1-cyanocyclohexane, azo-bis-isobutyronitrile and 1-tert-butylazo-cyanocyclohexane, 2,2'-azo-bis-(2-methyl)butyronitrile, 2,2'-azobis(2-methylpropionitrile), 2,2'-azobis(2-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. Alternatively, the initiator may comprise isoascorbic acid, which is also available from Sigma-Aldrich.

[0046] 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.

[0047] Alternatively, the initiator may optionally also comprise ferric(II) heptahydrate, potassium persulfate, or a combination thereof. Based on the weight of the silicone-(meth)acrylate copolymer, the initiator (C) may be used in an amount sufficient to provide 0.01% to 3%, alternatively 0.1% to 1.5%. Alternatively, based on the combined weight of the starting materials (A), (B), (C), (D), and (E) used in the emulsion polymerization, the initiator may be used in an amount of 0.15% to 0.23%.

[0048] 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 R13 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: R 18 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.

[0049] 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.

[0050] 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.

[0051] Based on the weight of the starting material (F) silicone-(meth)acrylate copolymer in the aqueous emulsion, the amount of (D-1) cationic surfactant may be from 0.1% to 5%. Alternatively, on the same basis, the amount of cationic surfactant may be at least 0.1%, alternatively at least 0.2%, alternatively at least 0.3%, alternatively at least 0.4%, alternatively at least 0.5%; while the amount of cationic surfactant may be at most 5%, alternatively at most 4%, alternatively at most 3%, alternatively at most 2%, alternatively at most 1%. Alternatively, on the same basis, the amount of cationic surfactant may be from 0.2% to 4%, alternatively 0.3% to 3%, alternatively 0.4% to 2.5%, and alternatively 0.5% to 2%.

[0052] 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; (vii) Alkyl polyethylene glycol ethers based on C10 Guerbert alcohol and ethylene oxides such as LUTENSOLS ™ XP 79.

[0053] 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.

[0054] 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 ™ Octylphenoxy polyethoxyethanol (40EO) sold under the trademark X-405; and ECOSURF. ™ EH alcohol ethoxylates, such as ECOSURF ™ EH-40. All of these surfactants are sold by Dow Chemical Company.

[0055] Other useful commercial nonionic surfactants are produced by Stepan Corporation under the trademark MAKON. ™ 10. Nonylphenoxy polyethoxyethanol (10EO) for sale; polyoxyethylene 23 lauryl ether (Laureth-23), commercially sold by Sigma Aldrich, Inc., St. Louis, Missouri, USA; and RENEX. ™ 30, a polyoxyethylene ether alcohol available from Fisher Scientific.

[0056] Alternatively, the nonionic surfactant may comprise a silicone polyether (SPE). The silicone polyether may have a rake-like structure in which polyoxyethylene or polyoxyethylene-polyoxypropylene copolymer units are grafted onto a siloxane backbone, or the SPE may have an ABA block copolymer structure in which A represents the polyether moiety and B represents the ABA-structured siloxane moiety. Suitable SPEs include DOWSIL from Dow Chemical Company, Midland, Michigan, USA. ™ OFX-5329 fluid, trade name DOWSIL ™ 67. Additives. Such silicone polyethers 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. Silicone polyethers may be added before or during step 1) of the emulsion polymerization method described above. Alternatively, silicone polyethers may be added to the leather treatment composition after the formation of the aqueous emulsion, for example by mixing.

[0057] The starting material (D-2) nonionic surfactant can be delivered in the diluent, and the amount used is sufficient to provide 0.1% to 10% surfactant based on the weight of the starting material (F) silicone-(meth)acrylate copolymer in the aqueous emulsion. Alternatively, on the same basis, the amount of nonionic surfactant may be at least 0.1%, alternatively at least 0.2%, alternatively at least 0.3%, alternatively at least 0.4%, alternatively at least 0.5%, alternatively at least 1%, alternatively at least 2%, alternatively at least 3%, alternatively at least 4%; while the amount of nonionic surfactant may be at most 10%, alternatively at most 9%, alternatively at most 8%, alternatively at most 7%, alternatively at most 5%, alternatively at most 4%, alternatively at most 3%, alternatively at most 2%, alternatively at most 1%. Alternatively, on the same basis, the amount of nonionic surfactant may be 1% to 10%, alternatively 2% to 10%, alternatively 3% to 10%, alternatively 5% to 9%, alternatively 6% to 8%, and alternatively 7%. Alternatively, based on the weight of the starting material (F) silicone-(meth)acrylate copolymer in the aqueous emulsion, the starting material (D-1) cationic surfactant and (D-2) nonionic surfactant may be present in a combined amount of ≤10%. Alternatively, based on the combined weight of the starting materials (A), (B), (C), (D), and (E) used in the emulsion polymerization, surfactant (D) may be used in an amount of 2% to 3.5%.

[0058] The starting material (E) is water. Water is generally not limited; for example, it can be treated or untreated. Examples of processes that can be used to purify water include distillation, filtration, deionization, and combinations of two or more of these, such that the water can be deionized, distilled, and / or filtered. Alternatively, the water can be untreated (e.g., tap water, i.e., supplied by a municipal water supply or well water, used without further purification). The amount of water is sufficient to form an aqueous emulsion for emulsion polymerization in step 1) of the method described above. Additional water may be added after step 1). For example, the aqueous emulsion prepared as described above may be diluted with additional water to obtain the desired amount of starting material before treating the leather substrate with the resulting leather treatment composition. Based on the combined weight of all the starting materials in step 1), water may be added in amounts of 20% to 97%, alternatively 30% to 90%, alternatively 40% to 80%, alternatively 50% to 97%, alternatively 50% to 90%, and alternatively 60% to 80%. Alternatively, on the same basis, water may be added in amounts of at least 20%, at least 30%, at least 40%, at least 50%, and at least 60%; while the amount of water may be at most 97%, at most 96%, at most 95%, and at most 80%. Alternatively, based on the combined weight of the starting materials (A), (B), (C), (D), and (E) used in the emulsion polymerization to prepare (F) the organosilicon-(meth)acrylate copolymer, the amount of water may be from 54% to 82%.

[0059] The silicone-(meth)acrylate copolymer (F) can be prepared by emulsion polymerization of a starting material comprising the macromonomer (A) and initiator (C) as described above (and optionally comonomer (B)). Alternatively, the silicone-(meth)acrylate copolymer can be a reaction product of a starting material consisting essentially of the macromonomer (A) and initiator (C) (and, when present, comonomer (B) and / or chain transfer agent). Alternatively, the silicone-(meth)acrylate copolymer is a reaction product of a starting material consisting of starting materials (A) and (C) (and, when present, (B) and / or (H)). It is not desirable to be bound by theory, but it is assumed that the starting material (D) surfactant and (E) water do not copolymerize with the starting materials (A) and (C) (and, when present, (B) and / or (H)), but the starting materials (D) and (E) merely act as mediators for copolymerization. However, the possibility that one or more of the starting materials (D) and / or (E) or any other starting material added during the method may participate in the copolymerization of the starting materials including (A) and (C) and any optional starting materials (i.e. (B) and / or (H)) (if present) should not be excluded in this document.

[0060] The silicone-(meth)acrylate copolymer comprises a unit formula (F-1):

[0061] , where each R 1 is a monovalent hydrocarbon group having 1 to 12 carbon atoms independently selected; each D 2 is independently a divalent hydrocarbon group having 2 to 12 carbon atoms; 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)oxyalkylene 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 the subscript b2 has at least 5 silicon atoms; the subscripts a, b1, and b2 represent the weight fractions of the units in the copolymer, and the values of the subscripts a, b1, and b2 are such that 0.25 < a ≤ 1; and 0 ≤ (b1 + b2) < 0.75; and the silicone-(meth)acrylate copolymer further comprises a terminal portion. In the unit formula (F-1), R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R, D, and D 2 are as described and exemplified above for formulas (A-1), (B-1), and (B-2). Alternatively, in the unit formula (F-1) of the silicone-(meth)acrylate copolymer, each R 1 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; each R 4 is independently selected from the group consisting of R and OSi(R 5 )3, where each R is methyl; each R 5 is independently selected from the group consisting of R and OSi(R6 A group consisting of 3 groups; where each R 6 Independently select a group consisting of free R and OSiR3; the condition is that R is selected. 4 R 5 and R 6 The organosilicon-(meth)acrylate copolymer macromonomer has 10 to 16 silicon atoms per molecule. Alternatively, the subscript a can have values ​​such that 0.50 ≤ a ≤ 1, alternatively 0.63 ≤ a ≤ 1, alternatively 0.75 ≤ a ≤ 1, and alternatively a = 1. Alternatively, the subscript b1 can have values ​​such that 0 ≤ b1 < 0.75, alternatively 0 ≤ b1 ≤ 0.5, alternatively 0 ≤ b1 < 0.25, and alternatively b1 = 0. Alternatively, the subscript b2 can have values ​​such that 0 ≤ b2 < 0.75, alternatively 0.01 ≤ b2 ≤ 0.5, alternatively 0.05 ≤ b1 < 0.25, and alternatively b1 = 0.25. Alternatively, a = 1, b1 = 0, and b2 = 0.

[0062] 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 0.45 μm PTFE syringe filter before injection. Samples were analyzed using a Waters e2695 LC pump and autosampler equipped with two 5 μm 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.

[0063] The additional starting material that may be added in step 1) of the method for preparing the copolymer described above includes a (H) chain transfer agent. Suitable chain transfer agents include thiols, such as alkyl thiols, for example n-octylthiol, n-dodecylthiol, dodecylthiol (dodecanethiol), and / or 2,2-dimethyldecylthiol. Alternatively, the chain transfer agent may be water-soluble, such as mercaptoacetic acid and / or 2-mercaptoethanol. Suitable chain transfer agents are known in the art and have been disclosed, for example, in Peter Nesvadba's "Radical Polymerization in Industry," *Performance Chemical Research*, GASF Schweiz AG, Basel, Switzerland, and *Encyclopedia of Radicals in Chemistry, Biology and Materials*, Online. © 2012 John Wiley & Sons, Ltd.).

[0064] The starting material (H) is optional and can be added in an amount of 0% to 1% based on the combined weight of the starting material (A) and, when present, the starting material (B). Alternatively, on the same basis, the chain transfer agent (H) can be used in an amount of 0.5% to 0.6%.

[0065] The starting material (I) is optionally a manganese ion source, which may be a manganese (II) compound. Suitable manganese compounds include manganese (II) acetate, manganese (II) nitrite, manganese (II) propionate, manganese (II) oxide, manganese (II) hydroxide, manganese (II) chloride, manganese (II) phosphate, manganese (II) perchlorate, their hydrates (e.g., manganese (II) acetate tetrahydrate), and combinations thereof. Alternatively, the manganese ion source may comprise manganese (II) acetate or manganese (II) acetate tetrahydrate, or combinations thereof. Suitable manganese ion sources are commercially available from Millipore Sigma of St. Louis, Missouri, USA; Feischel Technologies Inc. of Waltham, Massachusetts, USA; and City Chemical LLC of Connecticut, USA. The amount of manganese ion source depends on various factors, including the selection and amount of other starting materials used; however, based on the combined weight of starting material (A) and (if present) starting material (B), the amount can be from 0.1 ppm to 5,000 ppm. Alternatively, based on the combined weight of all starting materials in the leather treatment composition, the amount of manganese ion source can be >0 ppm, alternatively at least 0.5 ppm, alternatively at least 1 ppm, alternatively at least 1.5 ppm; while the amount of manganese ion source can be up to 10 ppm, alternatively up to 5 ppm, alternatively up to 4 ppm, and alternatively up to 3 ppm, and alternatively up to 2 ppm. Alternatively, based on the combined weight of starting materials (A), (B), (C), (D), and (E) used in the emulsion polymerization, the amount of manganese ion source can be from 0.0004% to 0.004%.

[0066] 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 thereof. Suitable phenolic compounds are commercially available, for example, from Millibo Sigma-Aldrich, St. Louis, Missouri, USA. The amount of phenolic compounds 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 leather treatment composition, the amount of phenolic compounds 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 compounds can be at most 500 ppm, alternatively at most 400 ppm, alternatively at most 350 ppm, and alternatively at most 320 ppm. Alternatively, based on the combined weight of starting materials (A), (B), (C), (D), and (E) used in the emulsion polymerization, the amount of phenolic compounds can be from 0.009% to 0.014%.

[0067] 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 comprise 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. Alternatively, the amount of the phenolic compound may be from 0.009% to 0.015% based on the combined weight of the starting materials (A), (B), (C), (D), and (E) used in the emulsion polymerization. The inhibitor described above may be added before or during step 1) of the polymerization reaction of the starting material (A) and, when present, (B). Alternatively, the inhibitor may be added to the leather treatment composition after the formation of the organosilicon-(meth)acrylate copolymer.

[0068] The starting material (K) is optionally a biocide. The biocide may be added before or during step 1) of the polymerization reaction of the starting material (A) and, when present (B), the organosilicon-(meth)acrylate copolymer to prepare the biocide. Alternatively, an inhibitor may be added to the leather treatment composition after the formation of the organosilicon-(meth)acrylate copolymer. 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 aqueous leather treatment composition, the amount of biocide may be >0% to 5% when used. Examples of starting materials (K) include (K-1) fungicides, (K-2) herbicides, (K-3) insecticides, (K-4) antimicrobial agents, or combinations thereof. Suitable biocides are disclosed, for example, in U.S. Patent 9,480,977.

[0069] The leather treatment composition may optionally also include a starting material (M) solvent. The solvent can be used to reduce viscosity and / or improve the coalescence of binder particles to promote coating formation after the leather treatment composition is applied to a leather substrate (e.g., during drying). Examples of suitable coalescence solvents are alcohols, ketones, glycol esters, and glycol ethers. Examples of coalescence solvents are monohydric alcohols (such as isopropanol), glycol ethers, glycol esters, and glycol ether esters. Suitable coalescence solvents may be marketed under the trade name DOWANOL. ™ DALPAD ™ CARBITOL ™ and CELLOSOLVE ™ Available commercially from Dow Chemical Company. Alternatively, the coalescing solvent may include butyl carbitol. Based on the combined weight of all starting materials in the leather treatment composition, the amount of coalescing solvent in the leather treatment composition may be up to 10%, alternatively 1% to 5%, alternatively up to 3%, alternatively up to 1%, and alternatively up to 0.1%. The coalescing solvent (type and amount) may be selected such that it does not adversely affect the stability of the leather treatment composition in emulsion form.

[0070] The leather treatment composition may optionally further comprise an amount of (Q) softening additive sufficient to impart softness without significantly reducing stain and / or oil repellency, the softening additive being selected from alkyl polysiloxanes of formula (Q-1): , where each R 19It is an independently selected monovalent saturated hydrocarbon group having 1 to 18 carbon atoms, and the subscript aa has an average value of 20 to 300; or a combination (Q-2) comprising 60% to 70% by weight of (Q-1) alkyl polysiloxane based on the combined weight of all starting materials in the (Q-2) combination, 29% to 39% by weight of (Q-2-1) silicone resin based on the combined weight of all starting materials in the (Q-2) combination, and 0% to 2% by weight of (Q-2-2) amino-functionalized polysiloxane based on the combined weight of all starting materials in the (Q-2) combination, wherein the silicone resin has a hardness of ≥20 as measured by a type A hardness tester according to JIS K 6249:2003, and the amino-functionalized polysiloxane has a functional group equivalent of 100 g / mol to 20,000 g / mol, wherein the equivalent means the molecular weight of the amino-functionalized polysiloxane per mole of nitrogen atoms, and has a functional group equivalent as measured by a type A hardness tester according to JIS K 6249:2003. The measurement using method 2283:2000 at 25℃ is 10mm. 2 / s to 100,000mm 2 / s kinematic viscosity. Alternatively, on the same basis, (Q-2-2)amino-functionalized polyorganosiloxane may be present in amounts of 1% to 2%.

[0071] (Q-1) Alkyl polysiloxanes have the following formula: , where each R 19 It is an independently chosen monovalent saturated hydrocarbon group with 1 to 18 carbon atoms, and the subscript aa has an average value of 20 to 300. R 19 The monovalent saturated hydrocarbon group can be an alkyl group, alternatively an alkyl group with 1 to 6 carbon atoms. Alternatively, the alkyl group may have 1 to 3 carbon atoms, alternatively 1 to 2 carbon atoms. Alternatively, each R... 19 Methyl groups may be used. Suitable alkyl polysiloxanes (e.g., bis-trimethylsiloxy-terminated polydimethylsiloxanes) are known in the art and may be used, for example, as XIAMETER. ™ The 200 fluid was commercially available from Dow Chemical Company in Midland, Michigan, USA.

[0072] 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.

[0073] The starting material (Q) softening additive can be delivered in a second aqueous emulsion comprising the (Q) softening additive, (D') a surfactant (which may be as described above for the starting material (D) surfactant), and (E') water (which may be as described above for the starting material (E)). The second aqueous emulsion can be prepared by known methods, such as those described in U.S. Patent Application Publication 2020 / 0332148, by varying the type and amount of the starting material as described herein.

[0074] The leather treatment composition described above also comprises a polyisocyanate. The polyisocyanate is exemplified by a reactive aliphatic polyisocyanate resin. The reactive aliphatic isocyanate resin may have an NCO content of 8.0% to 10.6%. Suitable polyisocyanates are known in the art and are commercially available. Suitable polyisocyanates include BINDER LS-3492 from Dow Chemical.

[0075] When selecting starting materials to add to the aqueous copolymer emulsion prepared as described above in the method including step (I) and the leather treatment composition formed in the method including each step (I) described 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, silicone polyethers can be used simultaneously as nonionic surfactants and wetting agents. The starting materials used in the aqueous emulsion and / or leather treatment composition may differ from each other. Examples of suitable optional additional starting materials and their amounts can be found, for example, in U.S. Patents 9,200,404, 10,100,377, and 1,151,8905.

[0076] The leather treatment compositions described herein can be formulated using starting materials that do not contain fluorocarbons. For example, the leather treatment compositions may be free of any starting materials containing fluorine atoms covalently bonded to carbon atoms. Furthermore, the leather treatment compositions may be free of crosslinking agents. For example, the leather treatment compositions may be free of isocyanates, such as reactive aliphatic polyisocyanate resins. It is not wishy-bound to be bound by theory, but it is believed that such crosslinking agents may be detrimental to the stain-repellent and / or oil-repellent properties of coatings prepared from the leather treatment compositions described herein.

[0077] The leather treatment composition prepared as described above can be used to treat leather. For example, a method for treating leather includes: I) applying the leather treatment composition described above to the surface of a leather substrate, and II) drying the substrate. Step I) can be carried out by any convenient method. The leather treatment composition can be applied to the substrate by any convenient method. For example, the leather treatment composition can be applied to the substrate by methods selected from the group consisting of: padding, spraying methods (such as air atomization spraying, air-assisted spraying, airless spraying, high-volume low-pressure spraying, and air-assisted airless spraying), scraping, roller coating, casting, rotary coating, dip coating, gravure coating, bar coating, screen coating, curtain coating, brush coating, and combinations thereof. There is no specific limitation on the amount of leather treatment composition applied to the substrate, and it can have a wet coating thickness of 10 μm to 200 μm, which corresponds to a dry coating thickness of 2 μm to 70 μm. Alternatively, a typical application rate of the leather treatment composition can be 2.0 g dry weight / m² (g / m²). 2 Up to 100g / m 2 However, the method should be sufficient to deliver a sufficient amount of organic acrylic adhesive and organosilicon-(meth)acrylate copolymer to impart stain and oil resistance to leather according to the method described below.

[0078] Step II) can be performed by any convenient method, such as, for example, by heating the substrate in an oven. Heating the substrate can be performed to remove all or part of the water. The exact temperature depends on various factors, including the temperature sensitivity of the type of leather selected and the desired drying time. Drying can be performed by any convenient method, such as air drying or heat drying of the coated substrate. The conditions for heat drying depend on various factors, including the selected substrate. For example, when the substrate contains natural leather, the heat drying temperature can be ≤120°C. Alternatively, for synthetic leather substrates, the heat drying temperature can be ≤180°C, alternatively ≤150°C, for a duration sufficient to remove most or all of the water. Alternatively, the temperature can be ≥100°C to promote water removal. Alternatively, the leather treatment composition applied to the substrate can be dried in a temperature range of 20°C to 100°C, alternatively 85°C to 100°C, to provide a coated leather substrate having a dried coating of the leather treatment composition on at least one surface of the leather substrate. The drying and curing methods can vary depending on, for example, the specific starting materials, quantities, and type of leather used to prepare the leather treatment composition. Examples of drying methods include air drying at room temperature, hot air drying at, for example, 85°C, and infrared heating. The method may optionally also include III) repeating steps I) and II) once or more to increase the thickness of the coating on the substrate. There are no particular limitations on the thickness of the film formed on the substrate.

[0079] The leather treatment methods described in this article can be used to apply coatings to leather, including natural leather and leather-like materials such as artificial leather, synthetic leather, and vinyl leather. Examples of leather-like materials include polyurethane, polyvinyl chloride, polyolefins, polyamides, and LUXSENSE, a silicone brand from Dow. ™ Silicone-based synthetic leather. Similarly, the leather treatment compositions described herein can be applied to natural leathers derived from, for example, cattle, sheep, goats, pigs, horses, kangaroos, deer, crocodiles, or snakes. The leather treatment compositions can be applied to leathers such as mineral-tanned or vegetable-tanned leathers, including full-grain leather, brushed or corrected-grain leather, and split leather, with or without pretreatment with an impregnation resin mixture, and with or without subsequent coating. Prior to application of the water-based leather treatment composition, the leather may be smoothed or embossed to provide a flat surface for coating or to reduce the porosity of brushed or split leather. Alternatively, the leather treatment composition can be applied directly to a substrate or indirectly to a primer layer. Coatings made from the leather treatment compositions of the present invention can include a base coat, a colored coat, and a top coat, comprising any of a clear coat, a dyed or translucent coat, or a colored coat.

[0080] Examples of the resulting treated leather base are automotive parts (e.g., armrests, dashboards, seats, and other interior parts present in a vehicle); clothing such as coats, trousers, flight jackets, motorcycle clothing, shoes, and gloves; luggage or handbags; accessories such as belts, wallets, and notebooks; furniture; or saddles (e.g., for bicycles or motorcycles).

[0081] Example

[0082] The following embodiments are provided to illustrate the invention to those skilled in the art, and these embodiments should not be construed as limiting the scope of the invention as set forth in the claims. The starting materials used in these embodiments are summarized in Table 1 below.

[0083] Table 1 - Starting Materials

[0084] In this Reference Example 1, an organosilicon-(meth)acrylate copolymer emulsion (emulsion 1) was prepared as follows. 3.75 g of ECOSURF... ™ EH40, 39.97 g 3MT-ALMA, 0.4 g 2.5% aqueous solution of 4-methoxyphenol, 0.006 g hydroquinone, and 0.12 g 0.7% aqueous solution of manganese(II) acetate tetrahydrate, along with 93.83 g water, were added to a wide-mouth flask. An aqueous emulsion was prepared using an ultrasonic mixer (Fisherbrand Model 705 sonic breaker, amplitude 50, power approximately 62 W, ​​duration 2 minutes). The aqueous emulsion was then transferred to a tank 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 contents of the wide-mouth flask were stirred for 6 hours. The contents of the wide-mouth flask were then cooled to RT, and the resulting emulsion 1 was poured into a bottle.

[0085] Referring to Example 2, the leather treatment composition was prepared as follows: All starting materials (except isocyanate) shown in Table 2 below were added to a plastic cup. The cup was placed in a dental mixer (Brand: RohChem High-Speed ​​Mixer Benelux / Model: DAC 150.1FV) and mixed at 2700 rpm for 1 minute. Then, isocyanate (if used) was added, and the sample was mixed again at 2700 rpm for 1 minute.

[0086] Table 2 - Leather Treatment Compositions

[0087] 91 PUD contains 2.5% active ingredient concentration = 20g PU / 1.72g emulsion prototype in adhesive.

[0088] In this reference example 3, the leather treatment coating sample from Table 2 was then applied to a leather substrate by applying a 2×340µm wet coating, and then cured at 80°C in an oven (brand: Memmert / model: UF110 or UF110 Plus, both with forced air).

[0089] In this Reference Example 4, the water and alcohol repellency of the coated sample prepared according to Reference Example 3 were tested using AATCC 193, and the Kaydol oil repellency of the coated sample prepared according to Reference Example 3 was tested using AATCC TM118. The results are shown in Table 3 below.

[0090] Table 3 - AATCC performance results of Base 1 (white, base-coated leather) samples with various formulations.

[0091] The results in Table 3 show that samples F5 and F7, using a combination of emulsion 1 and an acrylic binder, provided unexpected improvements in oil repellency compared to samples without emulsion 1 (samples F4 and F6, respectively). Sample F3 lacked an organic acrylic binder and contained only an organic polyurethane binder, and did not exhibit the same good water and alcohol repellency. Sample F5 provided satisfactory results and contained both an organic polyurethane binder and an organic acrylic binder, while sample F7 contained no polyurethane binder, indicating that the PU binder was optional. Sample F1 failed the AATCC-118 test, indicating that emulsion 1 alone did not provide sufficient Kaydol oil repellency under the test conditions.

[0092] The testing methods used in this article are as follows.

[0093] AATCC TM193-2007e4(2017)e2 - Test method for water repellency in liquids: resistance to water / alcohol solutions.

[0094] The resistance of the treated substrate to wetting by a range of selected water:alcohol solutions with varying surface tensions was evaluated using the water / alcohol test method (AATCC 193). The water repellency rating is the highest-numbered test liquid that does not wet the fabric surface (scaled from zero to eight, where level eight indicates the most water-repellent surface). The droplets were observed for 10 seconds ± 2 seconds. Water and isopropanol were used in the above examples.

[0095] AATCC TM118-2020e test method for oil repellency and hydrocarbon resistance.

[0096] The oil repellency test method (AATCC TM118) is used to measure the resistance of treated surfaces to a range of selected liquid hydrocarbons with varying surface tensions. The oil repellency rating is the highest-numbered test liquid that does not wet the fabric surface. Observe the droplets for 30 seconds ± 2 seconds. The fabric's oil repellency rating is the numerical value of the highest-numbered test liquid that does not wet the substrate within the 30-second time period. The rating scale is: A = Pass; clear, very round droplets; B = Barely Pass; partially darkened round droplets; C = Fail; noticeable and / or complete wetting; D = Fail; complete wetting.

[0097] Definition and use of terms

[0098] 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 4.

[0099] Table 4 – Abbreviations

Claims

1. A leather treatment composition, the leather treatment composition comprising: (I) An organic binder, the organic binder comprising an organic acrylic polymer; (II) A silicone-(meth)acrylate copolymer, the silicone-(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 A group consisting of 3, of which 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 having 1 to 12 units, and a divalent hydrocarbon group having 2 to 4 carbon atoms; Each R 5 Independently select R and DSi(R) 6 Groups consisting of 3; 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 subscripts a, b1 and b2 have values such that 0.25 < a ≤ 1; and 0 ≤ (b1 + b2) < 0.75, and (a + b1 + b2 + 0 1), provided that the silicone-(meth)acrylate copolymer further comprises a terminal portion; (III) A surfactant; (IV) Water; and (V) An aliphatic polyisocyanate resin.

2. The composition according to claim 1, wherein the organic binder further comprises a polyurethane binder.

3. The composition according to claim 1 or claim 2, wherein the silicone-(meth)acrylate copolymer has: Each R 1 It is methyl. Each R 2 It is methyl. Each D 2 It is propylidene. Subscript a = 1, Subscript b1 = 0, and Subscript b2 = 0.

4. The composition according to any one of claims 1 to 3, wherein the composition further comprises additional starting materials selected from the group consisting of a manganese ion source, a phenolic compound, a biocide, a silicone polyether, a solvent, a matting additive, a rheology modifier, a softening additive, and a combination of two or more of them.

5. The composition according to claim 4, wherein the manganese ion source is present, and the manganese ion source comprises manganese(II) acetate, manganese(II) acetate tetrahydrate, or a combination thereof.

6. The composition according to claim 4 or claim 5, wherein the phenolic compound is present, and the phenolic compound is selected from the group consisting of hydroquinone, monomethyl ether of hydroquinone, tert-butyl hydroquinone, and a combination of two or more of them.

12. The method according to claim 2, 4 and any one of claims 7 to 11, wherein (I) the manganese ion source is present, and the manganese ion source comprises manganese(II) acetate, manganese(II) acetate tetrahydrate, or a combination thereof.

7. A method for preparing the composition according to any one of claims 1 to 6, wherein the method comprises: (I) Mixing starting materials, the starting materials comprising i) An aqueous composition, the aqueous composition comprising an organic binder and water, ii) An aqueous emulsion, the aqueous emulsion comprising the silicone-(meth)acrylate copolymer, the surfactant and water, and iii) An isocyanate.

8. The method of claim 7, further comprising adding an additional starting material to the starting material during step (I), or adding an additional starting material to one or more of i), ii) and iii) prior to step (I), wherein the additional starting material is selected from the group consisting of: phenolic compounds, manganese ion sources, organosilicon polyethers (different from the surfactant used for starting material (III)), rheology modifiers, matting additives, biocides, additional water, solvents, softening additives, and combinations of two or more of the above.

9. The method according to claim 7 or claim 8, further comprising preparing the organosilicon-(meth)acrylate copolymer prior to step (I) by a method comprising: 1) Copolymerize the starting materials, said starting materials comprising (A) Organosilicon-(meth)acrylate macromonomers 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; Optional (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 combinations 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 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 6 This results in the organosilicon-(meth)acrylate copolymer macromonomer of formula (B-2) having at least 5 silicon atoms per molecule; The 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 The starting material (B) is present in an amount ranging from 0% to <75% by weight, based on the combined weight of starting materials (A) and (B); and The starting materials (A) and (B) are copolymerized in the presence of an additional starting material, wherein the additional starting material comprises: (C) Initiator; Optional (H) chain transfer agent; The optional manganese ion source (I); and Optional (J) of the phenolic compounds; and One of the conditions (i) or (ii) is satisfied. Condition (i) further includes step 1) adding a solvent before or during step 1), removing the solvent after forming the silicone-(meth)acrylate copolymer (F), and forming an aqueous emulsion comprising the silicone-(meth)acrylate copolymer (F), (D) a surfactant, and (E) water; and Condition (ii) is that step 1) includes an emulsion polymerization reaction; the additional starting material further comprises (D) the surfactant and (E) the water; and The product of step 1) comprises an aqueous emulsion containing (F) the organosilicon-(meth)acrylate copolymer, (D) the surfactant and (E) the water.

10. The method of claim 9, wherein the method further comprises adding (G) the isocyanate in step I) after mixing all other starting materials.

11. The method according to claim 9 or claim 10, wherein the starting material (A) is 3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxane-3-yl)propyl methacrylate.

12. The method according to any one of claims 9 to 11, wherein the initiator in (C) comprises: 2,2'-azobis(2-methylpropanediamine) dihydrochloride.

13. The method according to any one of claims 9 to 12, wherein the chain transfer agent (H) is present, and the chain transfer agent comprises dodecyl mercaptan.

14. The method according to any one of claims 9 to 13, wherein the isocyanate in (G) comprises a reactive aliphatic polyisocyanate resin.

15. A method for treating leather, wherein the method comprises: I) Applying the leather treatment composition according to any one of claims 1 to 6, or the leather treatment composition prepared by any one of claims 7 to 14, to the surface of a leather substrate, and II) Dry the substrate.

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