Modified organic silicon leather and preparation method thereof

Abstract

The invention discloses a preparation method of modified organic silicon leather. Therefore, 100 parts of UV-based and oligosiloxane-modified acrylate resin OSPA with the solid content of 50%-60%, 0.5-5 parts of oil-soluble color paste, 0.5-1 part of a wetting dispersant, 5-20 parts of leather collagen powder and the like are firstly mixed to prepare a slurry A material, then a polyisocyanate curing agent B is added, and the slurry A material is uniformly mixed to prepare a slurry B material; the preparation method comprises the following steps: uniformly stirring the material A and the material B into paste, coating the paste on the surface of a base material such as superfine fibers or non-woven fabrics, heating and curing, and spraying a leather feeling agent, so as to prepare the synthetic leather which has the characteristics of an organic silicon surface and multiple properties of a polyacrylate coating, such as good water resistance, vapor permeability, aging resistance and mechanical properties. The OSPA resin in the synthetic leather is modified acrylate resin, and the structure of the modified acrylate resin simultaneously contains a 2-hydroxybenzophenone derivative group and a heptamethyltrisiloxane or trimethylsilyl terminated polydimethylsiloxane chain segment.

Description

Technical Field

[0001] The present invention belongs to the field of modified organic silicon leather and functional materials, and specifically relates to a method for preparing modified organic silicon leather based on an acrylic resin co-modified with a 2-hydroxybenzophenone derivative ultraviolet (UV) absorbing group and oligosiloxane and leather collagen powder. Background Art

[0002] Silicone leather (abbreviated as silicone leather) is artificial leather made from addition silicone rubber as raw material. Silicone leather, with polydimethylsiloxane as resin skeleton, has good weather resistance, aging resistance, high and low temperature resistance, and the leather surface is waterproof, anti-fouling, easy to clean and flame retardant. Therefore, it has not only become a research and development hotspot in the fields of silicone, leather and new functional materials in recent years, but also one of the most popular new materials in the market recently. For example, documents CN117779479A, CN 115652651A, CN117487456A, CN115595800A, etc. have used a layer-by-layer stacking method, that is, by first coating and curing a layer of adhesive silicone base coating material on the surface of the base fabric, and then coating an intermediate layer composed of vinyl silicone oil, hydrogen-containing silicone oil, filler, catalyst, etc., and then coating a layer of silicone surface layer after curing, to obtain a type of silicone leather with good application performance and feel. However, technicians in the application process also found that the physical and mechanical properties (such as tear strength and breaking strength, etc.) of silicone leather made solely based on hydrophobic silicone rubber are inferior to those of natural leather and need to be improved urgently.

[0003] As for the production process, the silicone leather currently produced based on addition silicone rubber often requires three layers of primer, middle layer and surface layer to produce silicone leather. Obviously, this process is relatively cumbersome and complicated.

[0004] As we all know, small molecule oligosiloxanes have similar hydrophobic, aging-resistant, and flame-retardant properties as traditional silicone polymers, but they are highly compatible with aliphatic or aromatic organic resins. Therefore, introducing oligosiloxanes into acrylic resin systems is expected to combine the advantages of both, that is, to give the target resin the unique adhesion and mechanical strength of acrylic resins, and to give the target resin the surface properties and feel similar to silicone leather produced by polysiloxanes. Obviously, this can not only improve the defects of existing addition-type silicone leathers, but also expand the application scope of silicone leather to many production fields such as interior leather for automobiles and ships, sports shoe leather, luggage leather, interior wall decoration materials for home decoration, and accessories for electronic products such as sports bracelets, iPads, and mobile phone jackets. Summary of the invention

[0005] Aiming at the defects that the mechanical strength and friction fastness of addition-type organic silicon leather are poor, and the processing and production process requires three layers of coating of adhesive base coating + middle layer + surface layer to produce leather (the leather making process is relatively cumbersome and complicated), the present invention discloses a one-step method for preparing organic silicon leather based on light aging resistance, a structure containing ultraviolet (UV) absorption groups and oligosiloxane-modified acrylic ester resin as a film-forming substance, and skin collagen fiber powder as a functional filler. To this end, the present invention adopts the following technical scheme:

[0006] A method for preparing modified organic silicone leather comprises two steps of slurry preparation and modified organic silicone leather preparation:

[0007] (1) Preparation of leather slurry: 100.0 parts of UV-based and oligosiloxane-modified acrylate resin (OSPA) with a solid content of 50%-60%, 0.5-5.0 parts of oil-soluble color paste, 0.5-1.0g of oil-soluble wetting dispersant, 5.0-20.0 parts of skin collagen fiber powder, and 10.0-20.0 parts of diluent solvent (DS) are weighed by mass, and the mixture is stirred, dispersed and mixed evenly, and vacuum degassing is performed to obtain material A; then, polyisocyanate curing agent is weighed according to a molar ratio of hydroxyl (C-OH) contained in material A OSPA to -NCO in polyisocyanate curing agent of about 1:1-1.2, and the content is diluted with diluent solvent to about 50%, thereby obtaining material B; then, material A and material B are stirred and mixed evenly, and the viscosity of the system is adjusted to about 5000-20000mPa.s with a thickener, and the obtained fluid is the leather slurry.

[0008] (2) Preparation of modified silicone leather: Fix the base on the test bench, and evenly apply the leather slurry on the surface of the base with a wire rod or a scraper. Control the amount of slurry so that the thickness of the coating after drying is controlled to be about 150-300 μm. Then, stick a layer of masking release paper, and then heat to 80-120°C to cure for 20-30 minutes. Remove the release paper, and spray the leather feel agent on the leather surface. The resulting leather is the modified silicone leather made based on OSPA resin.

[0009] The UV group and oligosiloxane modified acrylic resin, wherein the UV group is a 2-hydroxybenzophenone derivative group that can obviously absorb ultraviolet light with a λmax of about 243-325nm; the oligosiloxane is a heptamethyltrisiloxane (polyether) group or a single-end trimethylsilyl polydimethylsiloxane (polyether) group [referred to as polydimethylsiloxane (polyether) group] with a polymerization degree (n) of about 4-40.

[0010] The UV-based and oligosiloxane-modified acrylic resin has a main component of a multi-component copolymer of oligosiloxane acrylate-co-acrylate-co-hydroxy vinyl monomer-co-other vinyl functional monomer-co-vinyl UV absorber or a multi-component copolymer of oligosiloxane acrylate-co-acrylate-co-acrylonitrile-co-hydroxy vinyl monomer-co-other vinyl functional monomer-co-vinyl UV absorber; the hydroxy vinyl monomer is a (meth) hydroxyalkyl acrylate or a hydroxyalkyl allyl ether, and the alkyl group in the hydroxyalkyl group is an alkylene containing 2-4 methylene groups; the other vinyl functional monomers are vinyl silanes or (meth) acrylic monomers that can provide resin cross-linking or adhesion properties; the vinyl UV absorber is an acrylate or allyl ether compound containing a 2-hydroxybenzophenone derivative group.

[0011] The UV-based and oligosiloxane-modified acrylic resin, the main component of which is heptamethyltrisiloxane (polyether) acrylate-co-C 1-18 Copolymer of acrylate-co-hydroxyalkyl acrylate-co-vinylsilane-co-2-hydroxy-4-propyleneoxybenzophenone, heptamethyltrisiloxane (polyether) acrylate-co-C 1-18 Copolymer of acrylate-co-acrylonitrile-co-hydroxyalkyl acrylate-co-vinylsilane-co-2-hydroxy-4-propyleneoxybenzophenone; heptamethyltrisiloxane (polyether) acrylate-co-C 1-18 Copolymer of acrylate-co-allyl hydroxyalkyl ether-co-vinylsilane-co-2-hydroxy-4-acryloxybenzophenone, heptamethyltrisiloxane (polyether) acrylate-co-C 1-18 Copolymer of acrylate-co-acrylonitrile-co-allyl hydroxyalkyl ether-co-vinylsilane-co-2-hydroxy-4-acryloxybenzophenone; heptamethyltrisiloxane (polyether) acrylate-co-C 1-18 Copolymer of acrylate-co-acrylonitrile-co-allyl hydroxyalkyl ether-co-vinylsilane-co-4-(β-hydroxy-γ-allyloxy)propoxy-2-hydroxybenzophenone, heptamethyl trisiloxane (polyether) acrylate-co-C 1-18 Copolymer of acrylate-co-allyl hydroxyalkyl ether-co-2-hydroxy-4-(meth)acryloxybenzophenone or monotrimethylsilyl-terminated polydimethylsiloxane (polyether) acrylate-co-C 1-18 Copolymer of acrylate-co-allyl hydroxyalkyl ether-co-vinyl silane-co-2-hydroxy-4-propyleneoxybenzophenone, monotrimethylsilyl-terminated polydimethylsiloxane (polyether) acrylate-co-C 1-18Copolymer of acrylate-co-acrylonitrile-co-allyl hydroxyalkyl ether-co-vinylsilane-co-2-hydroxy-4-propyleneoxybenzophenone, monotrimethylsilyl-terminated polydimethylsiloxane (polyether) acrylate-co-C 1-18 Copolymer of acrylate-co-hydroxyalkyl acrylate-co-vinylsilane-co-2-hydroxy-4-propyleneoxybenzophenone, monotrimethylsilyl-terminated polydimethylsiloxane (polyether) acrylate-co-C 1-18 Copolymer of acrylate-co-acrylonitrile-co-hydroxyalkyl acrylate-co-vinylsilane-co-2-hydroxy-4-propyleneoxybenzophenone, monotrimethylsilyl-terminated polydimethylsiloxane (polyether) acrylate-co-C 1-18 Copolymer of acrylate-co-hydroxyalkyl acrylate-co-vinylsilane-co-2-hydroxy-4-(acryloyloxy)benzophenone, monotrimethylsilyl-terminated polydimethylsiloxane (polyether) acrylate-co-C 1-18 Copolymer of acrylate-co-acrylonitrile-co-hydroxyalkyl acrylate-co-vinylsilane-co-2-hydroxy-4-(acryloyloxy)benzophenone, monotrimethylsilyl-terminated polydimethylsiloxane (polyether) acrylate-co-C 1-18 One of the copolymers such as acrylate-co-hydroxyalkyl acrylate-co-acrylonitrile-co-2-hydroxy-4-(acryloyloxy)benzophenone, wherein the polyether group is a polyoxyethylene polyoxypropylene ether group or a polyoxypropylene ether group.

[0012] The specific preparation method of the UV-based and oligosiloxane-modified acrylic resin is as follows:

[0013] Weigh 5.0-30.0 parts of oligosiloxane acrylate (OSA), 46.0-90.0 parts of acrylate, 0-10 parts of acrylonitrile, 3.0-8.0 parts of hydroxyl olefin monomer (HA), 1-2 parts of other olefin functional monomers, and 1-4 parts of olefin ultraviolet absorber (AUV) by mass, stir and mix, and ultrasonically disperse for 10-20 minutes to obtain a total of about 100 parts of monomer mixture A; then, add 0.5%-1.0% (i.e. 0.5-1.0 part) of free radical initiator based on the mass of A to obtain mixture B. Divide B into two parts, (I) and (II), (I) accounts for about 1 / 3-1 / 4 of the total mass of B, and (II) accounts for about 2 / 3-3 / 4 of the total mass of B, and set aside.

[0014] Take (I) and an appropriate amount of organic solvent (S1), stir and heat to 75-85°C for reaction for 10-30 minutes, then add (II) dropwise, control the dropping speed of (II) so that it is dripped within 2 hours, and then continue to keep warm and react for 2-4 hours to obtain a transparent to slightly turbid viscous liquid, which is a copolymer of oligosiloxane acrylate-co-acrylate-co-acrylonitrile-co-hydroxyolefin monomer-co-other olefin functional monomer-co-olefin UV absorber or a copolymer of oligosiloxane acrylate-co-acrylate-co-hydroxyolefin monomer-co-other olefin functional monomer-co-olefin UV absorber, referred to as UV-based and oligosiloxane modified acrylate resin (OSPA), with a solid content of about 50%-60%.

[0015] The oligosiloxane acrylate has a structure as shown in formula (1)-(2), which is a (polyether) acrylate having a heptamethyltrisiloxane segment at one end of the molecule [see formula (1), also known as heptamethyltrisiloxane (polyether) acrylate], or a (polyether) acrylate having a trimethylsilyl-terminated polydimethylsiloxane segment at one end of the molecule [see formula (2), referred to as polydimethylsiloxane (polyether) acrylate]; in formula (1) and (2), the polyether group is a polyoxyethylene polyoxypropylene ether group, wherein a, a1=0-3, b, b1=0-10, a+b=0-10, a1+b1=0-10; M, M'=H or CH3; R=H or CH3; n=4-40.

[0016]

[0017] The oligosiloxane acrylate can be prepared by the esterification and dehydration reaction of the (polyether) oligosiloxane (OS-OH) containing C-OH in the structure shown in formula (3)-(4) and unsaturated olefinic carboxylic acid (VC) or can be directly ordered from relevant manufacturers.

[0018] The (polyether) oligosiloxane containing C-OH in the structure is a small molecule compound or oligomer having a heptamethyltrisiloxane (polyether) group [see formula (3)] or a monotrimethylsilyl-terminated polydimethylsiloxane (polyether) group having a polymerization degree n of about 4-40 [see formula (4)] connected to one end of the molecule, and containing C-OH, and is selected from 3-hydroxypropyl-1,1,1,3,5,5,5-heptamethyltrisiloxane, 3-hydroxyethyloxypropyl-1,1,1,3,5,5,5-heptamethyltrisiloxane, and a=0-3, b=0- 10. One of 3-(hydroxy-terminated polyoxyethylene polyoxypropylene propyl)-1,1,1,3,5,5,5-heptamethyltrisiloxanes with a+b=0-10 or one of single-terminated hydroxypropyl polydimethylsiloxane with a1=0, b1=0, n=4-40, single-terminated hydroxyethyloxypropyl polydimethylsiloxane with a1=1, b1=0, n=4-40, and single-terminated hydroxyethyloxypropyl polydimethylsiloxane with a1=0-3, b1=0-10, a1+b1=0-10, n=4-40;

[0019]

[0020] The oligosiloxane containing C-OH in the structure can be generally 1,1,1,3,5,5,5-heptamethyltrisiloxane or polydimethylsiloxane (CH3)3SiO[(CH3)2SiO] with n=4-40 and one end being trimethylsilyl and the other end being dimethylhydrogensilane. n It is prepared by the hydrosilylation addition reaction of Si(CH3)2H with allyl alcohol, or hydroxyethyl allyl ether, or hydroxy-terminated polyoxyethylene polyoxypropylene allyl ether with a=0-3, b=0-10, a+b=0-10 in the presence of platinum catalyst, and is commissioned to Anhui Aiyota Silicone Oil Co., Ltd., Zhejiang Runhe New Materials Co., Ltd., Shaanxi Andyjier New Materials Co., Ltd. and others for synthesis and ordering.

[0021] The alkenyl carboxylic acid is a compound containing a reactive C=C double bond and a carboxyl group in its structure, and is selected from one of acrylic acid, methacrylic acid, 2-butenoic acid, 5-hexenoic acid and the like.

[0022] The esterification reaction of the oligosiloxane (OS-OH) containing C-OH in the structure and the unsaturated olefinic carboxylic acid (VC), the molar ratio of OS-OH to VC is about 1:1.2-10, the reaction temperature is 80-110°C, the reaction time is about 4-8h, and the esterification reaction catalyst is aluminum acetylacetonate; the specific reaction steps are: according to the molar ratio of OS-OH to VC is about 1:1.2-10, OS-OH and VC are weighed respectively, and then 0.1% of the total mass of OS-OH and VC is added -0.5% of hydroquinone inhibitor, 0.1%-0.2% of esterification reaction catalyst, 50%-100% of solvent (S2), stir and mix, heat to 80-110°C for esterification and water extraction reaction for 4-8h; after the reaction, first distill and recover the solvent, and evaporate the residual VC under reduced pressure, and then wash the product with 2% Na2CO3 aqueous solution and deionized water for 3 times respectively, and then dry it over anhydrous magnesium sulfate to obtain a colorless transparent to translucent liquid, which is the target product - oligosiloxane acrylate (OSA).

[0023] The acrylic acid ester is a acrylate having a structure containing C 1-18 Alkyl aliphatic or alicyclic (meth) acrylate, such as aliphatic acrylic acid C 1-18 Alkyl esters, aliphatic methacrylate C 1-18 Alkyl esters, C 5-10 Alicyclic hydrocarbon (meth)acrylates, etc., are selected from a mixture of two or more of methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, dodecanol (meth)acrylate, hexadecanol (meth)acrylate butyl, octadecyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, etc.

[0024] The hydroxyethyl monomer (HA) is a compound containing a C-hydroxyl group and an alkenyl group in its molecular structure, and is selected from hydroxyalkyl (meth)acrylates, such as hydroxyethyl acrylate (HEAA), hydroxypropyl acrylate (HPAA), hydroxyethyl methacrylate, hydroxypropyl methacrylate, or hydroxyalkyl allyl ethers, such as hydroxyethyl allyl ether, hydroxybutyl allyl ether, etc.

[0025] The other alkenyl functional monomers are small molecular compounds containing silaneoxy or carboxyl groups and alkenyl groups in their molecular structures, and are selected from alkenyl silanes such as (meth)acryloxypropyltrimethoxysilane, (meth)acryloxypropyltriethoxysilane, (meth)acryloxypropylmethyldimethoxysilane, (meth)acryloxypropylmethyldiethoxysilane or (meth)acrylic acid, 2-butenoic acid, etc.

[0026] The alkenyl ultraviolet (UV) absorber is a substance containing an alkenyl group and a 2-hydroxybenzophenone derivative group in its structure and capable of absorbing ultraviolet light with a wavelength (λmax) of about 243-325 nm, and is selected from one of 4-propyleneoxy-2-hydroxybenzophenone (also known as 2-hydroxy-4-propyleneoxybenzophenone), 2-hydroxy-4-(methacryloyloxy)benzophenone, 4-(β-hydroxy-γ-allyloxy)propoxy-2-hydroxybenzophenone, and the like.

[0027] The free radical initiator is an oil-soluble initiator, which is selected from one of benzoyl peroxide (BPO), azobisisobutyronitrile (AIBN), percarbonate and the like.

[0028] The organic solvent S1 is aromatic hydrocarbons, esters, alcohol ethers, alcohol ether esters, ketones, etc., and is selected from one or a mixture of two of benzene, toluene, propylene glycol dimethyl ether, ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, propylene glycol methyl ether acetate, etc., and environmentally friendly esters, alcohol ethers, and alcohol ether ester solvents are preferably selected.

[0029] The water extraction solvent S2 used in the OSA synthesis is selected from one of benzene, cyclohexane, methylcyclohexane, heptane, etc.

[0030] The dilution solvent DS is selected from one or a mixture of 2-3 of ethyl acetate, butyl acetate, ethylene glycol dimethyl ether, propylene glycol dimethyl ether (DMP), etc.;

[0031] The oil-soluble color paste is a general color paste used in the processing of solvent-based acrylic resins, such as Colanyl Black N131-CN 0030 black color paste, DF616 permanent red F5, DF618 permanent red F2, DF816 standard medium yellow, etc., which are purchased from Clariant Chemicals (China) Co., Ltd., Henan Wangong Environmental Protection Materials Co., Ltd., Zhengzhou Shichuang Chemical Products Sales Co., Ltd. and other units; the wetting and dispersing agent is an oil-soluble or solvent-based wetting and dispersing agent produced by BYK, such as BYK-ATU, BYK-190, BYK-163, BYK-110, etc.

[0032] The leather collagen powder, also known as leather collagen fiber powder, is a powdery substance obtained by recycling, crushing and decolorizing the scraps produced in the production process of natural leather such as pig skin, cow skin, sheep skin, etc. It is treated with 1% octylsilane-ethanol solution and then dried before use.

[0033] The curing agent is a polyisocyanate containing 2-3 -NCO functional groups in the structure, a polyether diol or a polyester diol with diisocyanate grafted (-g-) at both ends, etc., and N3390, 4,4'-dicyclohexylmethane diisocyanate (HMDI), isophorone diisocyanate (IPDI), polyether diol grafted (-g-) di(isophorone diisocyanate) or polyester diol-g-di(isophorone diisocyanate) produced by Bayer or Sikotron are selected; the thickener is the associative nonionic polyurethane thickener 8W of Rohm&Hass.

[0034] The base is a release paper whose surface is treated with a fluorine release agent, or a non-woven fabric, microfiber fabric, etc. made from polyester, spandex, polyurethane, etc.; the feel agent is a substance sprayed on the surface of leather or synthetic leather to make the leather surface feel smooth or comfortable and oily like sheepskin, and is selected from the oil / water dual-use DC-Q2-3238 or similar products produced by Dow Corning Corporation of the United States.

[0035] The beneficial effects of the present invention are as follows: by utilizing molecular design and a series of chemical reactions, the present invention first synthesizes a modified acrylic resin (OSPA) containing an oligosiloxane segment and a UV absorbing group in its structure by copolymerizing a newly synthesized oligosiloxane acrylate OSA, namely, heptamethyltrisiloxane (polyether) acrylate or n=4-40 monotrimethylsilyl polydimethylsiloxane (polyether) acrylate with aliphatic or alicyclic acrylate, hydroxyl olefin monomers, other alkenyl functional monomers containing silane alkoxy or carboxyl groups in the structure, acrylonitrile, alkenyl ultraviolet absorbers and the like. -acrylate-co-acrylonitrile-co-other olefin functional monomers-co-olefin UV absorbers and other copolymers; then use OSPA as a film-forming substance, natural leather collagen powder as an added component, and polyisocyanate containing 2-3 -NCO functional groups (polyether or polyester polyol) in the structure as a curing component, and compound each component into a leather slurry, and then use a one-step method to coat the slurry on the surface of non-woven fabrics or ultrafine fiber base fabrics, etc., and after curing, spray the surface with a hand feeling agent, thereby obtaining a type of modified silicone leather with silicone properties on the surface and acrylic resin composite material properties inside. Applications show that the modified silicone leather of the present invention not only has a plump, moisturizing and slippery feel similar to natural leather, good water-repellent, dust-proof, heat-resistant, aging-resistant and breathable properties, but also has good mechanical strength. Obviously, this provides a feasible solution to the shortcomings of the currently available silicone leather. DETAILED DESCRIPTION

[0036] The present invention will be further described below in conjunction with embodiments, but the present invention is not limited to the embodiments.

[0037] (I) Preparation of resin raw materials

[0038] (1) Synthesis of the reaction precursor material - oligosiloxane acrylate (OSA)

[0039] In a three-necked round-bottom flask equipped with a thermometer, a reflux condenser and an electric stirrer, OS-OH [see formula (3)-(4)] and VC are weighed respectively according to a molar ratio of C-OH-containing (polyether) oligosiloxane (OS-OH) to unsaturated olefinic carboxylic acid (VC) of about 1:1.2-10, and then 0.3% of hydroquinone inhibitor, 0.1% of aluminum acetylacetonate catalyst and 80% of cyclohexane solvent are added based on the total mass of OS-OH and VC, the mixture is stirred and mixed, and the temperature is raised to 90°C for water extraction reaction for 6 hours; after the reaction is completed, the cyclohexane solvent is firstly distilled and recovered at 90°C under normal pressure, and then heated to 40°C for 2 hours. 表 =0.09MPa, the residual VC was evaporated under reduced pressure, and then the product was washed three times with 2% Na2CO3 and deionized water respectively, and dried over anhydrous magnesium sulfate to obtain a colorless transparent to translucent liquid, which is the precursor raw material of the reaction - oligosiloxane acrylate (OSA) with the structure shown in formula (1)-(2). The raw materials and amounts of OSA synthesis in each embodiment are shown in Table 1.

[0040] Table 1 List of raw materials and dosage for the synthesis of oligosiloxane acrylate (OSA)

[0041]

[0042] *HMTS-C3H6OH: 3-hydroxypropyl-1,1,1,3,5,5,5-heptamethyltrisiloxane; HMTS-C3H6OC2H4OH: 3-(hydroxyethyloxypropyl)-1,1,1,3,5,5,5-heptamethyltrisiloxane; HMTS-C3H6(OC3H6)3OH: 3-(hydroxy-terminated polyoxypropylene propyl)-1,1,1,3,5,5,5-heptamethyltrisiloxane with a=0, b=3; MPDS-C3H6OC2H4OH: single-terminated hydroxyethyloxypropyl polydimethylsiloxane; MPDS-C3H6(OC3H6)6OH: a=0, b=6 single-terminated hydroxy-terminated polyoxypropylene propyl polydimethylsiloxane

[0043] (2) Synthesis of UV-based and oligosiloxane-modified acrylate resin (OSPA)

[0044] According to mass, 5.0-30.0g OSA, 57.0-82.0g acrylate monomer mixture composed of soft acrylate monomer (such as butyl acrylate, etc.), hard acrylate monomer (such as methyl methacrylate, etc.) and alicyclic acrylate, 5.0g acrylonitrile (AN), 5.0g hydroxyl olefin monomer (HA), 1.0g methacryloxypropyl trimethoxysilane (KH-570), 2.0g vinyl UV absorber (AUV) were weighed, stirred and mixed, and ultrasonically dispersed for 20 minutes with an ultrasonic wave of 1000W power to obtain a total of about 100.0g monomer mixture A; then, 0.6g BPO was added according to the total amount of A to obtain monomer mixture B. B was divided into two parts (I) and (II), (I) accounted for about 1 / 4 of the mass of B, and (II) accounted for about 3 / 4 of the mass of B, and used for later use.

[0045] In a three-necked reaction flask equipped with a thermometer, a reflux condenser and an electric stirrer, add (I) and 66.67-100.0g of propylene glycol dimethyl ether, stir and heat to 80°C for 20 minutes, then dropwise add (II) and allow it to drip completely within 2 hours, then continue to keep warm at 80°C for 4 hours, and the reaction is completed to obtain a transparent viscous liquid, i.e., a modified acrylic resin containing a 2-hydroxybenzophenone derivative (UV) group and an oligosiloxane segment in the structure - OSA-co-acrylate-co-acrylonitrile-co-hydroxyethyl monomer-co-methacryloxypropyltrimethoxysilane-co-alkenyl UV absorber, denoted as OSPA, with a solid content of about 50%-60%. The raw materials and amounts of the UV-based and oligosiloxane-modified acrylic resin OSPA synthesized in Examples 1-5 are shown in Table 2.

[0046] Table 2 List of raw materials and dosage for synthesis of UV-based and oligosiloxane-modified acrylic resin (OSPA)

[0047]

[0048] (II) Embodiment

[0049] Example 1

[0050] (1) Preparation of leather slurry

[0051] Take 100.0g of a multi-polymer of 60% solid content OSPA-1 (3-acryloxypolyoxypropylenepropyl-1,1,1,3,5,5,5-heptamethyltrisiloxane)-co-butyl acrylate-co-methyl methacrylate-co-cyclohexyl methacrylate-co-acrylonitrile-co-hydroxypropyl acrylate-co-methacryloxypropyltrimethoxysilane-co-(2-hydroxy-4-acryloxybenzophenone), 0.5g of Colanyl Black N131-CN 0030 black color paste [Clariant Chemicals (China) Co., Ltd.], 0.5g of BYK-ATU dispersant, 5.0 g skin collagen powder, 10.0 g ethyl acetate (EA) / propylene glycol dimethyl ether (DMP, 1:1, wt / wt), stirred and dispersed for 20 min using a disperser with a speed of about 1000 r / m, and vacuumed and degassed to obtain a total of about 116.0 g of uniform fluid, recorded as slurry A;

[0052] Take another 5.49g of polyisocyanate curing agent N-3390, dilute it with 5.49g EA / DMP (1:1, wt / wt) to a solid content of 50%, recorded as material B; stir material A and material B to mix evenly, and then add 1.0g of Rohm&Haas 8W thickener to make a paste with a viscosity of about 5000mPa.s, which is leather making slurry-1.

[0053] (2) Preparation of modified silicone leather SiL-1

[0054] Take a polyester microfiber base cloth (Changshu Jinda Nonwoven Products Co., Ltd.) or release paper, flatten it and fix it on the test bench, use RDS-70 wire rod to evenly apply leather slurry-1 on the surface of the base cloth or release paper, control the amount of slurry so that the coating thickness after drying is about 160μm, and then stick a layer of fluorine texture release paper, cure at 90℃ for 30min, remove the release paper, and then spray the leather surface with a concentration of about 0.5% DC-Q2-3238 leather feel agent-ethanol solution, hang it in a drying room at 80℃ for 1h, and the obtained leather sample is the modified silicone leather (SiL-1) prepared by the present invention based on UV-based and oligosiloxane modified acrylate resin OSPA-1.

[0055] Example 2

[0056] (1) Preparation of leather slurry

[0057] Take 100.0g of a multi-polymer of 60% OSPA-2, [3-(methacryloyloxyethyloxypropyl)-1,1,1,3,5,5,5-heptamethyltrisiloxane]-co-ethyl acrylate-co-butyl acrylate-co-methyl methacrylate-co-isobornyl methacrylate-co-acrylonitrile-co-hydroxyethyl acrylate-co-methacryloyloxypropyltrimethoxysilane-co-(2-hydroxy-4-methacryloyloxybenzophenone), 5.0g of universal DF616 permanent red F5 color paste (Zhengzhou Shichuang Chemical Products Sales Co., Ltd.), 1.0g BYK-ATU dispersant, 20.0 g skin collagen powder, 20.0 g ethyl acetate (EA) / DMP (1:1, wt / wt) were diluted with solvent, and stirred and dispersed for 30 min using a disperser with a speed of about 1000 r / m, and vacuumed and degassed to obtain a total of about 143.0 g of uniform fluid, which was recorded as slurry A2;

[0058] Take another 18.70g of polytetramethylene glycol (Mn=1000)-g-di(isophorone diisocyanate) curing agent, dilute it with 18.70g EA / DMP (1:1, wt / wt) to a solid content of 50%, and record it as B2 material; stir and mix slurry A2 and B2, and then add 1.5g 8W thickener (Rohm&Haas Company) to make a fluid with a viscosity of about 18000mPa.s, which is leather slurry-2.

[0059] (2) Preparation of modified silicone leather SiL-2

[0060] Take a spandex (i.e. polyurethane) ultrafine fiber base cloth or release paper, lay it flat and fix it on the test bench, use an RDS-70 wire rod to evenly apply slurry-2 on the surface of the base cloth or release paper, control the amount of slurry so that the coating thickness after drying is about 290 μm, and then stick a layer of masking release paper on it, and cure it at 120°C for 20 minutes; remove the release paper, and then spray 0.5% DC-Q2-3238 leather feel agent-ethanol solution on the leather surface, hang it in a drying oven at 90°C for 1 hour, and the obtained leather sample is the modified silicone leather (SiL-2) prepared by the present invention based on UV-based and oligosiloxane-modified acrylate resin OSPA-2.

[0061] Example 3

[0062] (1) Preparation of leather slurry

[0063] Take 100.0g of a multi-polymer of 60% solid content OSPA-3 (3-acryloxypropyl-1,1,1,3,5,5,5-heptamethyltrisiloxane)-co-butyl acrylate-co-isooctyl acrylate-co-methyl methacrylate-co-cyclohexyl methacrylate-co-acrylonitrile-co-hydroxyethyl allyl ether-co-methacryloxypropyl trimethoxysilane-co-(4-β-hydroxy-γ-allyloxypropoxy-2-hydroxybenzophenone), 2.0g of universal DF616 permanent red F5 color paste (Zhengzhou Shichuang Chemical Products Sales Co., Ltd.), 0.6g BYK-163 dispersant, 10.0g leather collagen powder, 10.0g EA / DMP (1:1, wt / wt) were diluted with solvent, and stirred and dispersed for 25 minutes using a disperser with a speed of about 1000r / m, and vacuumed for degassing to obtain a total of about 121.6g of uniform fluid, which was recorded as slurry A3; 4.82g of 4,4'-dicyclohexylmethane diisocyanate (HMDI) curing agent was taken and diluted with 4.82g EA / DMP (1:1, wt / wt) to a solid content of 50%, which was recorded as B3 material;

[0064] Slurry A3 and material B3 were stirred and mixed, and then 1.2 g of 8W thickener (Rohm & Haas) was added to prepare a uniform fluid with a viscosity of about 10000 mPa.s, which was leather making slurry-3.

[0065] (2) Preparation of modified silicone leather SiL-3

[0066] Take polyester non-woven fabric or release paper, lay it flat and fix it on the test bench, use RDS-70 wire rod to evenly apply leather slurry-3 on the surface of non-woven fabric or release paper, control the amount of slurry so that the coating thickness after drying is about 203μm, and then stick fluorine texture release paper, cure at 90℃ for 30min, remove the release paper, and then spray about 0.5% DC-Q2-3238 leather feel agent-ethanol solution on the leather surface, hang it in a drying room at 80℃ for 1h, and the obtained leather sample is the modified silicone leather (SiL-3) prepared by the present invention based on UV-based and oligosiloxane modified acrylate resin OSPA-3.

[0067] Example 4

[0068] (1) Preparation of leather slurry

[0069] Take 100.0g of OSPA-4 (50% solid content) - a multi-polymer of methacryloyloxyethyloxypropyl polydimethylsiloxane-co-butyl acrylate-co-methyl methacrylate-co-cyclohexyl methacrylate-co-acrylonitrile-co-hydroxypropyl acrylate-co-methacryloyloxypropyl trimethoxysilane-co-(2-hydroxy-4-methacryloyloxybenzophenone), 1.0g of universal DF616 permanent red F5 color paste (Zhengzhou Shichuang Chemical Products Sales Co., Ltd.), 0.5g of BYK-ATU dispersant, 10.0g of skin collagen powder, 10.0g EA / DMP (1:1, wt / wt) was diluted with solvent, and the mixture was dispersed with a dispersing machine at a speed of about 1000 r / m for 30 min. The mixture was vacuumed and degassed to obtain a total of about 121.5 g of uniform fluid, which was recorded as slurry A4. 15.40 g of polyoxalic acid hexamethylene glycol diol (Mn1000)-g-bis(hexamethylene diisocyanate) curing agent was taken and diluted with 15.40 g of EA / DMP (1:1, wt / wt) to a solid content of 50%, which was recorded as material B4.

[0070] Slurry A4 and material B4 were stirred and mixed, and then 1.0 g of 8W thickener (Rohm & Haas) was added to form a uniform fluid with a viscosity of about 8000 mPa.s, which was leather making slurry-4.

[0071] (2) Preparation of modified silicone leather SiL-4

[0072] Take a spandex non-woven fabric or release paper, lay it flat and fix it on the test bench, use an RDS-70 wire rod to evenly apply the leather slurry-4 on the surface of the non-woven fabric or release paper, control the amount of slurry so that the coating thickness after drying is about 180 μm, and then stick a layer of fluorine texture release paper, cure at 90°C for 30 minutes, remove the release paper, and then spray the leather surface with a concentration of about 0.5% DC-Q2-3238 leather feel agent-ethanol solution, hang it in a drying oven at 80°C for 1 hour, and the obtained leather sample is the modified silicone leather (SiL-4) prepared by the present invention based on the UV-based and oligosiloxane-modified acrylate resin OSPA-4.

[0073] Example 5

[0074] (1) Preparation of leather slurry

[0075] Take 100.0g of OSPA-5 (55% solid content) - a multi-polymer of acryloxy polyoxypropylene propyl polydimethylsiloxane-co-butyl acrylate-co-methyl methacrylate-co-isobornyl methacrylate-co-acrylonitrile-co-hydroxyethyl acrylate-co-methacryloxypropyl trimethoxysilane-co-(2-hydroxy-4-methacryloxybenzophenone), 1.0g of universal DF616 permanent red F5 color paste (Zhengzhou Shichuang Chemical Products Sales Co., Ltd.), 0.5g of BYK-ATU dispersant, 10.0g of skin collagen powder, and 10.0g of EA / DMP (1:1, wt / wt) diluted with solvent, and dispersed with a disperser at a speed of about 1000r / m for 30min, and vacuum degassing to obtain a total of about 121.5g of uniform fluid, which is recorded as slurry A5;

[0076] 4.52 g of light-resistant polyurethane curing agent DESMODUR N100 (Covestro, -NCO content 22%, viscosity about 10000 mPa.s) was taken and diluted with 4.52 g of EA / DMP (1:1, wt / wt) to a solid content of 50%, recorded as material B5;

[0077] Slurry A5 and material B5 were stirred and mixed, and then 0.8 g of 8W thickener (Rohm & Haas Company) was added to prepare a uniform fluid with a viscosity of about 7500 mPa.s, which was leather making slurry-5.

[0078] (2) Preparation of modified silicon leather

[0079] Take a polyester microfiber base cloth or release paper, lay it flat and fix it on the test bench, use an RDS-70 wire rod to evenly apply the leather slurry-5 on the surface of the non-woven fabric or release paper, control the amount of slurry so that the coating thickness after drying is about 205 μm, and then stick a layer of fluorine texture release paper, cure at 90°C for 30 minutes, remove the release paper, and then spray the leather surface with a concentration of about 0.5% DC-Q2-3238 leather feel agent-ethanol solution, hang it in a drying room at 80°C for 1 hour, and the obtained leather sample is the modified silicone leather (SiL-5) prepared by the present invention based on the UV-based and oligosiloxane-modified acrylate resin OSPA-5.

[0080] Example 6

[0081] Without adding OSA-1, but other raw materials and amounts are the same as those in Example 1 in Table 2, under the same polymerization method and process conditions, 32.0 g of butyl acrylate, 5.0 g of cyclohexyl methacrylate, 20.0 g of methyl methacrylate, 5.0 g of acrylonitrile, 5.0 g of hydroxypropyl acrylate, 1.0 g of methacryloyloxypropyltrimethoxysilane, and 2.0 g of 4-allyloxy-2-hydroxybenzophenone were subjected to free radical copolymerization in 46.69 g of butyl acetate (BA) at 80° C. for 4 h to obtain an acrylate resin - butyl acrylate-co-cyclohexyl methacrylate-co-methyl methacrylate-co-acrylonitrile-co-hydroxypropyl acrylate-co-methacryloyloxypropyltrimethoxysilane-co-4-allyloxy-2-hydroxybenzophenone, recorded as PA-1.

[0082] Then, PA-1 was used instead of OSPA-1 in Example 1 to prepare slurry and acrylic resin synthetic leather in the same manner, which was used as Reference-1 of the present invention.

[0083] Example 7

[0084] Take 10.0g of commercially available hydrogenated silicone oil (PHMS, Tangshan Sanyou Silicon Co., Ltd., containing Si-H) with a content of about 0.18%. 0.018mol) and 162.0g of terminal vinyl silicone oil Bis-500 (Zhejiang Quzhou Jiancheng Silicone Co., Ltd., containing about 0.018mol of Vi) with a vinyl (Vi) content of 0.3wt% are stirred evenly at a molar ratio of Si-H:Vi=1:1, and 25g is taken, and then 1 drop of complex platinum catalyst KP22, 1.0g of universal DF616 permanent red F5 color paste, 0.5g BYK-ATU dispersant, 10.0g of skin collagen powder, and 10.0g of toluene solvent are added, and stirred and dispersed for 30min with a disperser at a speed of about 1000r / m, and vacuumed for degassing to obtain slurry A, and then slurry A is evenly coated on the surface of polyester microfiber cloth or release paper, and dried at 110°C for 30min for curing. The obtained silicone leather sample is used as reference-2 of the present invention.

[0085] Example 8

[0086] Methyl-terminated polyoxypropylene acrylate CH3(OC3H6)6OCOCH=CH2 with a=0, b=6 and PO number of about 6 was used to replace OSA-5 in Example 5 in Table 2, and free radical copolymerization of monomers such as acrylate was carried out in the same way to prepare reference resin PA-3 of the present invention which does not contain silicone segments but contains polyether acrylate segments - methyl-terminated polyoxypropylene acrylate-co-butyl acrylate-co-methyl methacrylate-co-isobornyl methacrylate-co-acrylonitrile-co-hydroxyethyl acrylate-co-methacryloxypropyltrimethoxysilane-co-(2-hydroxy-4-methacryloxybenzophenone), and then PA-3 was used to replace OSPA-5 in Example 5 to prepare slurry and prepare synthetic leather in the same way, which was used as Reference-3 of the present invention.

[0087] The modified silicone leathers SiL-1-SiL-5 prepared in Examples 1-8 and References 1-3 were taken and balanced for 24 hours at room temperature 25±2°C and relative humidity RH of about 48%, and performance tests were performed:

[0088] Tensile strength and elongation at break: refer to GB / T528-2009 standard, use dumbbell-shaped type I specimen and universal testing machine to test. Water absorption: take SiL silicone leather or reference, cut it into 1×1cm 2 The sample was weighed, immersed in water for 12 hours, taken out, and the surface moisture of the leather was washed with filter paper, and then weighed again. The water absorption of the silicone leather or reference before and after immersion was calculated, and the water absorption rate was calculated. Leather surface hydrophobicity: expressed by the static contact angle (WCA) of a water drop on the leather surface, using a JC-2000C1 static contact angle measuring instrument, and the water drop size was 5μL; aging resistance (1000h×85℃×RH85%): measured with a KK-SN-150 xenon lamp aging resistance test box in accordance with GB / T2423.24-1995 standard. Air permeability: measured with a TQ-A digital leather air permeability measuring instrument in accordance with GB / T 4689.22-1996 leather air permeability measurement method; friction fastness: tested with a friction force measuring instrument. The test results of each embodiment and reference are shown in Table 3.

[0089] Table 3 Performance test results of modified silicone leather SiL and reference

[0090]

[0091] *1000h×85℃×RH85%;◎——No change

[0092] It should be understood that the examples are used to explain the embodiments of the present invention, and the protection scope of the present invention is not limited by the examples within the scope of the subject matter of the present invention.

Claims

1. A method for preparing modified silicone leather, characterized in that: The steps include: 1) Preparation of leather slurry: by weight, take 100 parts of UV-based and oligosiloxane-modified acrylate resin OSPA, 0.5-5 parts of color paste, 0.5-1 parts of wetting dispersant, 5-20 parts of skin collagen powder, and 10-20 parts of dilution solvent DS, disperse and mix to obtain material A; then, weigh polyisocyanate curing agent B according to the molar ratio of C-OH group contained in UV-based and oligosiloxane-modified acrylate resin OSPA in material A to -NCO group in polyisocyanate of 1: (1-1.2); mix materials A and B, and adjust into a paste with a thickener to obtain leather slurry; 2) Preparation of modified silicone leather: Take a substrate, apply the leather slurry evenly on the surface of the substrate with a wire rod, heat and cure, and then spray the leather feel agent to obtain the modified silicone leather; The UV group and oligosiloxane modified acrylate resin OSPA, the UV group is 2-hydroxybenzophenone derivative group, the oligosiloxane is heptamethyltrisiloxane or single-end trimethylsilyl polydimethylsiloxane with a polymerization degree of 4-40.

2. The method according to claim 1, characterized in that The UV-based and oligosiloxane-modified acrylate resin OSPA, the main component of which is a multi-component copolymer of oligosiloxane acrylate-co-acrylate-co-hydroxy olefin monomer-co-olefin functional monomer-co-olefin UV absorber or a multi-component copolymer of oligosiloxane acrylate-co-acrylate-co-acrylonitrile-co-hydroxy olefin monomer-co-olefin functional monomer-co-olefin UV absorber; The oligosiloxane acrylate is one or more of heptamethyl trisiloxane propyl acrylate, heptamethyl trisiloxane polyether acrylate, trimethylsilyl-terminated polydimethylsiloxane propyl acrylate or trimethylsilyl-terminated polydimethylsiloxane polyether acrylate; the polyether group is polyoxyethylene polyoxypropylene ether group -C3H6O(C2H4O) a (C3H6O) b -, where a = 0-3, b = 0-10, a + b = 0-10; The hydroxy vinyl monomer is hydroxyalkyl acrylate, hydroxyalkyl methacrylate, hydroxyalkyl allyl ether, and the alkyl group is an alkylene group containing 2-4 methylene groups; The alkenyl functional monomer is a silane containing vinyl, acryloxypropyl or methacryloxypropyl and 2-3 alkoxy groups; The alkenyl ultraviolet absorber is an acrylate or allyl ether containing a 2-hydroxybenzophenone derivative group.

3. The method according to claim 1, characterized in that The UV-based and oligosiloxane-modified acrylate resin OSPA is obtained by a multi-radical copolymerization reaction of oligosiloxane acrylate with base acrylate, hydroxyl vinyl monomer, alkenyl alkoxy silane, and alkenyl UV absorber, or by a multi-radical copolymerization reaction of oligosiloxane acrylate with base acrylate, acrylonitrile, hydroxyl vinyl monomer, alkenyl alkoxy silane, and alkenyl UV absorber.

4. The method according to claim 3, characterized in that: The oligosiloxane acrylate has a structure as shown in formula (I) or formula (II): In the formula, a, a1 = 0-3, b, b1 = 0-10, a+b = 0-10, a1+b1 = 0-10; M, M' = H or CH3; R = H or CH3; n = 4-40; The matrix acrylate is aliphatic acrylate or alicyclic acrylate; The hydroxy olefin monomer is a reactive monomer containing a C-hydroxyl group and an olefin group; The alkenyl alkoxy silane is a reactive silane containing an acryloxy group or a reactive silane containing an alkenyl group and an alkoxy group; The alkenyl ultraviolet absorber is a reactant containing a 2-hydroxybenzophenone derivative ultraviolet absorption group and an alkenyl group.

5. The method according to claim 4, characterized in that The matrix acrylate is one or more of methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, dodecanol (meth)acrylate, hexadecanol (meth)acrylate, butyl octadecyl (meth)acrylate, cyclohexyl (meth)acrylate, cyclopentyl (meth)acrylate, and isobornyl (meth)acrylate; The hydroxyethyl monomer is one or more of hydroxyethyl acrylate, hydroxypropyl acrylate, and hydroxyethyl allyl ether; The alkenyl alkoxysilane is one or more of methacryloxypropyltrialkoxysilane, acryloxypropyltrialkoxysilane, methacryloxypropylmethyldialkoxysilane, acryloxypropylmethyldialkoxysilane, vinyltrialkoxysilane, and vinylmethyldialkoxysilane, and the alkoxy group is methoxy or ethoxy; The alkenyl ultraviolet absorber is one or more of 4-propyleneoxy-2-hydroxybenzophenone, 2-hydroxy-4-methacryloxybenzophenone, and 4-β-hydroxy-γ-allyloxypropoxy-2-hydroxybenzophenone.

6. The method according to claim 3, characterized in that The UV-based and oligosiloxane-modified acrylate resin OSPA is obtained by a method comprising the following steps: Weigh 5-30 parts of oligosiloxane acrylate, 46-90 parts of matrix acrylate, 0-10 parts of acrylonitrile, 3-8 parts of hydroxyl olefin monomer, 1-2 parts of functional olefin monomer, and 1-4 parts of olefin UV absorber by mass, and mix them by ultrasonic dispersion to obtain a monomer mixture A; then add 0.5%-1.0% of the total mass of free radical initiator according to the mass of A to obtain a mixture B; divide the mixture B into two parts, B1 and B2, for later use; Take B1 and an appropriate amount of solvent, stir and heat to 75-85°C for reaction for 10-30 minutes, then add B2 dropwise and keep warm for reaction for 2-4 hours to obtain UV-based and oligosiloxane-modified acrylate resin OSPA.

7. The method according to any one of claims 3 to 6, characterized in that: The oligosiloxane acrylate is prepared by esterification reaction of C-OH-containing oligosiloxane OS-OH and alkenyl carboxylic acid VC; The C-OH-containing oligosiloxane OS-OH has a structure as shown in formula (III) and / or formula (IV): In the formula, a, a1=0-3, b, b1=0-10, a+b=0-10, a1+b1=0-10; n=4-40; The alkenyl carboxylic acid VC is one or more of acrylic acid, methacrylic acid, 2-butenoic acid, and 5-hexenoic acid.

8. The method according to claim 7, characterized in that In the esterification reaction, the molar ratio of the C-OH-containing oligosiloxane OS-OH to the alkenyl carboxylic acid VC is 1:(1.2-10), the catalyst is aluminum acetylacetonate, the reaction temperature is 80-110°C, and the reaction time is 4-8h; The C-OH-containing oligosiloxane OS-OH is one or more of 3-hydroxypropyl-1,1,1,3,5,5,5-heptamethyltrisiloxane, 3-hydroxyethyloxypropyl-1,1,1,3,5,5,5-heptamethyltrisiloxane, 3-(hydroxy-terminated polyoxyethylene polyoxypropylene propyl)-1,1,1,3,5,5,5-heptamethyltrisiloxane with a=0-3, b=0-10, a+b=0-10, single-end hydroxypropyl polydimethylsiloxane, single-end hydroxyethyloxypropyl polydimethylsiloxane, and single-end hydroxy-terminated polyoxyethylene polyoxypropylene propyl polydimethylsiloxane.

9. The method according to claim 1, characterized in that: The color paste is a dispersion formed by mixing an oil-soluble dye or pigment with a coating additive and dispersing it in a resin or solvent; The wetting and dispersing agent is one or more of oil-soluble BYK-ATU, BYK-190, BYK-163, BYK-110; The skin collagen powder is a powder obtained by recycling, decolorizing and crushing pig skin, cow skin or sheep skin; The polyisocyanate curing agent is one or more of polyisocyanate containing 2-3 -NCO functional groups in the structure, polyether diol-g-diisocyanate, polyester diol-g-diisocyanate; The thickener is an associative nonionic polyurethane thickener 8W; The dilution solvent DS is one or more of ethyl acetate, butyl acetate, ethylene glycol dimethyl ether, and propylene glycol dimethyl ether; The substrate is polyester, nylon and / or polyurethane microfiber cloth or non-woven fabric; The hand feeling agent is oil / water dual-purpose type DC-Q2-3238.

10. The modified silicone leather obtained by the method according to any one of claims 1 to 9.

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