Silicone leather coating composition

Abstract

This disclosure relates to a method for preparing a carbinol-terminated silicone / polyurethane hybrid prepolymer coating composition (v), comprising: (A) a step of preparing a carbinol-terminated silicone / polyurethane hybrid prepolymer; and (B) a carbinol-terminated silicone / polyurethane hybrid prepolymer ((v)(a)) produced in (A) containing an optional cured silicone elastomer powder (v)(b), an optional silicon-free microparticle and / or fine particles (v)(c), each containing at least two or at least three silicon-bonded hydrogen (-Si-H) groups per molecule. The present invention relates to a method comprising the step of preparing a carbinol-terminated silicone / polyurethane hybrid prepolymer coating composition (v) by mixing a polyorganosiloxane (v)(d), a polyisocyanate having three or more isocyanate groups per molecule, in an amount such that the molar ratio of the -OH groups in (v)(a) to the -NCO groups in (v)(f) in the carbinol-terminated silicone / polyurethane hybrid prepolymer coating composition (v) is 0.95:1 to 1.05:1, and a platinum group metal catalyst (v)(g). The carbinol-terminated silicone / polyurethane hybrid prepolymer coating composition is prepared for use in silicone leather composite materials.

Description

[Technical Field]

[0001] This disclosure relates to a method for preparing a carbinol-terminated silicone / polyurethane hybrid prepolymer coating composition (v), (A) A step of preparing a carbinol-terminated silicone / polyurethane hybrid prepolymer, (B) A step to prepare a carbinol-terminated silicone / polyurethane hybrid prepolymer coating composition (v) by mixing the carbinol-terminated silicone / polyurethane hybrid prepolymer (component (v)(a)) produced in (A) with an optionally selected cured silicone elastomer powder (v)(b); optionally selected silicon-free particles and / or fine particles (v)(c); a polyorganosiloxane (v)(d) containing at least two or at least three silicon-bonded hydrogen (-Si-H) groups per molecule; a polyisocyanate crosslinking agent (v)(f) having three or more isocyanate groups per molecule, in an amount such that the molar ratio of the -OH groups in (v)(a) to the -NCO groups in (v)(f) in the carbinol-terminated silicone / polyurethane hybrid prepolymer coating composition (v) is 0.95:1 to 1.05:1; and a platinum group metal catalyst (v)(g). The present invention relates to a method including the following: Carbinol-terminated silicone / polyurethane hybrid prepolymer coating compositions are prepared for use in silicone leather composite materials. [Background technology]

[0002] A variety of synthetic alternatives have been developed to replace natural leather, primarily using polyurethane (PU) or polyvinyl chloride (PVC) materials. These are used in a wide range of applications, including furniture, decorations, handbags, suitcases, clothing, footwear, automotive interiors, and automotive seats. However, to meet increasingly stringent safety regulations, synthetic leather must meet stringent physical property requirements, such as flame retardancy and smoke concentration, as well as suitable adhesive strength to prevent the coating layer from peeling off during use, heat resistance, stain resistance, solvent resistance, and hydrolysis resistance. PU and / or PVC materials often fail to meet one or more of the aforementioned physical property requirements.

[0003] Silicone-based leather composites provide further synthetic alternatives to natural leather. Such silicone-based leather composites may have several advantages over the aforementioned PU and / or PVC-based synthetic leather materials. For example, silicone-based leather composites can be prepared using more environmentally friendly production methods, without using plasticizers, toxic heavy metals, or environmentally problematic solvents such as dimethylformamide (DMF), which often remain at least partially in synthetic PU and / or PVC leather products after manufacturing.

[0004] Silicone leather composites can be manufactured through several routes, but generally, they are produced using a textile support layer, two or more layers of hydrosilylated curable liquid silicone rubber compositions, and release paper. For example, a first liquid silicone rubber (LSR) composition may be coated onto the release paper and then cured to form a first layer or skin layer. A second LSR composition, usually having different properties from the first LSR composition, is bonded to the cured first layer to form an adhesive layer, and a textile support layer is bonded to the second LSR layer before curing. The second LSR composition is then cured to form a binder layer located between the skin layer and the textile support layer. If deemed appropriate for forming a silicone leather composite, one or more additional layers of hydrosilylated curable silicone elastomer compositions may be applied between the release paper and the textile layer. For example, a third layer may be provided as a protective topcoat on top of the skin layer. If necessary, the release paper is then removed.

[0005] Such silicone-based leather composite materials can exhibit superior performance compared to conventional PU and PVC synthetic leathers in terms of physical properties, for example, by providing better flexibility over a wide temperature range, as well as excellent UV resistance, heat resistance, and flame retardancy. The top coat is particularly important because it not only helps to provide advantageous properties such as stain resistance, but also provides a gentle feel against human skin and a superior tactile experience for the user.

[0006] However, due to the inherently weak intermolecular interactions between polysiloxane chains, silicone products have the disadvantage of insufficient mechanical strength and therefore insufficient abrasion resistance. Consequently, the use of silicone leather composites tends to be limited to application scenarios with low abrasion resistance requirements, while PU and PVC synthetic leathers are often used in applications requiring good abrasion resistance, such as automotive interiors.

[0007] Therefore, there is still a need to provide a silicone leather composite material that has improved abrasion resistance while retaining the advantages of physical properties compared to PU and PVC-based synthetic leathers. [Overview of the project]

[0008] A method for preparing a carbinol-terminated silicone / polyurethane hybrid prepolymer coating composition, (A) (I) Diisocyanate in an amount of 20-30% by weight of the starting components of step (A), (II) Alkanediol chain extender in an amount of 5 to 15% by weight of the starting components of step (A), (III) Carbinol-terminated polydimethylsiloxane in an amount of 25-45% by weight of the starting components of step (A), (IV) A solvent in an amount of 20-40% by weight of the starting components of step (A), and optionally, (V) A step of preparing a carbinol-terminated silicone / polyurethane hybrid prepolymer by mixing together a polyethertriol in an amount of 2% by weight or less of the starting components of step (A), If the molar ratio of OH:NCO is greater than 1.15:1, The process involves gradually introducing a suitable catalyst while heating the mixture to a predetermined reaction temperature of 60-90°C, stirring the mixture for a predetermined time of at least 90 minutes while maintaining the mixture at the predetermined reaction temperature, and then cooling the reaction product of the carbinol-terminated silicone / polyurethane hybrid prepolymer. (B) (v)(a) Carbinol-terminated silicone / polyurethane hybrid prepolymer, (v)(b) Any cured silicone elastomer powder, (v)(c) Any silicon-free organic particles and / or fine particles selected from at least one of polymethyl methacrylate (PMMA), ethylene-vinyl acetate copolymer (EVA), ethylene-acrylate copolymer (EAA), ethylene-butyl acrylate copolymer (EBA), ethylene-methyl acrylate copolymer (EMA), ethylene-ethyl acrylate copolymer (EEA), or polyurethane polymer, (v)(d) A polyorganosiloxane containing at least 2 or at least 3 silicon-bonded hydrogen (-Si-H) groups per molecule, present in an amount of 1 wt% to 10 wt% of the composition, (v)(f) A polyisocyanate crosslinking agent having 3 or more isocyanate groups per molecule, wherein the molar ratio of the -OH groups in (v)(a) to the -NCO groups in (v)(f) in the carbinol-terminated silicone / polyurethane hybrid prepolymer-based coating composition (v) is 0.95:1 to 1.05:1, and (v)(g) A platinum group metal-based catalyst, and preparing the carbinol-terminated silicone / polyurethane hybrid prepolymer-based coating composition (v) by mixing them, A method comprising the above is provided.

[0009] A method for preparing a carbinol-terminated silicone / polyurethane hybrid prepolymer-based coating composition, (v)(a) A silicone / polyurethane hybrid prepolymer, (v)(b) Any cured silicone elastomer powder, (v)(c) Any silicon-free organic particles and / or fine particles selected from at least one of polymethyl methacrylate (PMMA), ethylene-vinyl acetate copolymer (EVA), ethylene-acrylate copolymer (EAA), ethylene-butyl acrylate copolymer (EBA), ethylene-methyl acrylate copolymer (EMA), ethylene-ethyl acrylate copolymer (EEA), or polyurethane polymer, (v)(d) A polyorganosiloxane containing at least two or at least three silicon-bonded hydrogen (-Si-H) groups per molecule, present in an amount of 1 wt% to 10 wt% of the composition, (v)(f) A polyisocyanate crosslinking agent having three or more isocyanate groups per molecule, in an amount such that the molar ratio of the -OH groups in (v)(a) to the -NCO groups in (v)(f) in the carbinol-terminated silicone / polyurethane hybrid prepolymer system coating composition (v) is 0.95:1 to 1.05:1, and (v)(g) A platinum group metal-based catalyst, and a method is provided that includes mixing them.

BEST MODE FOR CARRYING OUT THE INVENTION

[0010] In one embodiment, the carbinol-terminated silicone / polyurethane hybrid prepolymer is in a first step A, (I) Diisocyanate in an amount of 20 to 30 wt% of the starting components of step (A), (II) An alkane diol chain extender in an amount of 5 to 15 wt% of the starting components of step (A), (III) Carbinol-terminated polydimethylsiloxane in an amount of 25 to 45 wt% of the starting components of step (A), (IV) A solvent in an amount of 20 to 40 wt% of the starting components of step (A), and optionally, (V) A polyether triol in an amount of 2 wt% or less of the starting components of step (A), are mixed together, The molar ratio of OH:NCO is greater than 1.15:1, The coating composition is prepared by gradually introducing a suitable catalyst while heating the mixture to a predetermined reaction temperature of 60-90°C, stirring the mixture for a predetermined time of at least 90 minutes while maintaining the mixture at the predetermined reaction temperature, and then cooling the reaction product of the carbinol-terminated silicone / polyurethane hybrid prepolymer, as described above and before step B.

[0011] To avoid any ambiguity, the molar ratio of OH:NCO greater than 1.15:1 relates to the total -OH content of all starting components, i.e., the cumulative molar ratio of the -OH content of components (II), (III), (IV) if the solvent contains -OH groups, and (V) if present, to the NCO groups of component (I).

[0012] Carbinol-terminated silicone / polyurethane hybrid prepolymer coating compositions are (i) Textile support layer and (ii) A silicone binder, which is a cured product of a two-component hydrosilylated curable silicone rubber composition designed to adhere to a textile support layer (i) and a skin layer (iii), and having a Shore A hardness of 20 to 40 as measured according to ASTM D2240, (iii) A silicone skin layer which is a cured product of a two-component hydrosilylated curable silicone rubber composition containing an adhesion promoter and has a Shore A hardness of 50 or greater (≧) when measured according to ASTM D2240, (iv) A silicone topcoat layer which is a cured product of a two-component hydrosilylated curable silicone topcoat containing an adhesion promoter, (v) Silicone / polyurethane hybrid prepolymer coating layer, Prepared for use in silicone leather composite materials, including The silicone binder (ii) is bonded between the textile support (i) and the skin layer (iii), the skin layer (iii) is located between the silicone binder layer (ii) and the silicone / polyurethane hybrid prepolymer coating layer, and the silicone topcoat layer (iv) is located on the silicone / polyurethane hybrid prepolymer coating layer (v).

[0013] Carbinol-terminated silicone / polyurethane hybrid prepolymer coating compositions obtained or obtainable by the above method are also provided.

[0014] Furthermore, a carbinol-terminated silicone / polyurethane hybrid prepolymer coating composition (v) is, (v)(a) Carbinol-terminated silicone / polyurethane hybrid prepolymer, (v)(b) Any cured silicone elastomer powder, (v)(c) Any optional silicon-free particles and / or fine particles selected from at least one of polymethyl methacrylate (PMMA), ethylene-vinyl acetate copolymer (EVA), ethylene-acrylate copolymer (EAA), ethylene-butyl acrylate copolymer (EBA), ethylene-methyl acrylate copolymer (EMA), ethylene-ethyl acrylate copolymer (EEA), or polyurethane polymer. (v)(d) A polyorganosiloxane containing at least two or at least three silicon-bonded hydrogen (-Si-H) groups per molecule, present in an amount of 1% to 10% by weight of the composition. (v)(f) A polyisocyanate crosslinking agent having three or more isocyanate groups per molecule, in an amount such that the molar ratio of the -OH group in (v)(a) to the -NCO group in (v)(f) in the carbinol-terminated silicone / polyurethane hybrid prepolymer coating composition (v) is 0.95:1 to 1.05:1, and A carbinol-terminated silicone / polyurethane hybrid prepolymer coating composition (v) is provided, which contains (v)(g) a platinum group metal catalyst.

[0015] Furthermore, a method for preparing a carbinol-terminated silicone / polyurethane hybrid prepolymer, (I) Diisocyanate in an amount of 20-30% by weight of the starting components of step (A), (II) Alkanediol chain extender in an amount of 5 to 15% by weight of the starting components of step (A), (III) Carbinol-terminated polydimethylsiloxane in an amount of 25-45% by weight of the starting components of step (A), (IV) A solvent in an amount of 20-40% by weight of the starting components of step (A), and optionally, (V) Mix together the starting components of step (A) with a polyethertriol in an amount of 2% by weight or less, A method is also provided, in which the molar ratio of OH:NCO is greater than 1.15:1, a suitable catalyst is gradually introduced while heating the mixture to a predetermined reaction temperature of 60-90°C, the mixture is stirred for a predetermined time of at least 90 minutes while maintaining the mixture at the predetermined reaction temperature, and then the reaction product of the carbinol-terminated silicone / polyurethane hybrid prepolymer is cooled.

[0016] A carbinol-terminated silicone / polyurethane hybrid prepolymer that can be obtained or obtained by the above method is provided.

[0017] Furthermore, the use of the above-mentioned carbinol-terminated silicone / polyurethane hybrid prepolymer in the above-mentioned carbinol-terminated silicone / polyurethane hybrid prepolymer coating composition for silicone leather composite materials, wherein the silicone leather composite material is (i) Textile support layer and (ii) A silicone binder, which is a cured product of a two-component hydrosilylated curable silicone rubber composition designed to adhere to a textile support layer (i) and a skin layer (iii), and having a Shore A hardness of 20 to 40 as measured according to ASTM D2240, (iii) A silicone skin layer which is a cured product of a two-component hydrosilylated curable silicone rubber composition containing an adhesion promoter and has a Shore A hardness of 50 or greater (≧) when measured according to ASTM D2240, (iv) A silicone topcoat layer which is a cured product of a two-component hydrosilylated curable silicone topcoat containing an adhesion promoter, (v) Silicone / polyurethane hybrid prepolymer coating layer, Includes, A silicone binder (ii) is bonded between a textile support (i) and a skin layer (iii), the skin layer (iii) is located between the silicone binder layer (ii) and a silicone / polyurethane hybrid prepolymer coating layer, and a silicone topcoat layer (iv) is located on the silicone / polyurethane hybrid prepolymer coating layer (v).

[0018] In one embodiment, the silicone / polyurethane hybrid prepolymer coating layer (v) is a carbinol-terminated silicone / polyurethane hybrid prepolymer coating layer having an elastic modulus of 10 MPa or more at 100% elongation, as determined according to ASTM D882.

[0019] A silicone leather composite material, (i) Textile support layer and (ii) A silicone binder, which is a cured product of a two-component hydrosilylated curable silicone rubber composition designed to adhere to a textile support layer (i) and a skin layer (iii), and having a Shore A hardness of 20 to 40 as measured according to ASTM D2240, (iii) A silicone skin layer which is a cured product of a two-component hydrosilylated curable silicone rubber composition containing an adhesion promoter and has a Shore A hardness of 50 or greater (≧) when measured according to ASTM D2240, (iv) A silicone topcoat layer which is a cured product of a two-component hydrosilylated curable silicone topcoat containing an adhesion promoter, (v) A silicone / polyurethane hybrid prepolymer coating layer which is a cured product of the above silicone / polyurethane hybrid prepolymer coating composition, Includes, A silicone leather composite material in which a silicone binder (ii) is bonded between a textile support (i) and a skin layer (iii), the skin layer (iii) is located between the silicone binder layer (ii) and a silicone / polyurethane hybrid prepolymer coating layer, and a silicone topcoat layer (iv) is located on the silicone / polyurethane hybrid prepolymer coating layer (v).

[0020] Furthermore, a method for preparing the above-mentioned silicone leather composite material, First, the process involves preparing a prepolymer as described above, then preparing a carbinol-terminated silicone / polyurethane hybrid prepolymer coating composition as described above, and then, (a) The release paper, (v)(a) Carbinol-terminated silicone / polyurethane hybrid prepolymer, (v)(b) Any cured silicone elastomer powder, (v)(c) A step of coating with a layer of a carbinol-terminated silicone / polyurethane hybrid prepolymer coating composition comprising any silicon-free particles and / or fine particles selected from at least one of polymethyl methacrylate (PMMA), ethylene-vinyl acetate copolymer (EVA), ethylene-acrylate copolymer (EAA), ethylene-butyl acrylate copolymer (EBA), ethylene-methyl acrylate copolymer (EMA), ethylene-ethyl acrylate copolymer (EEA), or polyurethane polymer, A step of curing the composition to provide a carbinol-terminated silicone / polyurethane hybrid prepolymer coating layer (v), (b) A step of applying a layer of silicone skin composition onto a cured carbinol-terminated silicone / polyurethane hybrid prepolymer coating layer (v), and curing the composition to provide a silicone skin layer (iii), (c) A step of applying a layer of silicone binder composition onto a cured silicone skin layer (iii), applying a textile layer (i) onto the silicone binder composition, curing and / or laminating the composition to form a silicone binder layer (ii) between the textile support layer (i) and the skin layer (iii), (d) A step of removing the release paper from the cured carbinol-terminated silicone / polyurethane hybrid prepolymer coating layer (v), A method is provided which includes the steps of (e) applying a layer of a two-component hydrosilylated curable silicone topcoat composition onto a cured carbinol-terminated silicone / polyurethane hybrid prepolymer coating layer (v), and curing the topcoat composition to form a silicone topcoat layer (iv).

[0021] Carbinol-terminated silicone / polyurethane hybrid prepolymer Carbinol-terminated silicone / polyurethane hybrid prepolymers are derived from the following starting components, namely: (I) Diisocyanate in an amount of 20-30% by weight of the starting components of step (A), (II) Alkanediol chain extender in an amount of 5 to 15% by weight of the starting components of step (A), (III) Carbinol-terminated polydimethylsiloxane in an amount of 25-45% by weight of the starting components of step (A), (IV) Solvent in an amount of 20-40% by weight of the starting components of step (A), and optionally (V) Prepared from a polyethertriol in an amount of 2% by weight or less of the starting component of step (A), The molar ratio of OH:NCO is greater than 1.15:1.

[0022] To avoid any doubt, the carbinol-terminated silicone / polyurethane hybrid prepolymers described herein are those in which all isocyanate groups have reacted with the carbinol groups, leaving carbinol functional groups as terminal groups and no isocyanate terminal groups remaining. As stated above, the molar ratio of OH:NCO is greater than 1.15:1 with respect to the total -OH content of all starting components, i.e., the -OH content of components (II), (III), (IV) if the solvent contains -OH groups, and (V) if present, : the cumulative molar ratio of NCO groups in component (I).

[0023] Diisocyanate component (I) The diisocyanate component (I) is any suitable aromatic diisocyanate, such as polymethylene polyphenyl diisocyanate, diphenylmethane diisocyanate, polymeric diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate, xylylene diisocyanate, phenylene diisocyanate, tolylene diisocyanate, and naphthalene diisocyanate; or Aliphatic or alicyclic polyisocyanates, such as hexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate (IPDI), dicyclohexylmethane diisocyanate, and tetramethylxylylene diisocyanate; or mixtures of two or more thereof may be used.

[0024] Aliphatic or alicyclic diisocyanates, such as IPDI, are preferred. The diisocyanate component (I) is present in the starting components for producing the carbinol-terminated silicone / polyurethane hybrid prepolymer in an amount of 20-30% by weight, or 20-26% by weight. It has been found that to ensure good JSPS abrasion resistance results in silicone leather composites, the starting components must contain at least 20% by weight of diisocyanate (JSPS testing equipment is used to evaluate the abrasion resistance of leather, fabrics, vinyl, seams, plastics, and other materials).

[0025] Alkanediol chain extender (II) Alkanediol chain extenders (II) are short-chain organic diols having 2 to 6 carbon atoms per molecule, such as ethylene glycol, 1,3-propanediol, and / or 1,4-butanediol. The hydroxyl content of alkanediol chain extenders (II) can be determined according to ASTM-D4274-11. Alkanediols are present in the starting components for preparing carbinol-terminated silicone / polyurethane hybrid prepolymers in amounts of 5 to 15% by weight, or 6 to 13.5% by weight, or 7 to 11% by weight.

[0026] Carbinol-terminated polydialkylsiloxane polymer (III) Typically, carbinol-terminated polydialkylsiloxane polymers (III) have a hydroxyl value of 40 mg KOH / g or greater, as measured according to ASTM-D4274-11, and are carbinol-terminated polydimethylsiloxane polymers.

[0027] To avoid any ambiguity, the terminal carbinol (C-OH) group is a C-OH group attached to terminal silicon via a suitable non-hydrolyzable organic bond, such as the following: -Z 5 z’ -D d -OH In the formula, Z 5 is a divalent alkylene group containing 1 to 6 carbon atoms, or 2 to 6 carbon atoms, or 2 to 4 carbon atoms, z' is 0 or 1, and D is the average formula (-OC n’ H 2n’ It is one or more linear or branched polyethers containing repeating units having the formula )[wherein n' is an integer from 2 to 6, and d is an integer from 1 to 6, or from 2 to 4]. Suitable commercially available carbinol-terminated polydimethylsiloxanes include, for example, DOWSIL(trademark) BY16-201 from Dow Silicones Corporation or KF-6000 and KF-6001 from Shin-Etsu Chemical Co. Ltd. Carbinol-terminated polydialkylsiloxane polymers are present in amounts of 25-45% by weight, 25-42% by weight, 25-40% by weight, 25-38% by weight, or 30-38% by weight in the starting components for preparing carbinol-terminated silicone / polyurethane hybrid prepolymers. The presence of more than 45% by weight of carbinol-terminated polydialkylsiloxane polymers has been found to lead to insufficient JSPS abrasion resistance results (less than 4500). As an alternative, a carbinol-terminated polydialkylsiloxane polymer of 42% by weight or less, or a carbinol-terminated polydialkylsiloxane polymer of 38% by weight or less, is used, and in either case, a good JSPS abrasion resistance result of at least 5000 is guaranteed.

[0028] Solvent (IV) Any suitable solvent can be used as solvent (IV). Preferably, solvent (IV) does not contain any -OH groups, or solvent (IV) does not contain any -OH groups. The solvent is an essential component because in the absence of a solvent, the overall viscosity of the starting components becomes too high, making good mixing impossible. Examples of suitable solvents include glycol ethers such as ethylene glycol dimethyl ether (CH3O(CH2)2OCH3) and ethylene glycol dibutyl ether, and / or (but not limited to) ethylene glycol methyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol diacetate, and dipropylene glycol monoethyl ether acetate, with the following structure: CH3OCH2CH(CH3)OC(=O)CH3 Examples include one or more esters of glycol ethers, such as dipropylene glycol methyl ether acetate (DPMA), which have the properties of [unclear]. If the solvent contains -OH groups, these -OH groups are included in the calculation of the -OH group:NCO group molar ratio, and these -OH groups will potentially interact with NCO groups during the polymerization process. Therefore, in order to ensure that the solvent can evaporate and not participate in the chemical reaction with the NCO groups, it is preferable that the -OH groups are absent.

[0029] Polyethertriol (V) Component (V) is optional and is a polyethertriol in an amount of 2% by weight or less of the starting components of step (A). Component (V) may be any suitable polyethertriol. For example, polyethertriol (V) is A polyethertriol with a hydroxyl value of 647-676 mg KOH / g, sold by Dow Chemical Company under the trade name VORANOL (trademark) CP 260 polyol, or A polyethertriol with a hydroxyl value of 370-396 mg KOH / g, sold by Dow Chemical Company under the trade name VORANOL (trademark) CP 450 polyol, or It may be HF-302 polyether polyol, which is commercially available from Zhejiang Hengfeng New Material Co., Ltd.

[0030] As mentioned above, the molar ratio of OH:NCO is greater than 1.15:1. This molar ratio relates to the cumulative molar ratio of the total -OH content of all starting components, i.e., the -OH content of components (II), (III), (IV) if the solvent contains -OH groups, and (V) if present, to the NCO groups of component (I).

[0031] As described above, typically the solvent does not contain any -OH groups, and naturally the polyethertriol component (V) is optional. Therefore, typically the OH:NCO molar ratio relates to the -OH content of components (II) and (III) when solvent (IV) does not contain -OH groups and component (V) is omitted, or to the cumulative molar ratio of the -OH content of (V) when components (II) and (III) are present and solvent (IV) does not contain -OH groups. Similarly, it may also relate to the -OH content of components (II), (III), (IV), and (V) when they all contain -OH groups.

[0032] Carbinol-terminated silicone / polyurethane hybrid prepolymers are prepared by gradually introducing a suitable catalyst while heating a mixture of the above starting components to a predetermined reaction temperature of 60-90°C or 60-80°C, stirring the mixture for at least 90 minutes or 2-5 hours while maintaining the mixture at the predetermined reaction temperature, and then cooling the reaction product of the carbinol-terminated silicone / polyurethane hybrid prepolymer.

[0033] catalyst Any suitable catalyst can be used to catalyze the preparation of the aforementioned prepolymer. Examples of suitable catalysts for catalyzing the preparation of the aforementioned prepolymer include, but are not limited to, suitable known polyurethane catalysts, such as tin, bismuth, zinc, mercury, or catalysts of a mixture of Sn, Bi, Zn, and Hg, such as a suitable Bi / Zn catalyst. Examples include carboxylates of tin, bismuth, zinc, and / or mercury.

[0034] Suitable tin catalysts include, for example, tin triflates, organotin metal catalysts such as triethyl tin tartrate, tin octoate, tin oleate, tin naphthenate, butyl tin tri-2-ethylhexoate, tin butyrate, carbomethoxyphenyl tin trisberate, isobutyl tin triseroate, and diorganosin salts, particularly diorganosin dicarboxylate compounds such as dibutyltin dilaurate (DBTDL), dioctyltin dilaurate (DOTDL), dimethyltin dibutyrate, dibutyltin dimethoxide, dibutyltin diacetate (DBTDA), dibutyltin bis(2,4-pentanedione), dibutyltin dibenzoate, steric tin octoate, and dimethyltin dineodecanoate (dimethyltin Examples include dineodecanoate (DMTDN), dioctyltin dineodecanoate (DOTDN), and dibutyltin dioctoate. A commercially available example of tin catalyst (v)(e) is the dibutyltin dilaurate-based catalyst sold by Evonik under the trade name Dabco® T-12.

[0035] Alternatively, the catalyst may be a suitable Bi / Zn catalyst, for example, one commercially available from Guangzhou Yourun Synthetic Material Co., Ltd. (Guangdong, China) under the trade name BX-EM 23.

[0036] The carbinol-terminated silicone / polyurethane hybrid prepolymer prepared according to the above process can then be used in step B, the preparation of a carbinol-terminated silicone / polyurethane hybrid prepolymer-based coating composition.

[0037] Unexpectedly, -NCO-terminated silicone / polyurethane hybrid prepolymers prepared by the reaction of diisocyanates such as isophorone diisocyanate (IPDI) with carbinol-terminated polydimethylsiloxane polymers and optionally diols such as 1,4-butanediol (BDO) in an eco-solvent containing excess diisocyanate to secure the -NCO terminus were not stable and tended to gel over long-term storage, e.g., more than two months. However, the carbinol-terminated silicone / polyurethane hybrid prepolymers described herein were found to be able to be stored for much longer periods without gelling.

[0038] The solute components (i.e., components excluding the solvent) of the carbinol-terminated silicone / polyurethane hybrid prepolymer coating composition are as follows: (v)(a) The above carbinol-terminated silicone / polyurethane hybrid prepolymer, (v)(b) Any cured silicone elastomer powder, (v)(c) Any optional silicon-free particles and / or fine particles selected from at least one of polymethyl methacrylate (PMMA), ethylene-vinyl acetate copolymer (EVA), ethylene-acrylate copolymer (EAA), ethylene-butyl acrylate copolymer (EBA), ethylene-methyl acrylate copolymer (EMA), ethylene-ethyl acrylate copolymer (EEA), or polyurethane polymer. (v)(d) A polyorganosiloxane containing at least two or at least three silicon-bonded hydrogen (-Si-H) groups per molecule, present in an amount of 1% to 10% by weight of the composition. (v)(f) A polyisocyanate crosslinking agent having three or more isocyanate groups per molecule, in an amount such that the molar ratio of the -OH group in (v)(a) to the -NCO group in (v)(f) in the carbinol-terminated silicone / polyurethane hybrid prepolymer coating composition (v) is 0.95:1 to 1.05:1, and (v)(g) Platinum group metal catalyst.

[0039] In step (B) of this specification, the carbinol-terminated silicone / polyurethane hybrid prepolymer coating composition (v) in step (B) is made by mixing the above components together.

[0040] The optional cured silicone elastomer powder (v)(b) may be selected from the same particles as those described with respect to component (g) of the silicone topcoat (iv) in the silicone leather composite material, which is described in detail below.

[0041] (v)(c) Optional silicon-free particles and / or fine particles (v)(c) are selected from at least one of polymethyl methacrylate (PMMA), ethylene-vinyl acetate copolymer (EVA), ethylene-acrylate copolymer (EAA), ethylene-butyl acrylate copolymer (EBA), ethylene-methyl acrylate copolymer (EMA), ethylene-ethyl acrylate copolymer (EEA), or polyurethane polymer, or silicon-free particles and / or fine particles (v)(c) are selected from PMMA and / or polyurethane particles and / or fine particles.

[0042] To avoid any doubt, silicon-free mechanical particles or microparticles are silicon-free and tolerate only trace amounts of impurities. That is, silicon-free mechanical particles are substantially free of silicon atoms and silicon-containing compounds. In one alternative form, silicon-free mechanical particles or microparticles have a number-average particle size of 0.5 to 500 μm, determined using a field emission scanning electron microscope, such as the FEI Nova NanoSEM® 630 scanning electron microscope manufactured by Thermo Fisher Scientific. For example, the determination of the number-average particle size can be achieved by taking a field emission scanning electron microscope image of the particles, then randomly selecting 10 particles from the image, and measuring the diameter of each particle in the image. The average diameter is then calculated for the selected particles. Silicon-free mechanical particles or microparticles are preferably thermally stable up to a temperature of at least 180°C. They are required to be thermally stable throughout the entire curing process, which is typically held at a temperature of 80°C to 180°C. "Thermally stable" means that silicon-free particles or microparticles do not thermally decompose at temperatures below 180°C. This is determined by placing a sample of silicon-free particles or microparticles in a suitable container and then placing the container in an oven preheated to 180°C and atmospheric pressure for 30 minutes. After 30 minutes in the oven, the sample is visually evaluated to determine whether the particles or microparticles appear to be in their original form (if they are in their original form, they are considered thermally stable up to 180°C (pass)), or whether they have visually decomposed in any way that is visually apparent, for example, by aggregation, liquefaction, carbonization, and / or disintegration.

[0043] In a preferred embodiment, the total amount of particles in the carbinol-terminated silicone / polyurethane hybrid prepolymer coating composition used to prepare the carbinol-terminated silicone / polyurethane hybrid prepolymer coating layer (v), i.e., (v)(b) + (v)(c), is 10% to 40% by weight of the composition, in their weight percentages.

[0044] The polyorganosiloxane (v)(d), containing at least two or at least three silicon-bonded hydrogen (-Si-H) groups per molecule, may be selected from any one of the crosslinking agents defined in component (c) of the silicone topcoat (iv) in the silicone leather composite material described in detail below, and is typically present in an amount of 1% to 10% by weight of the composition used to prepare the aforementioned carbinol-terminated silicone / polyurethane hybrid prepolymer coating layer (v), but is preferably a resin crosslinking agent, such as an MQ resin having Si-H dimethyl-terminated groups, for example, a Si-H dimethyl-terminated polysiloxane having a viscosity of 25 mPa·s at 25°C and a silicon-bonded hydrogen content of about 9,000 ppm.

[0045] Polyisocyanate crosslinking agents (v)(f) having three or more isocyanate groups per molecule are present in the carbinol-terminated silicone / polyurethane hybrid prepolymer coating composition (v) in such an amount that the molar ratio of the -OH groups in (v)(a) to the -NCO groups in (v)(f) is 0.95:1 to 1.05:1. Polyisocyanates having three or more isocyanate groups per molecule are

[0046] [ka] It could be an aliphatic polyisocyanate trimmer, such as one of the following.

[0047] The content of polyisocyanates (v)(f) having three or more isocyanate groups per molecule is about 10% to 30% by weight in the carbinol-terminated silicone / polyurethane hybrid prepolymer coating composition used to prepare the above-mentioned carbinol-terminated silicone / polyurethane hybrid prepolymer coating layer (v), but this may vary depending on the number of NCO groups per molecule in light of the required molar ratio described above. and The platinum group metals in platinum group metal catalysts are platinum, ruthenium, osmium, rhodium, iridium, and palladium, or compounds of such metals. Typically, the platinum group metal catalyst (v)(g) is a platinum or ruthenium-based catalyst, or a platinum-based catalyst described with respect to component (d) of the silicone topcoat (iv) in a silicone leather composite material, with Karstedt catalysts being preferred.

[0048] Any curing catalyst (v)(e) The carbinol-terminated silicone / polyurethane hybrid prepolymer coating composition (v) may also contain an optional curing catalyst (v)(e) for curing the carbinol-terminated silicone / polyurethane hybrid prepolymer coating composition, the optional polyurethane curing catalyst (v)(e), if present, may be selected from any of the catalysts used in the preparation of the carbinol-terminated silicone / polyurethane hybrid prepolymer described above.

[0049] If present, any polyurethane curing catalyst (v)(e) may be present in an amount of 0.01 to 3% by weight of the composition, or 0.03 to 1.5% by weight of the carbinol-terminated silicone / polyurethane hybrid prepolymer coating composition, or 0.03 to 0.75% by weight of the composition.

[0050] Surprisingly, while the use of -NCO-terminated silicone / polyurethane hybrid prepolymers to produce silicone / polyurethane hybrid prepolymer compositions that rely on trifunctional polyols (crosslinking agents) also tends to gel during storage, the carbinol-terminated silicone / polyurethane hybrid prepolymer coating composition (v) was found to be far more stable during longer storage periods.

[0051] Carbinol-terminated silicone / polyurethane hybrid prepolymer coating compositions are prepared in a suitable solvent, which evaporates during the heat-curing process. Any suitable solvent can be used to assist in the preparation of the carbinol-terminated silicone / polyurethane hybrid prepolymer coating compositions, but is typically selected to evaporate during the curing process. The solvent is preferably selected from solvents defined as solvent(IV) used in the preparation of the carbinol-terminated silicone / polyurethane hybrid prepolymer.

[0052] Carbinol-terminated silicone / polyurethane hybrid prepolymer coating compositions can be prepared by any desired method.

[0053] The above-described carbinol-terminated silicone / polyurethane hybrid prepolymer coating composition, used to prepare the aforementioned carbinol-terminated silicone / polyurethane hybrid prepolymer coating layer (v), is stored in two parts, a first part and a second part. The polyisocyanate (v)(f) having three or more isocyanate groups per molecule and the platinum group metal catalyst (v)(g) are separated from the remaining components during storage (in the second part). The aforementioned optional tin or Bi / Zn catalyst (v)(e), if present, may be present in the first part or in the second part, and all remaining components are retained in the first part until they are mixed together.

[0054] The above-described carbinol-terminated silicone / polyurethane hybrid prepolymer coating composition is such that the molar ratio of the -OH groups of (v)(a) in the carbinol-terminated silicone / polyurethane hybrid prepolymer coating composition (v) to the -NCO groups in (v)(f) is 0.95:1 to 1.05:1, and the carbinol-terminated silicone / polyurethane hybrid prepolymer (v)(a) is designed to react with the polyisocyanate (v)(f), which has three or more isocyanate groups per molecule, in combination with the other components of the composition. This reaction / curing process is carried out at any preferred temperature, such as 100 to 160°C or 120 to 150°C.

[0055] Carbinol-terminated silicone / polyurethane hybrid prepolymer coating compositions can be cured at temperatures of 100°C to 200°C, for example, 100°C to 160°C or 120°C to 150°C for 2 to 10 minutes.

[0056] As mentioned above, the carbinol-terminated silicone / polyurethane hybrid prepolymer coating composition is (i) Textile support layer and (ii) A silicone binder, which is a cured product of a two-component hydrosilylated curable silicone rubber composition designed to adhere to a textile support layer (i) and a skin layer (iii), and having a Shore A hardness of 20 to 40 as measured according to ASTM D2240, (iii) A silicone skin layer which is a cured product of a two-component hydrosilylated curable silicone rubber composition containing an adhesion promoter and has a Shore A hardness of 50 or greater (≧) when measured according to ASTM D2240, (iv) A silicone topcoat layer which is a cured product of a two-component hydrosilylated curable silicone topcoat containing an adhesion promoter, (v) A silicone / polyurethane hybrid prepolymer coating layer produced by curing a carbinol-terminated silicone / polyurethane hybrid prepolymer coating composition, It is prepared for use in silicone leather composite materials containing [the specified ingredient].

[0057] In a silicone leather composite material, the silicone binder (ii) is bonded between the textile support (i) and the skin layer (iii), the skin layer (iii) is located between the silicone binder layer (ii) and the silicone / polyurethane hybrid prepolymer coating layer, and the silicone topcoat layer (iv) is located on the silicone / polyurethane hybrid prepolymer coating layer (v). Therefore, the silicone / polyurethane hybrid prepolymer coating layer (v) is located between the skin layer (iii) and the silicone topcoat layer (iv).

[0058] In addition to the carbinol-terminated silicone / polyurethane hybrid prepolymer coating layer, which is the cured product of the above-mentioned carbinol-terminated silicone / polyurethane hybrid prepolymer coating composition (v), the following is provided for the silicone leather composite material.

[0059] Textile support layer (i) of silicone leather composite material The textile support layer (i) can be made from any suitable textile material, such as woven, knitted, or nonwoven fabrics made from natural fibers such as cellulose fibers like cotton, linen, silk, and wool, and / or synthetic fibers and / or microfibers. Examples of synthetic fibers and / or microfibers include, but are not limited to, polyamide fibers such as polyester, viscose rayon, and nylon, polyurethane, acrylic, polyolefin, and polyethylene; and elastic fiber materials such as spandex, acetate, polylactic acid, glass fiber, and carbon fiber, which can be used as a mixture of any two or more of the above. The textile support layer (i) is designed to enhance the mechanical strength of the silicone leather composite material.

[0060] Silicone binder layer (ii) of silicone leather composite material The silicone binder layer (ii) is a cured product of a preferred two-component hydrosilylated curable silicone rubber composition designed to adhere to the textile support layer (i) and the skin layer (iii). The selected silicone binder layer (ii) has a relatively low Shore A hardness of 20 to 40 as measured according to ASTM D2240. The silicone binder layer (ii) may have any desired average dry film thickness, e.g., 50 μm to 1 mm, or 50 to 750 μm, or 50 to 500 μm, or 100 to 500 μm, or 100 to 300 μm. In a preferred embodiment, the silicone binder layer (ii) has a high elongation at break, e.g., at least 600% elongation at break as determined according to ASTM D412, or at least 750% elongation at break as determined according to ASTM D412. The silicone binder layer (ii) can be cured at any preferred temperature, for example, 100-200°C, or 125-180°C, or 130-170°C, or 135-160°C, for a period of 20 minutes or less, or 1-10 minutes, or 1.5-5 minutes, or 1.5-4 minutes.

[0061] A suitable commercial example of a hydrosilylated, curable liquid silicone rubber composition designed to function as a binder layer is Dowsil® LCF 8400 Binder from Dow Silicones Corporation. Dowsil® LCF 8400 Binder is supplied to customers in a two-part form to avoid premature curing, and the two parts of Dowsil® LCF 8400 Binder are mixed together in a 1:1 ratio before use (SILASTIC LCF 8400 Binder is applied to the fabric and cured at a temperature of 100-200°C for 1-10 minutes). Another commercially available example of such an adhesive or bonding layer is SILASTIC® LX-2401 LSR, also commercially available from Dow Silicones Corporation. As previously mentioned, the silicone binder (ii) is designed to be sandwiched between the textile support layer (i) and the skin coating layer (iii) and to adhere to both of them.

[0062] Silicone skin layer (iii) of silicone leather composite material The silicone skin layer (iii) is a cured product of a two-component hydrosilylated curable silicone rubber composition containing an adhesion promoter, and the silicone skin layer has a Shore A hardness of 50 or greater (≧) when measured according to ASTM D2240. In a preferred embodiment, the silicone skin layer (iii) has an elongation at break of less than 500% or 200-400% as determined according to ASTM D412. The silicone skin layer (iii) is designed to form a protective synthetic leather that is typically bonded to a silicone binder (ii), otherwise it is typically used alone (i.e., without a topcoat) or sandwiched between the silicone binder (ii) and a suitable topcoat. However, as disclosed herein, the silicone skin layer (iii) is sandwiched between the silicone binder (ii) and a carbinol-terminated silicone / polyurethane hybrid prepolymer coating layer (v). The silicone skin layer (iii) can be formed using any suitable two-component hydrosilylated curable silicone rubber composition containing an adhesion promoter, provided that the above requirements are met. The silicone skin layer (iii) has a Shore A durometer greater than or equal to 50 (≧), or greater than that of the silicone binder (ii) which is 50-90, or 60-90, when measured according to ASTM D2240.

[0063] The silicone skin layer (iii) also includes an adhesion promoter. For example, the adhesion promoter may include one or more acrylicoxysilanes, isocyanatoalkylsilanes, methacrylates, and / or alkoxysilanes having epoxy groups in the molecule.

[0064] Examples of acrylicoxysilanes include 3-acryloxpropyl-trimethoxysilane, 3-acryloxpropyl-methyldimethoxysilane, 3-acryloxpropyl-dimethylmethoxysilane, 3-acryloxpropyl-triethoxysilane, or similar acrylicoxy-substituted alkyl-containing alkoxysilanes.

[0065] An isocyanatoalkylsilane must contain at least one isocyanatoalkyl group per molecule, for example, an isocyanatopropyl group, which may be, for example, (isocyanatoalkyl)trialkoxysilane or (isocyanatopropyl)dialkoxy(alkyl)silane, in each case each alkyl group contains 1 to 6 carbon atoms or 1 to 4 carbon atoms, and each alkoxy group contains 1 to 6 carbon atoms or 2 to 4 carbon atoms. Specific examples include (3-isocyanatopropyl)trimethoxysilane, (3-isocyanatopropyl)trimethoxysilane, (3-isocyanatopropyl)dimethoxy(methyl)silane, (3-isocyanatopropyl)diethoxy(methyl)silane, (3-isocyanatopropyl)dimethoxy(ethyl)silane, and (3-isocyanatopropyl)diethoxy(ethyl)silane.

[0066] The methacrylate may contain alkoxysilanes containing a methacrylic group, such as methacryloxymethyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyldimethylmethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxyisobutyltrimethoxysilane, or similar methacryloxy-substituted alkoxysilanes.

[0067] An example of an alkoxysilane having an epoxy group in the molecule that can be used as an adhesion promoter is given by formula:

[0068] [ka] [In the formula, each R 5 These are alkyl groups having 1 to 6 carbon atoms, and are either identical or different, with each R being an alkyl group having 1 to 6 carbon atoms. 6is the same or different and is an alkoxy group having 1 to 6 carbons, z = 0, 1 or 2, or a mixture thereof, and may be present in an amount of 1 to 6% by weight of the composition. Alternatively, each R 5 is an alkyl group having 1 to 3 carbons, or 1 to 2 carbons. Alternatively, each R 6 is an alkoxy group having 1 to 3 carbons, or 1 to 2 carbons. Preferably, z is 0 or 1, or z is 0. Specific examples include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 4-glycidoxybutyltrimethoxysilane, 5,6-epoxyhexyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, or 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane.

[0069] Alternatively, the adhesion promoter i) one or more alkoxysilanes having an epoxy group in the molecule as defined above, (ii) an organometallic condensation reaction catalyst containing an organoaluminum compound or an organozirconium compound, and optionally, (iii) a linear organopolysiloxane oligomer containing at least one alkenyl group and at least one hydroxy group or alkoxy group per molecule, may include a mixture and / or reaction product of.

[0070] The organometallic condensation reaction catalyst (ii) containing an organoaluminum compound or an organozirconium compound may be selected from zirconates, organoaluminum chelates, and / or organometallic catalysts containing zirconium chelates.

[0071] Zirconate-based catalysts have the general formula: Zr[OR 5 4 [where each R 5The compounds may include a monovalent primary, secondary, or tertiary aliphatic hydrocarbon group that may be the same or different, and may contain 1 to 20 carbon atoms, or 1 to 10 carbon atoms, or be branched. Optionally, the zirconate may contain a partially unsaturated group. 5 Preferred examples include, but are not limited to, methyl groups, ethyl groups, propyl groups, isopropyl groups, butyl groups, tertiary butyl groups, and branched secondary alkyl groups, such as 2,4-dimethyl-3-pentyl groups. 5 If the same, preferably R 5 These are isopropyl groups, branched secondary alkyl groups, or tertiary alkyl groups, particularly tertiary butyl groups. Specific examples include zirconium tetrapropylate and zirconium tetrabutyrate, tetra-isopropyl zirconate, zirconium(IV) tetraacetylacetonate (sometimes called zirconium AcAc4), zirconium(IV) hexafluoroacetylacetonate, zirconium(IV) trifluoroacetylacetonate, tetrakis(ethyltrifluoroacetylacetonate) zirconium, and tetrakis(2,2,6,6-tetramethylheptanethionate) zirconium. Examples include zirconium(IV) dibutoxybis(ethylacetonate), zirconium tributoxyacetylacetate, zirconium butoxyacetylacetonate bisethylacetonate, zirconium butoxyacetylacetonate bisethylacetonate, diisopropoxybis(2,2,6,6-tetramethyl-heptanethionate)zirconium, or similar zirconium complexes having β-diketones (including their alkyl-substituted and fluorine-substituted forms) used as ligands.

[0072] Suitable aluminum-based condensation catalysts include Al(OC3H7)3 and Al(OC3H7)2(C3COCH2COC 12 H 25 ), Al(OC3H7)2(OCOCH3), and Al(OC3H7)2(OCOC 12 H 25One or more of the following may be listed, but are not limited to these.

[0073] The organometallic condensation catalyst (ii) may be present in the composition in an amount of 0.1 to 5% by weight, 0.1 to 3% by weight, or 0.1 to 2% by weight. If the adhesion promoter contains the cumulative amounts of (i), (ii), and (iii), it may be present in an amount of about 0.3 to 6% by weight, or 0.3 to 4% by weight, of the composition.

[0074] A linear organopolysiloxane oligomer (iii) containing at least one alkenyl group and at least one hydroxyl or alkoxy group per molecule may be, for example, a methylvinylpolysiloxane in which both molecular ends are dimethylhydroxysiloxy units, or a copolymer of methylvinylsiloxane in which both molecular ends are dimethylhydroxysiloxy units and dimethylsiloxane units.

[0075] The organopolysiloxane oligomer (iii) may be a mixture of organopolysiloxane molecules, some of which have silanol-terminated groups at both ends, and some of which have only one silanol-terminated group, such as a dimethylhydroxysiloxy-terminated unit, and the other terminal unit is, for example, a dimethylmethoxysiloxy-terminated unit, a trimethylsiloxy-terminated unit, or a dimethylvinylsiloxy-terminated unit. Preferably, more than 50% by weight, more preferably 60-100% of the organopolysiloxane oligomer (iii) contains molecules having silanol-terminated groups at both ends.

[0076] Organopolysiloxane oligomer (iii) preferably contains at least 3% by weight, more preferably at least 5% by weight, of vinyl groups, and may contain up to 35 or 40% by weight of vinyl groups. Most preferably, organopolysiloxane oligomer (iii) contains 5 to 30% by weight of vinyl groups. Organopolysiloxane oligomer (iii) preferably has a number-average molecular weight of 100 to 10,000 g / mol when measured using gel permeation chromatography with test GB / T 21863-2008. Organopolysiloxane oligomer (iii) preferably has a viscosity of 0.1 to 300 mPa·s, or 0.1 to 200 mPa·s, or 1 to 100 mPa·s (measured using a Brookfield DV 3T rheometer at 25°C). Organopolysiloxane oligomer (iii) may be present in the composition in an amount of 0.1 to 5% by weight, 0.1 to 3% by weight, or 0.1 to 2% by weight.

[0077] The silicone skin layer (iii) may have any preferred average dry film thickness, for example, the binder layer may have any desired thickness, e.g., 50 μm to 1 mm, 50 to 750 μm, or 50 to 500 μm, or 50 to 350 μm, or 50 to 250 μm. The silicone skin layer (iii) may be cured at any preferred temperature, e.g., about 100°C to 150°C, or 110°C to 135°C, or 110°C to 125°C for 30 seconds to 5 minutes, or 30 seconds to 2.5 minutes.

[0078] Except for the need to introduce the above-mentioned suitable adhesion promoters, commercial examples of suitable liquid silicone rubber compositions that can be cured to function as a skin layer (iii) are Dowsil® LCF 8300 Skin and Dowsil® LCF 8500 Skin, both manufactured by Dow Silicones Corporation, and in view that these are both hydrosilylated curable liquid silicone rubber compositions, they are provided to the user in a two-component form that is mixed together before use to avoid premature curing during storage before use.

[0079] Both Dowsil® LCF 8300 Skin and Dowsil® LCF 8500 Skin have high Shore A durometer values ​​of 65-70, and Dowsil® LCF 8300 Skin has a relatively lower viscosity compared to Dowsil® LCF 8500 Skin. Dowsil® LCF 8500 Skin has a much higher viscosity because it is a fumed silica-reinforced version of the former with high mechanical strength. Therefore, a mixture of Dowsil® LCF 8300 Skin and Dowsil® LCF 8500 Skin may be used as a silicone skin layer (iii) if necessary. Another suitable commercially available material that can be used as a skin layer (iii) is SILASTIC® LX-2351 LSR, which is also commercially available from Dow Silicones Corporation.

[0080] Silicone topcoat layer (iv) of silicone leather composite material A silicone topcoat layer (iv) for the silicone skin composite material described herein can be prepared using any two-component hydrosilylated curable silicone topcoat composition. The two-component hydrosilylated curable silicone topcoat composition must contain an adhesion promoter, for example, one of the adhesion promoters identified as suitable for the silicone skin layer (iii) described above.

[0081] Examples of suitable silicone topcoats (iv) are: Component (iv)(a) One or more organopolysiloxane polymers having at least two unsaturated groups per molecule, wherein the unsaturated groups are selected from alkenyl groups, alkynyl groups, or mixtures thereof, and having a viscosity of 100 to 500,000 mPa·s at 25°C, Component (iv)(b) A silica-reinforced filler that has been optionally hydrophobized, Component (iv)(c) A polyorganosiloxane containing at least two or at least three silicon-bonded hydrogen (-Si-H) groups per molecule, Component (iv)(d) Hydrosilylation catalyst, Regarding component (iv)(e) silicone skin layer (iii), the adhesion promoter as described above, or zirconium acetylacetonate in an amount of 1 to 5% by weight of the composition, 1,3,5-tris[3-(trimethoxysilyl)propyl]-1,3,5-triazine-2,4,6(1H,3H,5H)-trione and / or one or more formulas in an amount of 1 to 6% by weight of the composition:

[0082] [ka] [In the formula, R 5 R is an alkyl group having 1 to 6 carbon atoms. 6 [An epoxysilane having an alkoxy group with 1 to 6 carbon atoms, where z = 0, 1, or 2], or a combination thereof, Components (iv)(f) Eco-solvent and, optionally, The cured product of a composition comprising component (iv)(g) cured silicone powder may also be a cured product of a composition containing the above.

[0083] In such a composition: (iv)(a) Organopolysiloxane polymers Component (iv)(a) of the two-component hydrosilylated curable silicone topcoat composition is one or more organopolysiloxane polymers having at least two unsaturated groups per molecule, wherein the unsaturated groups are selected from alkenyl groups, alkynyl groups, or mixtures thereof, and have a viscosity of 100 to 500,000 mPa·s at 25°C.

[0084] Organopolysiloxane polymer (iv)(a) is a polymer of formula (I): R a SiO (4-a) / 2 (I) [In the formula, each R is independently selected from aliphatic hydrocarbyl groups, aromatic hydrocarbyl groups, or organyl groups (i.e., any organic substituent having one free valence at a carbon atom, regardless of the type of functional group) as long as it contains the required number of unsaturated groups.] The group may be in a pendant position (on a D or T siloxy group) or terminal (on a M siloxy group). Saturated aliphatic hydrocarbyls are exemplified, but are not limited to, monovalent saturated hydrocarbon groups, i.e., alkyl groups typically containing 1 to 20 carbon atoms, such as methyl, ethyl, propyl, pentyl, octyl, undecyl, and octadecyl, as well as cycloalkyl groups such as cyclohexyl. Unsaturated aliphatic hydrocarbyls are exemplified, but are not limited to, monovalent saturated hydrocarbon groups, i.e., alkyl groups containing 2 to 10 carbon atoms, such as vinyl, allyl, butenyl, pentenyl, isopropenyl, 5-hexenyl, cyclohexenyl, and hexenyl, as well as alkynyl groups. Aromatic hydrocarbon groups are exemplified by, but are not limited to, phenyl, tolyl, xylyl, benzyl, styryl, and 2-phenylethyl. Organyl groups are exemplified by, but are not limited to, halogenated alkyl groups such as chloromethyl and 3-chloropropyl, nitrogen-containing groups such as amino, amide, imino, and imide groups, and oxygen-containing groups such as polyoxyalkylene, carbonyl, alkoxy, and hydroxyl groups. Further organyl groups may include sulfur-containing groups, phosphorus-containing groups, and / or boron-containing groups. The subscript "a" may be 0, 1, 2, or 3, but is typically mainly 2 or 3.

[0085] Siloxy groups can be denoted by abbreviated nomenclature, i.e., "M", "D", "T", and "Q", when R is an organic group, typically a methyl group. The M group is a siloxy group with a=3, i.e., R3SiO 1 / 2 Correspondingly, the D group is a siloxy group with a=2, i.e., R2SiO 2 / 2 Correspondingly, the T group is a siloxy group with a=1, i.e., R1SiO 3 / 2 Corresponding to this, the Q group is a siloxy group with a=0, i.e., SiO 4 / 2 It corresponds to.

[0086] The molecular structure of organopolysiloxane polymers (iv)(a) is typically linear, but several branches may exist due to the presence of intramolecular T groups (as described above).

[0087] As described above, in order to achieve useful levels of physical properties in a silicone topcoat layer prepared by curing a two-component hydrosilylated curable silicone topcoat composition, the viscosity of the organopolysiloxane polymer (iv)(a) must be at least 100 mPa·s at 25°C. The upper limit of the viscosity of the organopolysiloxane polymer (iv)(a) is limited to a maximum viscosity of 500,000 mPa·s at 25°C.

[0088] The amount (wt%) of unsaturated groups present is determined using quantitative infrared analysis according to ASTM E168. Component (iv)(a) has viscosities of 100 mPa·s to 500,000 mPa·s at 25°C, or 200 mPa·s to 150,000 mPa·s at 25°C, or 200 mPa·s to 125,000 mPa·s at 25°C, or 200 mPa·s to 100,000 mPa·s at 25°C, or 200 mPa·s to 80,000 mPa·s when measured at 25°C. Viscosities in the range of 10,000 to 400,000 mPa·s can be measured using any Brookfield® rotational viscometer equipped with a CPA-52Z spindle. Other viscosities, unless otherwise specified, were measured using a Brookfield® rotational viscometer with spindle LV-62 and a rotational speed of 10 rpm for viscosities in the range of 15 to 10,000 mPa.s, or a Brookfield® rotational viscometer with spindle LV-4 (designed for viscosities in the range of 1,000 to 2,000,000 mPa.s) or a Brookfield® rotational viscometer with spindle LV-1 (designed for viscosities in the range of 15 to 20,000 mPa.s) and a suitable rotational speed for viscosities below 1,000 mPa.s. The organopolysiloxane polymer (iv)(a) may be selected from, for example, polydimethylsiloxanes, alkylmethylpolysiloxanes, alkylarylpolysiloxanes, or copolymers thereof, which contain alkenyl and / or alkynyl groups, and may have any preferred end groups, for example, they may be trialkyl or alkenyldialkyl, or they may be terminated with any other preferred combination of end groups, provided that each organopolysiloxane polymer (iv)(a) contains at least two unsaturated groups per molecule.

[0089] Therefore, organopolysiloxane polymer (iv)(a) may, for example, be dimethylvinyl-terminated polydimethylsiloxane, dimethylvinyl-terminated dimethylmethylphenylsiloxane, trialkyl-terminated dimethylmethylvinylpolysiloxane, or dialkylvinyl-terminated dimethylmethylvinylpolysiloxane copolymer. However, considering the presence of high levels of alkenyl and / or alkynyl groups such as vinyl groups, trialkyl-terminated dimethylmethylvinylpolysiloxane or dialkylvinyl-terminated dimethylmethylvinylpolysiloxane copolymer may be preferred.

[0090] For example, an organopolysiloxane polymer (iv)(a) containing two terminal unsaturated groups selected from alkenyl and / or alkynyl groups can be represented by general formula (II): R'R''R'''SiO-(R''R'''SiO) m -SiR'''R''R' (II) In formula (II), each R' may typically be an alkenyl or alkynyl group containing 2 to 10 carbon atoms. Examples of alkenyl groups include, but are not limited to, vinyl, propenyl, butenyl, pentenyl, hexenyl, alkenylated cyclohexyl groups, heptenyl, octenyl, nonenyl, decenyl, or similar linear and branched alkenyl groups, as well as alkenylated aromatic ring structures. Examples of alkynyl groups include, but are not limited to, ethynyl, propynyl, butynyl, pentynyl, hexynyl, alkynylated cyclohexyl groups, heptenyl, octinyl, noninyl, desinyl, or similar linear and branched alkenyl groups, as well as alkenylated aromatic ring structures.

[0091] R'' does not contain ethylenically unsaturated groups, and each R'' may be the same or different, and is individually selected from monovalent saturated hydrocarbon groups typically containing 1 to 10 carbon atoms and monovalent aromatic hydrocarbon groups typically containing 6 to 12 carbon atoms. R'' may be unsubstituted or may be substituted with one or more groups that do not interfere with the curing of the two-component hydrosilylated curable silicone topcoat composition described herein, such as halogen atoms. R'''' is R' or R'', and m is an integer.

[0092] Component (iv)(a) of a two-component hydrosilylated curable silicone topcoat composition may contain more than one organopolysiloxane polymer (iv)(a) having a viscosity of 100 to 500,000 mPa·s at 25°C. When a mixture of organopolysiloxane polymers is used in component (iv)(a), at least one, or one, may contain an unsaturated group selected from alkenyl groups, alkynyl groups, or mixtures thereof in amounts of at least 5% by weight of the polymer per molecule, or 5 to 15% by weight of the polymer per molecule, or 6 to 15% by weight of the polymer per molecule, or 7 to 15% by weight of the polymer per molecule, which can be determined using quantitative infrared analysis according to ASTM E168.

[0093] Component (iv)(a) is typically present in amounts ranging from 3% or 10% by weight of the two-component hydrosilylated curable silicone topcoat composition to 50% or 45% by weight of the composition, for example, the organopolysiloxane polymer (iv)(a) may be present in amounts ranging from 10% to 50% by weight or 10% to 45% by weight of the composition.

[0094] (iv)(b) Reinforcing filler Component (iv)(b) of a two-component hydrosilylated curable silicone topcoat composition is a reinforcing filler such as reinforcing silica. In many cases, silica and other reinforcing fillers (iv)(b) are treated with one or more known hydrophobic filler treatments to prevent a phenomenon called "creping" or "crepe hardening" during processing of the two-component hydrosilylated curable silicone topcoat composition.

[0095] Silica in a pulverized form is preferred as the reinforcing filler (iv)(b). Precipitated silica and / or fumed silica, or fumed silica, is particularly preferred because it typically has a relatively large surface area of ​​at least 50 m² / g (BET method according to ISO 9277:2010). Typically, fillers with a surface area of ​​50 to 450 m² / g (BET method according to ISO 9277:2010) or 50 to 300 m² / g (BET method according to ISO 9277:2010) are used. All types of silica are commercially available.

[0096] The amount of reinforcing filler (iv)(b) in the two-component hydrosilylated curable silicone topcoat compositions of this specification is 5 to 40% by weight, or 5 to 30% by weight. In some cases, the amount of reinforcing filler may be 7.5 to 30% by weight based on the weight of the two-component hydrosilylated curable silicone topcoat composition, or 10 to 30% by weight of the composition, or 15 to 30% by weight based on the weight of the composition.

[0097] If the reinforcing filler (iv)(b) is originally hydrophilic (e.g., untreated silica filler), it is typically treated with a treatment agent to make it hydrophobic. The surface treatment makes the filler more wettable to the organopolysiloxane polymer (iv)(a), so that these surface-modified reinforcing fillers (iv)(b) can be homogeneously incorporated into the organopolysiloxane polymer (iv)(a) without agglomerating. As a result, the mechanical properties at room temperature of the two-component hydrosilylated curable silicone topcoat composition and the cured material obtained therefrom are improved.

[0098] Surface treatment may be performed before introduction into the composition, or in situ (i.e., in the presence of at least some of the other components of the composition herein, by blending these components together at room temperature or above until the fillers are completely treated. Typically, the untreated reinforcing filler (iv)(b) is treated in situ with a treatment agent in the presence of the organopolysiloxane polymer (iv)(a), mixed, to obtain a silicone rubber base material to which other components may be added.

[0099] Typically, the reinforcing filler (ii) may be surface-treated with any applicable low molecular weight organosilicon compounds disclosed in the Art to prevent creping of the two-component hydrosilylated curable silicone topcoat composition during processing. For example, organosilazanes such as organosilanes, organopolysiloxanes, or hexaalkyldisilazanes, short-chain siloxane diols, or fatty acids, or fatty acid esters such as stearic acid esters, to make the filler hydrophobic, thereby making it easier to handle and to obtain a homogeneous mixture with the other components. Specific examples include, but are not limited to, silanol-terminated trifluoropropylmethylsiloxane, dimethylsilanol-terminated vinylmethyl (ViMe)siloxane, tetramethyldi(trifluoropropyl)disilazane, tetramethyldivinyldisilazane, silanol-terminated MePhsiloxane, liquid hydroxyl-terminated polydiorganosiloxane, hexaorganodisiloxane, and hexaorganodisilazane, each containing an average of 2 to 20 repeating diorganosiloxane groups per molecule. Small amounts of water may be added together with the silica treatment agent as a processing aid.

[0100] The filler may be introduced into a two-component hydrosilylated curable silicone topcoat composition in the form of a masterbatch or base containing the filler and the organopolysiloxane polymer. The organopolysiloxane polymer used in the masterbatch or base may have a structure similar to that of component (iv)(a), but alternatively, it may be an organopolysiloxane polymer having the same viscosity range as component (iv)(a), but with an alkenyl and / or alkynyl content of less than 5% by weight of the polymer. If necessary, the fumed silica may be treated in situ to make it hydrophobic by introducing a suitable hydrophobic agent into the mixture during the preparation of the masterbatch.

[0101] The two-component hydrosilylated and curable silicone topcoat compositions described herein are cured using a hydrosilylated curing package comprising an organohydrogenpolysiloxane (iv)(c) having two or more or three or more silicon-bonded hydrogen atoms per molecule, and a hydrosilylated catalyst (iv)(d).

[0102] (iv)(c) Organohydrogenpolysiloxane Component (iv)(c) is a crosslinking agent in the form of a polyorganosiloxane containing at least two or at least three silicon-bonded hydrogen (-Si-H) groups per molecule.

[0103] Typically, component (iv)(c) contains three or more -Si-H groups, which can cure the composition by causing hydrogen atoms to react with the unsaturated alkenyl or alkynyl groups in component (iv)(a) to form a network structure with them. Alternatively, especially if component (iv)(a) has more than two (>) alkenyl or alkynyl groups per molecule, some or all of component (iv)(c) may have two -Si-H groups per molecule.

[0104] The molecular structure of polyorganosiloxane (iv)(c), which contains at least two or three Si-H groups per molecule, is not particularly limited and may be linear, partially branched linear, cyclic, or silicone resin-based.

[0105] The silicon-bonded organic group used in component (iv)(c) may be exemplified by a methyl group, ethyl group, propyl group, butenyl group, pentenyl group, hexyl group, or a similar alkyl group, a phenyl group, tolyl group, xylyl group, or a similar aryl group, 3-chloropropyl, 3,3,3-trifluoropropyl, or a similar alkyl halogen, preferably a methyl group and a phenyl group.

[0106] Examples of polyorganosiloxanes (iv)(c) containing at least two or three silicon-bonded hydrogen groups per molecule include: (a) Branched and / or chain-extended dimethylhydrogensiloxy-terminated polydimethylsiloxanes, (b) Dimethylhydrogensiloxy-terminated dimethylsiloxane-methylhydrogensiloxane copolymer, (c)(CH3)2HSiO 1 / 2 Unit: (CH3)3SiO 1 / 2 Units, and SiO 4 / 2 Copolymers and / or silicone resins consisting of units (d)(CH3)2HSiO 1 / 2 Units and SiO 4 / 2 Copolymers and / or silicone resins consisting of units (e)(CH3)2HSiO 1 / 2 Unit, SiO 4 / 2 Units and (C6H5)3SiO 1 / 2 Copolymers and / or silicone resins consisting of units, and substitutes in which methyl is replaced by a phenyl group or other alkyl group, (f)(CH3)2HSiO 1 / 2 Si-H groups such as (CH3)2SiO 2 / 2 base, and SiO 4 / 2 Examples include, but are not limited to, silicone resins containing or consisting of these groups.

[0107] The above silicone resins may also contain T groups and / or D groups, or T groups. Other potential crosslinking agents (iv)(c) include: (g) 1,1,3,3-tetramethyldisiloxane, (h) 1,3,5,7-tetramethylcyclotetrasiloxane, (i) Tris(hydrogendimethylsiloxy)methylsilane, (j) Tris(hydrogendimethylsiloxy)phenylsilane, methylhydrogencyclopolysiloxane, (k) Trimethylsiloxy-terminated blocked methylhydrogenpolysiloxane, (l) Trimethylsiloxy-terminated blocked dimethylsiloxane / methylhydrogensiloxane copolymer, (m) Dimethylhydrogensiloxy-terminated blocked dimethylpolysiloxane, (n) Dimethylhydrogensiloxy-terminated blocked dimethylsiloxane / methylhydrogensiloxane copolymer, (o) Trimethylsiloxy-terminated blocked methylhydrogensiloxane / diphenylsiloxane copolymer, (p) Trimethylsiloxy-terminated blocked methylhydrogen siloxane / diphenylsiloxane / -dimethylsiloxane copolymer, (q) Trimethylsiloxy-terminated blocked methylhydrogensiloxane / methylphenylsiloxane / -dimethylsiloxane copolymer, (r) Dimethylhydrogensiloxy-terminated block / dimethylsiloxane / -diphenylsiloxane copolymer, and / or (s) Dimethylhydrogensiloxy-terminated blocked methylhydrogensiloxane / dimethylsiloxane / -methylphenylsiloxane copolymer may be an example. (t) Other examples include tetrakis(dimethylsiloxy)silane, terminalized hydrides, polyphenylmethylsiloxane terminalized hydrides, polyphenyl-(dimethylhydrosiloxy)siloxane, or phenyltris(dimethylsiloxy)silane. Alternatively, component (iv)(c), which is the crosslinking agent, may be a filler, for example, silica treated with one of the above.

[0108] In one alternative form, the crosslinking agent (iv)(c) may be a silicone resin containing a mixture of Q groups, T groups, D groups, and / or M groups having a viscosity of 10 to 5000 mPa·s at 25°C, or 10 to 1000 mPa·s at 25°C, or 10 to 500 mPa·s at 25°C, such as in the alternative forms (c), (d), and / or (e) described above.

[0109] Polyorganosiloxane (iv)(c), containing at least two or three -Si-H groups per molecule, is typically added in amounts such that the molar ratio of silicon-bonded hydrogen atoms in component (iv)(c) to all unsaturated groups in the composition is 0.5:1 to 20:1, or 0.5:1 to 5:1, or 0.6:1 to 3:1. If this ratio is less than 0.5:1, a sufficiently cured composition cannot be obtained. If this molar ratio is greater than 20:1, the hardness of the cured composition tends to increase when heated.

[0110] The silicon-bonded hydrogen (Si-H) content of component (iv)(c) is determined using quantitative infrared analysis in accordance with ASTM E168. In the present invention, the molar ratio of silicon-bonded hydrogen to alkenyl (vinyl) and / or alkynyl is important when it depends on the hydrosilylation curing process. Generally, this is determined by calculating the total weight % of alkenyl groups, e.g., vinyl [V], in the composition and the total weight % of silicon-bonded hydrogen [H] in the two-component hydrosilylation curable silicone topcoat composition, and assuming the molecular weight of hydrogen is 1 and the molecular weight of vinyl is 27, the molar ratio of silicon-bonded hydrogen to vinyl is 27 [H] / [V].

[0111] The molecular weight of this component is not particularly limited, but the viscosity is typically 15 to 50,000 mPa.s at 25°C, measured using a Brookfield DV 3T rheometer or, for viscosities in the range of 10,000 to 400,000 mPa.s, using any Brookfield® rotational viscometer equipped with a CPA-52Z spindle. Other viscosities, unless otherwise specified, were measured using a Brookfield® rotational viscometer equipped with an LV-62 spindle and a rotational speed of 10 rpm for viscosities in the range of 15 to 10,000 mPa.s, or a Brookfield® rotational viscometer equipped with an LV-4 spindle (designed for viscosities in the range of 1,000 to 2,000,000 mPa.s) or a Brookfield® rotational viscometer equipped with an LV-1 spindle (designed for viscosities in the range of 15 to 20,000 mPa.s) and a rotational speed of 10 rpm for viscosities less than 1,000 mPa.s.

[0112] Component (iv)(c) of the two-component hydrosilylated curable silicone topcoat composition is a polyorganosiloxane containing at least two or at least three silicon-bonded hydrogen (-Si-H) groups per molecule, which functions as a crosslinking agent for polymer (iv)(a) through an addition reaction between the silicon-bonded hydrogen atoms in component (iv)(c) and the alkenyl and / or alkynyl groups in component (iv)(a) under the catalytic activity of component (iv)(d), described later. Component (iv)(c) contains at least parts per million (ppm) of silicon-bonded hydrogen (Si-H), or at least 7,000 ppm, or 7,000 to 12,000 ppm, or 8,000 to 11,000 ppm, of silicon-bonded hydrogen, so that the silicon-bonded hydrogen atoms of this component react sufficiently with the alkenyl and / or alkynyl groups of component (iv)(a), typically alkenyl groups, especially vinyl groups, to form a network structure together, thereby curing the composition. The amount of silicon-bonded hydrogen present is also determined using quantitative infrared analysis according to ASTM E168.

[0113] Component (iv)(c) is typically present in the entire two-component hydrosilylated curable silicone topcoat composition in amounts of 5-30% by weight, 5-20% by weight, or 10-20% by weight of the composition, the amount present is typically determined by the molar ratio of silicon-bonded hydrogen atoms in component (iv)(c) to the total number of all unsaturated groups, such as alkenyl and alkynyl groups, often vinyl groups, as described above.

[0114] (iv)(d) Hydrosilylation catalysts The two-component hydrosilylated and curable silicone topcoat composition is cured via a hydrosilylation (addition) reaction catalyzed by a hydrosilylation (addition curing) catalyst (iv)(d), which is a metal selected from platinum group metals, i.e., platinum, ruthenium, osmium, rhodium, iridium, and palladium, or a compound of such metals. Due to the high activity levels of these catalysts in the hydrosilylation reaction, platinum and rhodium compounds are preferred.

[0115] The hydrosilylation catalyst (iv)(d) may be a platinum group metal; a support, such as activated carbon, a metal oxide such as aluminum oxide or silicon dioxide, silica gel or powdered charcoal, on which the platinum group metal is deposited; or a compound or complex of a platinum group metal. Preferably, the platinum group metal is platinum.

[0116] Examples of preferred hydrosilylation catalysts (iv)(d) include platinum-based catalysts, such as platinum black, platinum oxide (Adams catalyst), platinum on various solid supports, chloroplatinic acid, such as hexachloroplatinic acid (Pt oxidation state IV) (Speier catalyst), chloroplatinic acid in solution of alcohols, such as isooctanolic acid or amyl alcohol (Lamoreaux catalyst), and complexes of chloroplatinic acid with ethylenically unsaturated compounds, such as olefins and organosiloxanes containing ethylenically unsaturated silicon-bonded hydrocarbon groups, such as tetra-vinyl-tetramethylcyclotetrasiloxane-platinum complexes (Ashby catalyst). Examples of usable soluble platinum compounds include platinum-olefin complexes of the formula (PtCl2.(olefin)2 and H(PtCl3.olefin)), in which case the use of alkenes having 2 to 8 carbon atoms, such as ethylene, propylene, butene isomers and octene isomers, or cycloalkanes having 5 to 7 carbon atoms, such as cyclopentene, cyclohexene, and cycloheptene, is preferred. Other soluble platinum catalysts include, for example, platinum-cyclopropane complexes of the formula (PtCl2C3H6)2. The reaction products are those of hexachloroplatinic acid with alcohols, ethers, and aldehydes, or mixtures thereof, or those of hexachloroplatinic acid and / or its conversion products with vinyl-containing siloxanes such as methylvinylcyclotetrasiloxane in an ethanolic solution in the presence of sodium bicarbonate. Platinum complexes with vinylsiloxanes, such as platinum catalysts having phosphorus, sulfur, and amine ligands, e.g., (Ph3P)2PtCl2, and sym-divinyltetramethyldisiloxane, can also be used.

[0117] Therefore, specific examples of suitable platinum-based catalysts for (iv)(d) are: (i) A complex of chloroplatinic acid and an organosiloxane containing an ethylenically unsaturated hydrocarbon group, as described in U.S. Patent No. 3,419,593, (ii) Chloroplatanic acid in either hexahydrate or anhydrous form, (iii) A platinum-containing catalyst obtained by a method comprising reacting chloroplatinic acid with an aliphatic unsaturated organosilicon compound such as divinyltetramethyldisiloxane, (iv) Alkene-platinum-silyl complexes described in U.S. Patent No. 6,605,734, such as (COD)Pt(SiMeCl2)2 (wherein "COD" is 1,5-cyclooctadiene), and / or (v) Examples include the Karrstedt catalyst, which is a platinum divinyltetramethyldisiloxane complex, typically containing about 1% by weight of platinum in a vinylsiloxane polymer. While solvents such as organic solvents like toluene have historically been used as alternatives, the use of vinylsiloxane polymers is a far more preferred choice. These are described in U.S. Patents 3,715,334 and 3,814,730. In one preferred embodiment, component (iv)(d) may be selected from platinum coordination compounds. In one embodiment, hexachloroplatinic acid and its conversion products with vinyl-containing siloxanes, the Karrstedt catalyst, and the Speier catalyst are preferred.

[0118] The catalytic amount of the hydrosilylation catalyst is generally 0.01 ppm to 10,000 ppm, or 0.01 to 5,000 ppm, or 0.01 to 3,000 ppm, or 0.01 to 1,000 ppm, based on the weight of the two-component hydrosilylation-curable silicone topcoat composition, in parts by weight (ppm) of platinum group metals. In certain embodiments, the catalytic amount of the catalyst may range from 0.01 to 1,000 ppm, or 0.01 to 750 ppm, or 0.01 to 500 ppm, or 0.01 to 100 ppm, based on the weight of the two-component hydrosilylation-curable silicone topcoat composition, in terms of metal. The range may relate only to the metal content in the catalyst or to the catalyst as a whole (including its ligands), as specified, but typically these ranges relate only to the metal content in the catalyst. The catalyst may be added as a single species or as a mixture of two or more different species. Typically, depending on the form / concentration in which the catalyst is provided in the polymer or solvent, for example, the amount of component (iv)(d) present is in the range of 0.001 to 3.0% by weight of the composition, or 0.001 to 2.5% by weight of the composition, or 0.01 to 2.0% by weight of the two-component hydrosilylated curable silicone topcoat composition.

[0119] Component (iv)(e) Adhesion promoter Component (iv)(e) is an adhesion promoter used to assist in the adhesion of the silicone topcoat (iv) to the carbinol-terminated silicone / polyurethane hybrid prepolymer coating layer (v). Component (iv)(e) may be any of the adhesion promoters described above. However, one adhesion promoter particularly preferred for use as component (iv)(e) is a combination of one or more alkoxysilanes and / or 1,3,5-tris[3-(trimethoxysilyl)propyl]-1,3,5-triazine-2,4,6(1H,3H,5H)-trione having an epoxy group in the molecule as defined above, in an amount of 1 to 6% by weight of the composition, and zirconium acetylacetonate in an amount of 1 to 5% by weight of the composition.

[0120] In one embodiment, the alkoxysilane having an epoxy group in the molecule is selected from 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and / or 3-glycidoxypropylmethyldimethoxysilane.

[0121] Component (iv)(f) Eco-solvent Component (iv)(f) of the two-component hydrosilylated curable silicone topcoat composition is an eco-solvent, i.e., an environmentally friendly solvent that can be suitably used in applications such as cosmetic products, has minimal harmful effects if any, and excludes harmful solvents such as benzene, toluene, and xylene. Any suitable eco-solvent can be used, examples of which include isopentadecane, isohexadecane, isoheptadecane, isooctadecane, isononadecane, and mixtures thereof, or trimethyl-terminated polydimethylsiloxane having a viscosity of (≧) 5 mPa.s or more and (≦) 100 mPa.s or less at 25°C. It has been noted that using trimethyl-terminated polydimethylsiloxane with a viscosity of less than 5 mPa.s at 25°C appears to actually produce leather materials in which stretch marks become white. In one embodiment, the eco-solvent contains or consists of isohexadecane. The eco-solvent is present in the composition as a means of diluting the composition, and is present in the composition in an amount of 30 to 70% by weight of the two-component hydrosilylated curable silicone topcoat composition. The eco-solvent may be present in either or both of parts A and B, as desired or as needed.

[0122] Component (iv)(g) Any cured silicone elastomer powder If necessary, any suitable curable silicone elastomer powder may be used in the two-component hydrosilylated curable silicone topcoat composition. In one alternative embodiment, the curable silicone elastomer powder (iv)(g) has an average particle size of 0.01 to 100 μm, or 0.01 to 50 μm, or 0.01 to 25 μm, as measured using, for example, the Dow Silicone Corporation Corporate Test Method CTM 1138, which is publicly available upon request. The curable silicone elastomer powder may contain chemical functional groups, such as epoxy groups or (meth)acryloxy groups, or may be coated with, for example, a silica-treated coating.

[0123] Curable silicone elastomer powders are prepared from suitable curable silicone compositions. Examples of curable silicone compositions include silicone compositions that cure by addition (hydrosilylation), silicone compositions that cure by condensation, silicone compositions that cure with organic peroxides, and silicone compositions that cure with ultraviolet light. Silicone compositions that cure by addition and condensation are preferred due to their ease of handling.

[0124] Silicone elastomer powders are generally prepared by first dispersing a curable silicone composition in water or an aqueous surfactant solution, and then applying a mixing device such as a homogenizer, colloid mill, or ultrasonic vibrator to the dispersion to create a homogeneous aqueous emulsion of the curable silicone composition. To obtain a very stable emulsion with a small average particle diameter, the aqueous curable silicone emulsion is preferably prepared using a surfactant. Next, the curable silicone present in the aqueous emulsion is cured to produce an aqueous dispersion of cured silicone powder. This curing can be influenced by leaving the aqueous emulsion at room temperature or by heating the aqueous emulsion. When heating an aqueous curable silicone emulsion, the preferred heating temperature should not exceed 100°C, and the particularly preferred temperature is in the range of 40°C to 95°C. Techniques for heating water-curable silicone emulsions include directly heating the emulsion or adding the emulsion to hot water. Commercial examples that can be used as component (iv)(g) include, for example, Dowsil® 23N Additive, Dowsil® 603T additive, and Dowsil® 9701 Cosmetic Powder, all manufactured by Dow Silicones Corporation.

[0125] The cured silicone rubber powder is present in the two-component hydrosilylated curable silicone topcoat composition, i.e., when parts A and B are mixed together, in an amount of 2.5 to 20% by weight of the composition, or 2.5 to 15% by weight of the composition, or 2.5 to 10% by weight of the composition.

[0126] Optional additives A two-component hydrosilylated curable silicone topcoat composition may contain one or more additives. Examples of these optional additives include curing inhibitors, inorganic non-reinforcing fillers, conductive additives, pot life extenders, lubricants, flame retardants, pigments, colorants, chain extenders, heat stabilizers, compression set improving additives, anti-squeak agents, antioxidants, antistatic agents, antifouling agents, and light stabilizers, antifreeze agents, and / or biocides, as well as mixtures thereof.

[0127] inhibitors Since a hydrosilylation curing system is used, in order to obtain a longer action time or pot life of the two-component hydrosilylation curable silicone topcoat composition, a suitable inhibitor may be optionally incorporated into the composition to delay or suppress the activity of the catalyst.

[0128] Inhibitors of platinum metal catalysts, and more generally, of platinum group metal catalysts, are well known in the art. Examples of hydrosilylation or addition reaction inhibitors include hydrazine, triazole, phosphine, mercaptan, organic nitrogen compounds, acetylene alcohol, silylated acetylene alcohols such as methyl(tris(1,1-dimethyl-2-propynyloxy))silane, maleates, fumarates, ethylenically or aromatically unsaturated amides, ethylenically unsaturated isocyanates, olefin siloxanes, unsaturated hydrocarbon monoesters and diesters, conjugated en-yines, hydroperoxides, nitriles, and diaziridines. Alkenyl-substituted siloxanes, such as those described in U.S. Patent No. 3,989,667, may also be used, of which cyclic methylvinylsiloxane is preferred.

[0129] Another category of known platinum catalyst inhibitors includes acetylene compounds, disclosed in U.S. Patent No. 3,445,420. Acetylene alcohols such as 2-methyl-3-butyne-2-ol constitute a preferred type of inhibitor that suppresses the activity of platinum-containing catalysts at 25°C. Hydrosilylated curable silicone elastomer compositions containing these inhibitors typically require heating to temperatures above 70°C to cure at a practical rate.

[0130] Examples of acetylene alcohols and their derivatives include 1-ethynyl-1-cyclohexanol (ETCH), 2-methyl-3-butyne-2-ol, 3-butyne-1-ol, 3-butyne-2-ol, propargyl alcohol, 3,5-dimethyl-1-hexyne-3-ol, 1-ethynylcyclopentanol, 1-phenyl-2-propinol, 3-methyl-1-penten-4-in-3-ol, and mixtures thereof.

[0131] In some cases, when present, a low inhibitor concentration of about 1 mole of inhibitor per mole of metal in catalyst (iv)(d) provides satisfactory storage stability and curing rate. In other cases, inhibitor concentrations of up to 500 moles of inhibitor per mole of metal in catalyst (iv)(d) are required. The optimal concentration of a given inhibitor in a given composition is easily determined by routine experimentation. When present in a composition, depending on the concentration and form in which the selected inhibitor is provided / commercially available, the inhibitor is typically present in an amount of 0.0125 to 10% by weight of a two-component hydrosilylated curable silicone topcoat composition. Mixtures of the above may also be used.

[0132] If optional additives are to be used for two or more reasons, for example, as a non-reinforcing silica filler and a flame retardant, they may function in both roles when present. When present or in existence, the aforementioned additional components are present cumulatively in an amount of 0.1 to 30% by weight, or 0.1% to 20% by weight, of the two-component hydrosilylated curable silicone topcoat composition.

[0133] To prevent premature curing during storage, the two-component hydrosilylated curable silicone topcoat composition is stored in two parts, Part A and Part B, before use. Typically, Part A contains part of the organopolysiloxane polymer (iv)(a) and reinforcing filler (iv)(b), as well as the hydrosilylation catalyst (iv)(d), while Part B contains the remaining organopolysiloxane polymer (iv)(a) and reinforcing filler (iv)(b), along with the organohydrogenpolysiloxane crosslinking agent (iv)(c), and, if present, an inhibitor, which may vary depending on the choice of inhibitor used. The two-component composition may be designed to be mixed together in any preferred ratio depending on the amounts of organopolysiloxane polymer (iv)(a) and reinforcing filler (iv)(b) of portion B, and therefore may be mixed in a weight ratio of portion A:part B of 15:1 to 1:2, but preferably in a weight ratio of 2:1 to 1:2, or 1.5:1 to 1:1.5, or 1:1 of portion A:part B.

[0134] The two-component hydrosilylated curable silicone topcoat composition is cured at a temperature of 120°C to 175°C or 130°C to 160°C for 2 to 8 minutes after mixing. The average dry film thickness of the two-component hydrosilylated curable silicone topcoat is 5 to 20 μm.

[0135] Two preferred commercially available examples of the silicone topcoat layer (iv) are SILASTIC® LX-2010 topcoat and SILASTIC® LX-2011 topcoat, both of which are available from Dow Silicones Corporation.

[0136] Carbinol-terminated silicone / polyurethane hybrid prepolymer coating layer (v) of silicone leather composite material The carbinol-terminated silicone / polyurethane hybrid prepolymer coating layer (v) is provided by curing a suitable carbinol-terminated silicone / polyurethane hybrid prepolymer coating composition, and when the silicone leather composite material is completed, the silicone / polyurethane hybrid prepolymer coating layer (v) is located between the skin layer (iii) and the silicone topcoat layer (iv). The composition is prepared in a suitable solvent, which evaporates during the heat curing process.

[0137] The average dry film thickness of the carbinol-terminated silicone / polyurethane hybrid prepolymer coating layer (v) is 10 μm to 50 μm. This was determined by measuring the length and width of a release paper sample, coating the release paper with the carbinol-terminated silicone / polyurethane hybrid prepolymer coating composition, curing it, weighing the release paper coated with the resulting carbinol-terminated silicone / polyurethane hybrid prepolymer coating layer (v), and calculating the average thickness based on the following formula. Average dry film thickness of layer (v) = Weight of layer (v) / (Density) * width * length)

[0138] When the average dry film thickness of each layer was given, the weight of each layer was determined and used the above formula to obtain the same thickness as layer (v). In all cases, the density was determined according to ASTM D792.

[0139] Preferably, the silicone leather composite material described herein contains a carbinol-terminated silicone / polyurethane hybrid prepolymer coating layer (v) having an elastic modulus of 10 MPa or more as determined according to ASTM D882, or 20 MPa or more as determined according to ASTM D882, or 30 MPa or more as determined according to ASTM D882, in which case the first straight portion of the load-elongation curve is used to calculate the elastic modulus.

[0140] As described above, a method for preparing the silicone leather composite material described herein is also provided. This process is (a) A step of coating release paper with a layer of a carbinol-terminated silicone / polyurethane hybrid prepolymer coating composition, and curing the composition to provide a carbinol-terminated silicone / polyurethane hybrid prepolymer coating layer (v), (b) A step of applying a layer of silicone skin composition onto a cured carbinol-terminated silicone / polyurethane hybrid prepolymer coating layer (v), and curing the composition to provide a silicone skin layer (iii), (c) A step of applying a layer of silicone binder composition onto a cured silicone skin layer (iii), applying a textile layer (i) onto the silicone binder composition, curing and / or laminating the composition to form a silicone binder layer (ii) between the textile support layer (i) and the skin layer (iii), (d) A step of removing the release paper from the cured carbinol-terminated silicone / polyurethane hybrid prepolymer coating layer (v), (e) The process includes applying a layer of a two-component hydrosilylated curable silicone topcoat composition onto the cured carbinol-terminated silicone / polyurethane hybrid prepolymer coating layer (v), and curing the topcoat composition to form a silicone topcoat layer (iv).

[0141] It was found that problems were encountered when a two-component hydrosilylated curable silicone topcoat composition was applied to release paper as the first step of the process, followed by the application of a carbinol-terminated silicone / polyurethane hybrid prepolymer coating composition (v). Therefore, surprisingly, the problem was avoided by adding a topcoat on the cured carbinol-terminated silicone / polyurethane hybrid prepolymer coating layer (v) as the final step, and thus the above process was developed.

[0142] In one embodiment of the process for preparing the silicone leather composite material described herein, the process is as follows: (a) A step of coating the release paper with a layer of a carbinol-terminated silicone / polyurethane hybrid prepolymer coating composition, curing it at a temperature of 120°C to 180°C for 2 to 10 minutes to form a carbinol-terminated silicone / polyurethane hybrid prepolymer coating layer (v), and obtaining an average dry film thickness of 10 μm to 50 μm using the above method, (b) Applying a layer of silicone skin composition onto a cured carbinol-terminated silicone / polyurethane hybrid prepolymer coating layer (v), curing it at any suitable temperature, for example, 100-150°C, to produce a silicone skin layer (iii) having a thickness of 50 μm to 1 mm, 50-750 μm, or 50-500 μm, or 50-350 μm, or 50-250 μm, or an average dry film thickness of 70 μm to 200 μm using the above method, (c) A step of applying a layer of silicone binder composition onto a cured silicone skin layer (iii), applying a textile layer (i) onto the silicone binder, and curing the silicone binder (ii) between the textile support layer (i) and the skin layer (iii) at a temperature of 130°C to 180°C for 2 to 8 minutes and / or laminating them therebetween, wherein the thickness of the resulting layer is determined by the thickness requirements of the silicone leather composite material and the thickness of the other layers. (d) A step of removing the release paper from the cured carbinol-terminated silicone / polyurethane hybrid prepolymer coating layer (v), (e) Applying a layer of a two-component hydrosilylated curable silicone topcoat composition (iv) onto the cured carbinol-terminated silicone / polyurethane hybrid prepolymer coating layer (v), curing the topcoat at 130°C to 160°C for 2 to 8 minutes, thereby forming a silicone topcoat (v) having an average dry film thickness of 5 to 20 μm using the above method, and completing the silicone leather composite material. Includes.

[0143] Each individual part of the two-component hydrosilylated composition described above may be prepared by any preferred method. For this purpose, any mixing techniques and apparatus described in the prior art can be used. The specific apparatus used will depend on the components and the viscosity of each final curable composition. Suitable mixers include, but are not limited to, paddle-type mixers, such as planetary mixers, and kneading-type mixers. It may be desirable to cool the components during mixing to avoid premature curing of the composition. Therefore, as the first step of the process, parts A and B of each two-component composition may be mixed together, and if desired, the composition may be degassed, for example, in the case of a two-component hydrosilylated composition, for example, the skin layer and the binder layer.

[0144] The order in which the components of the hydrosilylated curable silicone elastomer composition are mixed in a two-component hydrosilylated curable silicone topcoat composition is not important. Prepare suitable portions A and B, and then, immediately before use, mix portions A and B together in a predetermined weight ratio of 15:1 to 1:2, for example, 1:1.

[0145] After preparation and / or mixing, each composition used to provide each layer in the silicone leather composite material may be applied according to the above process using any suitable application method, such as spraying, rolling, brushing, spin coating, dip coating, solvent casting, slot die coating, spray coating, knife coating, or gravure coating.

[0146] Any suitable release paper can be used, for example, Super Matte Release Paper ARX175DM manufactured by Japan Asahi, Matte Release Paper DE-7, DE-90, DE-43C, DE-73J manufactured by Dai Nippon Printing Co., Ltd. (Japan), or Semi Matte Release Paper DE-73M ​​also manufactured by Dai Nippon Printing Co., Ltd. (Japan).

[0147] Each curing step may be carried out by curing and drying in a suitable oven, for example, in a hot air oven, or in a conveyor oven in the case of a continuous process.

[0148] If desired, the final silicone leather composite material may be post-cured at a temperature of approximately 75°C to 180°C, but not necessarily, generally toward the lower end of the range, for example, 75°C to 120°C for 2 to 48 hours, or 6 to 36 hours, or 10 to 24 hours.

[0149] Silicone leather composite materials can be designed to have a wide variety of properties by considering the contents of different layers, and may have excellent flame retardancy, smoke density, heat resistance, stain resistance, solvent resistance, hydrolysis resistance, etc., depending on the requirements of the end use of the leather. However, as a result of providing a carbinol-terminated silicone / polyurethane hybrid prepolymer coating layer (v), significantly improved abrasion resistance was obtained, and both the carbinol-terminated silicone / polyurethane hybrid prepolymer and the carbinol-terminated silicone / polyurethane hybrid prepolymer coating composition (v) were also provided, and both were stable in storage before application and curing of the composition.

[0150] Potential end uses include, but are not limited to, furniture, decorations, handbags, binders, travel bags, clothing, phone covers, electronic product covers, book covers, footwear, car interiors, car seats, medical beds / seats, and wearable devices. [Examples]

[0151] In the following examples and comparative examples, several silicone leather composite materials were prepared and tested to demonstrate the advantages of incorporating a carbinol-terminated silicone / polyurethane hybrid prepolymer coating layer (v) as a means of improving abrasion resistance. All viscosities were measured at 25°C. The viscosity of the carbinol-terminated PU-PDMS prepolymer was measured using a Brookfield® rotational viscometer with a CPA-52Z spindle for viscosities in the range of 10,000 to 400,000 mPa.s. Other viscosities, unless otherwise specified, were measured using a Brookfield® rotational viscometer with an LV-62 spindle and a rotational speed of 10 rpm for viscosities in the range of 15 to 10,000 mPa.s. The amount (wt%) of unsaturated groups and / or silicon-bonded hydrogen present was determined using quantitative infrared analysis according to ASTM E168.

[0152] A series of examples of carbinol-terminated silicone / polyurethane hybrid prepolymers and comparative -NCO-terminated silicone / polyurethane hybrid prepolymers were prepared.

[0153] The materials used in the preparation of the prepolymer include the following: Isophorone diisocyanate (IPDI) having the following structure.

[0154] [ka]

[0155] Carbinol-terminated polydimethylsiloxane (PDMS) was a monoethylene glycol-terminated polydimethylsiloxane with a viscosity of approximately 48 mPa·s at 25°C and a KOH / g concentration of approximately 60 mg when measured according to ASTM-D4274-11.

[0156] The Bi / Zn catalyst is an organobismuth / zinc complex catalyst designed to catalyze the reaction between -NCO groups and -OH groups for polyurethane products, and is commercially available from Guangzhou Yourun Synthetic Material Co., Ltd (Guang Dong, China) under the trade name BX-EM 23.

[0157] The solvent used was dipropylene glycol methyl ether acetate (DPMA).

[0158] The polyethertriol used in the examples has an average molecular weight of 260 and is commercially available from Dow Chemical Company under the trade name VORANOL® CP 260 Polyol.

[0159] The amounts of each starting component used are provided in Tables 1a and 1c below, and details of the prepared prepolymers are provided in Tables 1b and 1d, respectively.

[0160] [Table 1]

[0161] Comparative prepolymers of the compositions in Table 1a were prepared using the following process: Isophorone diisocyanate (IPDI), solvent 1,4-butanediol, carbinol-terminated PDMS, and / or polyethertriol were thoroughly mixed in a reaction vessel with dipropylene glycol methyl ether acetate and DPMA solvent, and then the Zn / Bi catalyst was gradually added. The OH:NCO molar ratio was greater than 1.15:1. The resulting mixture was heated to approximately 70°C, then continuously stirred at approximately that temperature for a further 3 hours, and then cooled to 30-40°C. Finally, it was filled into containers or storage, or, as in this example, the resulting prepolymer product was immediately used in the preparation of silicone / polyurethane hybrid prepolymer coating compositions by missing it with the other components of the composition in solution. Meanwhile, the solvent evaporates during the curing process.

[0162] Details of the obtained prepolymer are shown in Table 1b.

[0163] [Table 2]

[0164] Furthermore, prepolymers for a series of examples were prepared using the compositions shown in Table 1c, and their details are provided in Table 1d below.

[0165] [Table 3]

[0166] [Table 4]

[0167] The same process was used for each composition in Tables 1a and 1c.

[0168] Tables 2a and 2b show a comparison of the viscosity characteristics of prepolymers prepared from the compositions in Tables 1a and 1c before and after aging.

[0169] [Table 5]

[0170] [Table 6]

[0171] The viscosities measured for Tables 2a and 2b were measured using a Brookfield® rotational viscometer equipped with a CPA-52Z spindle for viscosities in the range of 10,000 to 400,000 mPa.s. For other viscosities, the range of 15 to 10,000 mPa.s was measured using a Brookfield® rotational viscometer equipped with an LV-62 spindle and a rotational speed of 10 rpm. It can be seen that both comparative prepolymers with -NCO terminology gelled during aging. All of the examples in Comparative Example 3 and Table 2b of this disclosure showed only slight viscosity changes after the aging period. Therefore, unexpectedly, it can be seen that by using carbinol-terminated polymers, the prepolymers can be aged for a much longer period without significant viscosity increases or gelling during storage, unlike similar -NCO-terminated prepolymers.

[0172] Next, using the prepolymers prepared as shown in Tables 1a to 1d using the above process, comparative silicone / polyurethane hybrid prepolymer compositions were prepared using the starting components shown in Tables 3a and 3b.

[0173] [Table 7]

[0174] In the compositions shown in Table 3a (and Table 3b below), the amounts of the components are expressed in parts by weight per 100 parts by weight of each silicone / polyurethane hybrid prepolymer. The previously unspecified materials used to prepare the prepolymer compositions are as follows: The resinous SiH crosslinking agent is a Si-H dimethyl-terminated resinous Si-H polysiloxane having a viscosity of 25 mPa·s at 25°C and a silicon-bonded hydrogen content of approximately 9,000 ppm. The polyurethane microparticles used in the composition have an average particle size of 1 to 10 μm (according to supplier information) and are commercially available from Dainichiseika Color & Chemicals Mfg. Co. Ltd. under the trade name RHU-5070D Polyurethane microparticles. Crosslinking agent 1 is Desmodur® Z 4470 BA, which is a 70% IPDI trimer in n-butyl acetate (structure below) and is commercially available from Covestro AG as Desmodur® Z 4470 BA.

[0175] [ka]

[0176] Crosslinking agent 2 is the above-mentioned polyethertriol having an average molecular weight of 260, and is commercially available from The Dow Chemical Company under the trade name VORANOL® CP 260 Polyol.

[0177] In the above, when preparing NCO-terminated silicone / polyurethane hybrid prepolymer compositions (comparatives 1 and 2), a suitable NCO-terminated silicone / polyurethane (PU-PDMS) hybrid prepolymer is mixed with polyurethane microparticles, a resinous SiH crosslinking agent, and a Karstedt catalyst, along with crosslinking agent 2 (at an NCO:OH molar ratio of 0.95 to 1.05), to form a carbinol-terminated silicone / polyurethane hybrid prepolymer coating composition ready for application as a layer in a composite silicone leather material.

[0178] In the case of Comparison 3, the carbinol-terminated silicone / polyurethane hybrid prepolymer is mixed with polyurethane microparticles, a resinous SiH crosslinking agent, and a Karstedt catalyst, along with crosslinking agent 1 (at an NCO:OH molar ratio of 0.95 to 1.05), to form a carbinol-terminated silicone / polyurethane hybrid prepolymer coating composition ready for application as a layer in a composite silicone leather material.

[0179] [Table 8]

[0180] In the above examples, each composition was prepared using the same process as the comparative 3 prepolymer described above.

[0181] To test the abrasion resistance of a silicone leather composite material containing layers of different silicone / polyurethane hybrid prepolymer coatings prepared using the coating compositions shown in Tables 3a and 3b above, each of the silicone / polyurethane hybrid prepolymer coating compositions prepared above was used on a sample silicone leather composite material prepared as follows. (a) The release paper is coated with a layer of a silicone / polyurethane hybrid prepolymer coating composition prepared using one of the compositions detailed in Table 3a or Table 3b above. Then, a silicone / polyurethane hybrid prepolymer coating layer (v) is formed by curing at a temperature of 120°C to 180°C for 2 to 10 minutes, and an average dry film thickness of 10 μm to 50 μm is obtained using the above method. (b) A layer of silicone skin composition is applied to a cured silicone / polyurethane hybrid prepolymer coating layer (v) using commercially available SILASTIC® LX-2351 LSR and cured at any suitable temperature between 100 and 150°C to produce a silicone skin layer (iii) having an average dry film thickness of 70 μm to 200 μm using the above method. (c) A layer of a silicone binder composition in the form of SILASTIC® LX-2401 LSR is applied onto a cured silicone skin layer (iii), a textile layer (i) is applied onto the silicone binder, and the silicone binder (ii) is cured between the textile support layer (i) and the skin layer (iii) at a temperature of 130°C to 180°C for 2 to 8 minutes and / or laminated between them, wherein the average dry film thickness of the silicone binder layer (ii) using the above method is 200 μm to 250 μm. (d) Remove the release paper from the cured silicone / polyurethane hybrid prepolymer coating layer (v). (e) Preferably using gravure printing, a layer of SILASTIC® LX-2011 topcoat is applied as a topcoat to provide a topcoat that has a good feel and good stain resistance when cured. The topcoat is cured at 130°C to 160°C for 2 to 8 minutes to form a silicone topcoat (v) having an average dry film thickness of 5 to 20 μm using the above method, and the silicone leather composite material is completed.

[0182] Each silicone leather composite material produced using the above process was tested for its abrasion resistance. The abrasion resistance of each silicone leather composite material was tested using a Gakushin Model: GT-7020 manufactured by GOODTECHWILL Testing Machines Co., Ltd.

[0183] A silicone leather composite material was cut into 10 x 100 mm rectangles and then attached to the load test head of a Gakushin Model: GT-7020 using double-sided tape. Abrasive action was provided by a piece of cotton abrasive cloth (JIS L3102 6# 30 mm x 250 mm) placed on the movable curved platen of the Gakushin instrument. The platen moved back and forth at 30 cycles / min, and the total weight of each head was 1 kg. The test was stopped every 2000 cycles, and the effect on the surface of the leather composite material was observed and recorded.

[0184] [Table 9]

[0185] Comparative samples 1 and 2 were observed to have almost completely gelled after aging at room temperature (25°C) for 3 months, and clearly gelled after aging at 50°C for 2 weeks (Table 2a). Nevertheless, the JSPS abrasion results are acceptable. In contrast, the viscosity of Comparative sample 3 hardly changed after aging at 50°C for 2 weeks (measured in mPa.s at 25°C) (Table 2a), but when applied as a layer in the silicone leather composite material described herein, the silicone leather gave only insufficient JSPS abrasion results, which is thought to be due to the composition having too low an IPDI level and too much carbinol-terminated polydimethylsiloxane.

[0186] [Table 10]

[0187] Examples 1 to 6 were observed to have a good shelf life of over 12 months after aging at room temperature (25°C), the viscosity of the prepolymer remained almost unchanged after 2 weeks of aging at 50°C (measured in mPa·s at 25°C) (Table 2b), and no gelation was observed. Furthermore, they all gave good JSPS abrasion results.

Claims

1. A method for preparing a carbinol-terminated silicone / polyurethane hybrid prepolymer coating composition, (A) (I) Diisocyanate in an amount of 20-30% by weight of the starting components of step (A), (II) Alkanediol chain extender in an amount of 5 to 15% by weight of the starting components of step (A), (III) Carbinol-terminated polydimethylsiloxane in an amount of 25 to 45% by weight of the starting components of step (A), (IV) A solvent in an amount of 20 to 40% by weight of the starting components of step (A), and optionally, (V) A step to prepare a carbinol-terminated silicone / polyurethane hybrid prepolymer by mixing together a polyethertriol in an amount of 2% by weight or less of the starting components of step (A), The molar ratio of OH:NCO is greater than 1.15:

1. The process involves gradually introducing a suitable catalyst while heating the mixture to a predetermined reaction temperature of 60 to 90°C, stirring the mixture for a predetermined time of at least 90 minutes while maintaining the mixture at the predetermined reaction temperature, and then cooling the reaction product of the carbinol-terminated silicone / polyurethane hybrid prepolymer. (B) (v) (a) The carbinol-terminated silicone / polyurethane hybrid prepolymer, (v) (b) Any cured silicone elastomer powder, (v)(c) Any silicon-free particles and / or fine particles selected from at least one of the following: polymethyl methacrylate (PMMA), ethylene-vinyl acetate copolymer (EVA), ethylene-acrylate copolymer (EAA), ethylene-butyl acrylate copolymer (EBA), ethylene-methyl acrylate copolymer (EMA), ethylene-ethyl acrylate copolymer (EEA), or polyurethane polymer. (v) (d) A polyorganosiloxane containing at least two or at least three silicon-bonded hydrogen (-Si-H) groups per molecule, present in an amount of 1% to 10% by weight of the composition. (v)(f) A polyisocyanate crosslinking agent having three or more isocyanate groups per molecule, in an amount such that the molar ratio of the -OH group in (v)(a) to the -NCO group in (v)(f) in the carbinol-terminated silicone / polyurethane hybrid prepolymer coating composition (v) is 0.95:1 to 1.05:1, and (v)(g) A step of preparing the carbinol-terminated silicone / polyurethane hybrid prepolymer coating composition (v) by mixing with a platinum group metal catalyst, Methods that include...

2. A method for preparing a carbinol-terminated silicone / polyurethane hybrid prepolymer coating composition, wherein a polyurethane curing catalyst (v)(e) is also added to the carbinol-terminated silicone / polyurethane hybrid prepolymer coating composition.

3. A carbinol-terminated silicone / polyurethane hybrid prepolymer coating composition that can be obtained or obtained by the method described in claim 1 or 2.

4. Carbinol-terminated silicone / polyurethane hybrid prepolymer coating composition (v), (v) (a) The carbinol-terminated silicone / polyurethane hybrid prepolymer, (v) (b) Any cured silicone elastomer powder, (v)(c) Any optional silicon-free microparticles and / or fine particles selected from at least one of polymethyl methacrylate (PMMA), ethylene-vinyl acetate copolymer (EVA), ethylene-acrylate copolymer (EAA), ethylene-butyl acrylate copolymer (EBA), ethylene-methyl acrylate copolymer (EMA), ethylene-ethyl acrylate copolymer (EEA), or polyurethane polymer. (v) (d) A polyorganosiloxane containing at least two or at least three silicon-bonded hydrogen (-Si-H) groups per molecule, present in an amount of 1% to 10% by weight of the composition. (v)(f) A polyisocyanate crosslinking agent having three or more isocyanate groups per molecule, in an amount such that the molar ratio of the -OH group in (v)(a) to the -NCO group in (v)(f) of the carbinol-terminated silicone / polyurethane hybrid prepolymer coating composition (v) is 0.95:1 to 1.05:1, and (v)(g) Platinum group metal catalysts, together Includes, composition.

5. The carbinol-terminated silicone / polyurethane hybrid prepolymer coating composition according to claim 4, wherein the silicone / polyurethane hybrid prepolymer coating composition further comprises a polyurethane curing catalyst (v)(e).

6. A method for preparing a carbinol-terminated silicone / polyurethane hybrid prepolymer, (I) Diisocyanate in an amount of 20-30% by weight of the starting components of step (A), (II) Alkanediol chain extender in an amount of 5 to 15% by weight of the starting components of step (A), (III) Carbinol-terminated polydimethylsiloxane in an amount of 25 to 45% by weight of the starting components of step (A), (IV) A solvent in an amount of 20 to 40% by weight of the starting components of step (A), and optionally, (V) Mix together the starting components of step (A) with a polyethertriol in an amount of 2% by weight or less, A method comprising: having a molar ratio of OH:NCO greater than 1.15:1; gradually introducing a suitable catalyst while heating the mixture to a predetermined reaction temperature of 60 to 90°C; continuing to stir the mixture for a predetermined time of at least 90 minutes while maintaining the mixture at the predetermined reaction temperature; and then cooling the reaction product of the carbinol-terminated silicone / polyurethane hybrid prepolymer.

7. A carbinol-terminated silicone / polyurethane hybrid prepolymer that can be obtained or obtained from the method described in claim 6.

8. Use of a carbinol-terminated silicone / polyurethane hybrid prepolymer prepared according to claim 7 or claim 6 in a carbinol-terminated silicone / polyurethane hybrid prepolymer coating composition.

9. A silicone leather composite material, (i) Textile support layer, (ii) A silicone binder, which is a cured product of a two-component hydrosilylated curable silicone rubber composition designed to adhere to the textile support layer (i) and the skin layer (iii), and having a Shore A hardness of 20 to 40 as measured according to ASTM D2240, (iii) A silicone skin layer which is a cured product of a two-component hydrosilylated curable silicone rubber composition containing an adhesion promoter and has a Shore A hardness of 50 or greater (≧) when measured according to ASTM D2240, (iv) A silicone topcoat layer which is a cured product of a two-component hydrosilylated curable silicone topcoat containing an adhesion promoter, (v) A silicone / polyurethane hybrid prepolymer coating layer which is a cured product of the silicone / polyurethane hybrid prepolymer coating composition according to claim 3, 4, or 5, Includes, A silicone leather composite material wherein the silicone binder (ii) is bonded between the textile support (i) and the skin layer (iii), the skin layer (iii) is located between the silicone binder layer (ii) and the silicone / polyurethane hybrid prepolymer coating layer, and the silicone topcoat layer (iv) is located on the silicone / polyurethane hybrid prepolymer coating layer (v).

10. The silicone leather composite material according to claim 9, wherein the average dry film thickness of the carbinol-terminated silicone / polyurethane hybrid prepolymer coating layer (v) is 10 μm to 50 μm using the method disclosed herein.

11. The silicone leather composite material according to claim 9 or 10, wherein the silicone / polyurethane hybrid prepolymer coating layer (v) has an elastic modulus of 10 MPa or more, which is determined according to ASTM D882 using the first straight portion of the load-elongation curve to calculate the elastic modulus, and is provided in the silicone leather composite material between the silicone skin layer (iii) and the silicone topcoat layer (iv).

12. The silicone leather composite material according to claim 9, 10, or 11, which can withstand at least 5,000 cycles of JSPS abrasion resistance when measured using the method described herein.

13. A method for preparing the silicone leather composite material according to claim 9, comprising the steps of preparing the carbinol-terminated silicone / polyurethane hybrid prepolymer coating composition according to claim 1 or 2, and then, (a) A step of coating the release paper with a layer of the carbinol-terminated silicone / polyurethane hybrid prepolymer coating composition, and curing the composition to provide a carbinol-terminated silicone / polyurethane hybrid prepolymer coating layer (v), (b) A step of applying a layer of silicone skin composition onto the cured carbinol-terminated silicone / polyurethane hybrid prepolymer coating layer (v), and curing the composition to provide a silicone skin layer (iii), (c) A step of applying a layer of silicone binder composition onto the cured silicone skin layer (iii), applying a textile layer (i) onto the silicone binder composition, and curing and / or laminating the composition to form a silicone binder layer (ii) between the textile support layer (i) and the skin layer (iii), (d) A step of removing the release paper from the cured carbinol-terminated silicone / polyurethane hybrid prepolymer coating layer (v), (e) A step of applying a layer of a two-component hydrosilylated curable silicone topcoat composition onto the cured carbinol-terminated silicone / polyurethane hybrid prepolymer coating layer (v), and curing the topcoat composition to form a silicone topcoat layer (iv), Methods that include...

14. The method according to claim 13, wherein the silicone / polyurethane hybrid prepolymer coating composition is cured at a temperature of 120°C to 180°C for 2 to 10 minutes to obtain an average dry coating thickness of 10 μm to 50 μm using the method described herein.

15. The method according to claim 13 or 14, wherein the two-component hydrosilylated curable silicone topcoat composition is cured at a temperature of 130°C to 160°C for 2 to 8 minutes to form a silicone topcoat (v) having an average dry film thickness of 5 to 20 μm using the method disclosed herein.

16. Use of a layer of a carbinol-terminated silicone / polyurethane hybrid prepolymer coating layer (v) in or for furniture, decorations, handbags, binders, travel bags, clothing, telephone covers, electronic product covers, book covers, footwear, automotive interiors, automotive seats, wearable devices, and / or medical beds / seats, in a silicone / polyurethane composite leather material according to any one of claims 9 to 12, or prepared according to the method described in claims 13 to 15.

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