Light-cured organic silicon polyurethane leather and preparation method thereof

Abstract

The invention discloses a preparation method of light-cured organic silicon polyurethane leather. Therefore, polyether polysiloxane containing C-OH in the structure and unsaturated carboxylic acid are firstly subjected to esterification reaction to synthesize oligomeric siloxane acrylate PSA of which the molecular end group is connected with 1-2 polyether acrylate groups and the main chain contains phenyl siloxane and other chain links; then, the PSA is combined with 2-6 functional (polyether) urethane acrylate, an acrylate reactive diluent, a moisture curing bottom adhesion component, namely amino silane ring-opening modified epoxy resin, color paste, a dispersing agent, a photoinitiator and the like to prepare UV light curing and moisture curing dual-curing slurry, and then UV light irradiation curing, surface spraying of a leather feeling agent and other treatments are performed. The light-cured organic silicon polyurethane leather can be obtained. The light-cured organic silicon polyurethane leather prepared by the preparation method disclosed by the invention is bright in leather surface, oily, comfortable, waterproof, dustproof and easy to clean and care, and the finished leather also has good mechanical strength.

Description

Technical Field

[0001] The present invention belongs to the field of light-cured organosilicon-modified polyurethane synthetic leather and functional materials, and specifically relates to a method for preparing organosilicon-modified polyurethane synthetic leather by using a combination of light-cured oligosiloxane acrylate containing polyether groups and phenylsiloxane chain segments in the structure, multifunctional polyurethane acrylate and moisture-curable aminosilane ring-opening modified epoxy resin. Background Art

[0002] Silicone leather is a type of synthetic leather made from silicone rubber. Silicone leather has the characteristics of weather resistance, aging resistance, flame retardancy, surface waterproof and anti-fouling, easy cleaning, safety and non-toxicity, so it is widely used in automotive interior leather, shoe leather, luggage leather, etc. [see CN115652651, CN 117779479, CN 115595800, CN 117702498, etc.], but silicone leather made purely from silicone rubber (especially silicone leather that has not been enhanced by fumed silica, etc.) has poor mechanical strength because the main chain polydimethylsiloxane has a small force between the chains and is hydrophobic, resulting in poor mechanical strength of silicone rubber. Polyurethane synthetic leather, as one of the leather substitutes that has been widely used, not only has a natural and soft leather surface gloss, a strong leather feel, and good adhesion to the substrate, but also has excellent mechanical properties such as wear resistance, flexibility, and flex resistance [see Gao Lijun, Li Ying, Zhou Liming, et al. Research Progress of UV Curable Polyurethane Modification [J]. Engineering Plastics Application. 2023, 51(7): 160-164]. Therefore, combining silicone with polyurethane is expected to combine the advantages of both and improve the shortcomings of silicone leather.

[0003] In addition, it can be seen from the literature search that photocurable resin coating has the characteristics of fast curing speed, green, clean and efficient. It has been one of the research and development hotspots in the field of materials in recent years, and has been widely used in rapid prototyping of functional materials and coatings, 3D printing, packaging and potting of electronic components (see Yu Bing, Huang Haiqing, Huang Shengjun, et al. Research progress on 3D printing of silicone materials and their applications. Silicone Materials, 2023, 37(6): 58-67). However, whether the photocurable resin coating method can be used to prepare silicone-modified polyurethane leather is rarely reported in the literature. Summary of the invention

[0004] In view of the fact that there are few reports on the production of silicone polyurethane leather by light curing in the domestic market, the present invention discloses a method for preparing silicone polyurethane leather by light curing and moisture curing (i.e. dual curing) method based on oligosiloxane acrylate, 2-6 functional (polyether / polyester polyurethane) acrylate, moisture curable tackifying component aminosilane ring-opening modified epoxy resin, coating additives, photoinitiator and other combination materials. To this end, the present invention adopts the following technical scheme:

[0005] A method for preparing a light-cured silicone polyurethane leather comprises two steps of preparing a leather making slurry and preparing the silicone polyurethane leather:

[0006] (1) Preparation of leather slurry: Weigh 10-35 parts by mass of oligosiloxane (polyether) acrylate, 35-80 parts of a mixture of difunctional polyurethane acrylate and multifunctional acrylate, 10-30 parts of acrylate reactive diluent, 10-30 parts of moisture-curable tackifying component - aminosilane ring-opening modified epoxy resin (ASME), 1-5 parts of oil-soluble color paste, 0.5-1 part of wetting dispersant, and 1-5 parts of free radical photoinitiator, stir and disperse to mix, and evacuate to degas to obtain leather slurry for later use.

[0007] (2) Preparation of photocurable silicone polyurethane leather: Fix the substrate base on the experimental table, and evenly apply the leather slurry on the surface of the substrate using a coating apparatus, a wire rod or a scraper. Control the amount of slurry applied so that the thickness of the coating after curing is controlled to be about 150-300 μm. First, level it at room temperature for 3-5 minutes and then cure it with UV light for 2-4 minutes. Then, spray the leather feel agent and bake it at 80-90°C for 30-60 minutes. The resulting sample is the photocurable silicone polyurethane leather.

[0008] The oligosiloxane (polyether) acrylate has a structure as shown in formula (1)-(2), which is a polyorganosiloxane having 1-2 (polyether) acrylate groups connected to one or both ends of the molecule. It can be used as a single component or as a mixture of two components of formula (1) and formula (2). In formula (1) and (2), n=4-40, a=0-3, b=0-10, a+b=0-10, M=H or CH 3 ;n 1 , n 2 =0-40, n 1 +n 2 =4-40, R, R', R", R"' = CH 3 or ph (i.e. phenyl C 6 H 5 ), R, R', R", R"' may be the same or different, a1 = 0-3, b1 = 0-10, a1 + b1 = 0-10, M' = H or CH 3 In addition, the main chain of the polyorganosiloxane described in formula (1) is a polymethylphenylsiloxane with a trimethylsilyl group blocking one end; and the main chain of the polyorganosiloxane described in formula (2) is a polysiloxane skeleton with silylphenyl (Si-ph), silylmethyl (Si-CH 3 ) or Si-ph and Si-CH 3The siloxane copolymer preferably has a main chain of one of polydimethylsiloxane, polydiphenylsiloxane, polymethylphenylsiloxane or poly(dimethylsiloxane-co-diphenylsiloxane), poly(dimethylsiloxane-co-methylphenylsiloxane) and other copolymer segments.

[0009]

[0010] When the oligosiloxane (polyether) acrylate is used to prepare a leather slurry composition with two components of formula (1) and formula (2), the amount of the polyorganosiloxane (denoted as PSMA) having one (polyether) acrylate group connected to one end of the molecule as shown in formula (1) is generally about 0-15 parts, and the amount of the polyorganosiloxane (denoted as PSDA) having two (polyether) acrylate groups connected to both ends of the molecule as shown in formula (2) is about 10-35 parts, and the total mass of PSMA and PSDA is about 10-35 parts.

[0011] The oligosiloxane (polyether) acrylates represented by formulas (1)-(2) can be prepared by esterification reaction of a polyorganosiloxane (denoted as PS-OH) having a C-OH group at one end of the molecule represented by formula (3) or a polyorganosiloxane (HO-PS-OH) having a C-OH group at both ends of the molecule represented by formula (4) with an unsaturated carboxylic acid (VC), wherein n and n in formulas (3) and (4) are 1 、n 2 The definitions and value ranges of R, R', R", R'", a, b, a1, and b1 are the same as those in formula (1) and formula (2).

[0012]

[0013] The (polyether) polyorganosiloxane containing C-OH at one end of the molecule [PS-OH, see formula (3)] is selected from one of a=0, b=0, n=4-40 molecule with a hydroxypropyl at one end of the molecule, a=1, b=0, n=4-40 molecule with a hydroxyethyloxypropyl at one end of the molecule, a=0-3, b=0-10, a+b=0-10, n=4-40 molecule with a hydroxyl-terminated polyoxyethylene polyoxypropylene propyl at one end of the molecule; generally, a polymethylphenylsiloxane (CH4-40 molecule with one end of the molecule terminated with dimethylhydrogensilane and the other end terminated with trimethylsilyl can be used. 3 ) 3 SiO[(CH 3 )SiPhO] n Si(CH 3 ) 2H was prepared by hydrosilylation addition reaction with allyl alcohol, hydroxyethyl allyl ether, or hydroxyl-terminated polyoxyethylene polyoxypropylene allyl ether with a=0-3, b=0-10, a+b=0-10 in the presence of platinum catalyst, and was ordered from Anhui Aiyota Silicone Oil Co., Ltd., Zhejiang Runhe New Materials Co., Ltd. and other companies or commissioned by the fluorosilicone team of Shaanxi University of Science and Technology to synthesize it.

[0014] The (polyether) polysiloxane containing C-OH at both ends of the molecule [HO-PS-OH, see formula (4)], selected from n 1 , n 2 =0-40, n 1 +n 2 =4-40, R, R', R", R"' = CH 3 or ph and a1 = 0, b1 = 0 α, ω-bis (hydroxypropyl) block polysiloxane, or a1 = 1, b1 = 0 α, ω-bis (hydroxyethyloxypropyl) block polysiloxane, or a1 = 0-3, b1 = 0-10, a1 + b1 = 0-10 α, ω-bis (hydroxy-terminated polyoxyethylene polyoxypropylene propyl) block polysiloxane, can be used n 1 , n 2 =0-40, n 1 +n 2 =4-40, R, R', R", R"' = CH 3 or pH and the double-end hydrogen-containing polyorganosiloxane is terminated with dimethyl hydrogen silicon H(CH 3 ) 2 SiO[RR'SiO] n1 [R”R”'SiO] n2 Si(CH 3 ) 2 H is prepared by a hydrosilylation addition reaction with allyl alcohol, or hydroxyethyl allyl ether, or hydroxyl-terminated polyoxyethylene polyoxypropylene allyl ether with a1=0-3, b1=0-10, a1+b1=0-10 in the presence of a platinum catalyst. It is also processed and ordered from Anhui Aiyota Silicone Oil Co., Ltd., Zhejiang Runhe New Materials Co., Ltd. and other units or commissioned to the fluorosilicone team of Shaanxi University of Science and Technology for synthesis; the formula (4) molecule contains C-OH (polyether group) polyorganosiloxane at both ends, and the definitions and values ​​of the main chain polyorganosiloxane and the polyether group are the same as those of formula (2).

[0015] The unsaturated carboxylic acid (VC) is one of acrylic acid, methacrylic acid or 2-butenoic acid.

[0016] The esterification reaction of the (polyether-based) polyorganosiloxane (OSOH) containing C-OH at one or both ends of the molecule and the unsaturated carboxylic acid (VC), the molar ratio of OSOH to VC is controlled to be about 1:5-10, the esterification reaction catalyst is aluminum acetylacetonate, the inhibitor is hydroquinone, the esterification reaction temperature is 80-110°C, and the esterification reaction time is 4-10h; the specific preparation steps of the esterification reaction are as follows:

[0017] That is, the molar ratio of (polyether) polysiloxane (OSOH) containing C-OH at one or both ends of the molecule to unsaturated carboxylic acid (VC) is about 1:5-10, OSOH and VC are weighed respectively, and then 0.3%-0.6% of hydroquinone inhibitor, 0.1%-0.2% of aluminum acetylacetonate catalyst and 50%-100% of organic solvent are added based on the total mass of OSOH and VC, stirred and mixed, heated to 90-110° C., refluxed and water extracted reaction was carried out for 4-10 hours, the reaction was completed, the solvent was recovered by atmospheric distillation, and then heated to a pressure of P 表 = 0.085-0.09MPa under reduced pressure to evaporate the residual VC, and then the product was successively treated with a mass concentration of about 2% Na 2 CO 3 The aqueous solution and deionized water are washed 2-3 times respectively to remove the residual catalyst and inhibitor, and then dried and filtered to obtain a colorless transparent liquid, namely, the oligosiloxane (polyether) acrylate having a structure as shown in formula (1)-(2).

[0018] In the above preparation steps, the organic solvent is one of cycloalkanes such as cyclohexane, methylcyclohexane, or aromatic hydrocarbons such as benzene, toluene, etc.

[0019] The difunctional polyurethane acrylate has an average molecular weight (Mn) of about 2000-20000, and is a polyether polyurethane diacrylate or polyester polyurethane diacrylate having two reactive acrylate functional groups in its molecular structure obtained by chemical reaction of polyether diol or polyester diol having Mn=1000-2000 with diisocyanate and hydroxyalkyl acrylate. It is ordered from Zhongshan Qianyou Chemical Material Co., Ltd., Jiangxi Kunlong New Materials Co., Ltd., and Sikechuang Co., Ltd. or is processed and synthesized by entrusted manufacturers. Polytetramethylene glycol ether polyurethane diacrylate, polypropylene glycol ether polyurethane diacrylate or commonly known difunctional polyurethane acrylate such as US035-6F (Zhongshan Qianyou Chemical Material Co., Ltd.) obtained by reaction of polytetramethylene glycol or polypropylene glycol with diisocyanate (such as IPDI, HDI, HMDI, etc.), hydroxyethyl acrylate, etc. are preferably selected.

[0020] The multifunctional acrylate is a small molecule ester compound or a polyurethane acrylate prepolymer containing 3-6 acrylate functional groups in its structure, and is selected from one of pentaerythritol triacrylate, pentaerythritol tetraacrylate, polydipentaerythritol hexaacrylate, glycerol triacrylate, trimethylolpropane triacrylate, polyurethane acrylate with a functionality of 4-6 (such as tetrafunctional polyurethane acrylate HM6620, Jiangxi Kunlong New Materials Co., Ltd.), etc.

[0021] In the mixture of difunctional polyurethane acrylate and multifunctional acrylate, the amount of difunctional polyurethane acrylate is generally about 30-75 parts, the amount of multifunctional acrylate is about 5-30 parts, and the total weight of the two is about 35-80 parts.

[0022] The acrylate reactive diluent is generally a small molecule compound containing 1-2 acrylate groups in the structure and a viscosity of <200mPa.s or a diol oligomer containing acrylate groups. 1-12 The invention comprises one or a mixture of two to three of alkyl esters, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate with an average molecular weight (Mn) of 200-600, and polyethylene glycol di(meth)acrylate with an Mn of 200-400.

[0023] The oil-soluble color paste is a dispersion formed by an oil-soluble dye or pigment being dispersed in a resin or solvent under the action of a coating additive, and is selected from the black color paste Colanyl Black N131-CN 0030 produced by Clariant Chemicals (China) Co., Ltd., the leather color paste such as FRGF-8920 red, F-5629 fluorescent yellow, F-fluorescent sky blue color paste produced by Guangzhou Moke Chemical Co., Ltd., or the solvent-based resin universal color paste produced by Henan Wangong Environmental Protection Materials Co., Ltd., such as DF616 Permanent Red F5, DF618 Permanent Red F2, DF816 Standard Medium Yellow, etc.

[0024] The moisture-curable tackifying component aminosilane ring-opening modified epoxy resin is a substance that can increase the adhesion between the coating and the substrate and has 2-3 siloxy groups at the end group. The product is selected from the reaction of epoxy resin and aminosilane at a molar ratio of 1:2-2.2 at 60-70°C for 30-60 minutes; the epoxy resin is selected from one of bisphenol A type epoxy resins E51, E44, etc.; the aminosilane is selected from one of 3-aminopropyltrimethoxysilane (KH-540), 3-aminopropyltriethoxysilane (KH-550), 3-aminopropylmethyldimethoxysilane (KH-554), and 3-aminopropylmethyldiethoxysilane.

[0025] The photoinitiator is a compound that can absorb ultraviolet light of 200-400nm, generate free radicals and initiate polymerization of unsaturated monomers, and is selected from one or a mixture of two to three of 2-hydroxy-2-methyl-1-phenylpropane-1-one (1173), 1-hydroxycyclohexyl phenyl ketone (184), 2,4,6-(trimethylbenzoyl)diphenylphosphine oxide (TPO), 2-methyl-1-(4-methylthiophenyl)-2-morpholinyl-1-propanone (907), benzoin dimethyl ether (651), etc.; preferably, a composite photoinitiator formed by a composite of 1173 and TPO or 1173 and 184 (mass ratio is about 1:0.5-2) is selected.

[0026] The wetting and dispersing agent is selected from one of the oil-soluble wetting and dispersing agents BYK-ATU, BYK-110, BYK-163, etc. produced by German BYK Company.

[0027] The substrate is a fluorine release paper, a microfiber cloth or a non-woven fabric made of polyester and spandex, etc. The leather feel agent is an oil-water dual-purpose DC-Q2-3238 feel agent produced by Dow Corning, USA, which is generally diluted to a mass concentration of about 0.5%-1% for use.

[0028] The beneficial effects of the present invention are embodied in that: the present invention introduces polyether and phenylsiloxane chain segments having good miscibility with organic resins into the polyorganosiloxane structure through molecular design, effectively improving and solving the problems of immiscibility, phase separation, turbidity, etc. that are easily generated when traditional polyorganosiloxanes such as polydimethylsiloxanes encounter aliphatic acrylates, polyurethane acrylates, etc. due to large differences in polymer solubility parameters, thereby enabling the oligosiloxane acrylates (i.e., polyorganosiloxanes containing polyether acrylate groups at one or both ends of the molecule) prepared based on the present invention to achieve homogeneity and miscibility with photocurable monomers such as aliphatic acrylates, polyurethane acrylates, etc., and further enable room temperature photocuring. Secondly, the present invention combines a low-polysiloxane (polyether) acrylate containing polyether and silicon phenyl in the structure with a difunctional polyurethane acrylate and a multifunctional acrylate mixture, an acrylate reactive diluent, a moisture-curable primer component aminosilane ring-opening modified epoxy resin, a photoinitiator, etc. to prepare a light-cured + moisture-cured, i.e., dual-cured silicone polyurethane slurry. Since the components in the system have similar and compatible structures, the slurry can not only be effectively photocured to form silicone polyurethane leather after UV irradiation, but also the surface of the finished leather can also show the bright and moist hand feel, good waterproof and antifouling, aging resistance and mechanical strength unique to phenyl silicone rubber due to the surface enrichment of low surface energy polysiloxane segments after equilibrium at room temperature. DETAILED DESCRIPTION

[0029] The present invention will be further described below in conjunction with the embodiments.

[0030] Example 1

[0031] 1) Synthesis of oligosiloxane polyether acrylate diester——α,ω-bis(acrylate polyoxypropylene propyl) polymethylphenylsiloxane (PSDA-1)

[0032] In a three-necked flask equipped with a thermometer, a reflux condenser and an electric stirrer, 0.01 mol (about 63.70 g) of the structure shown in formula (4) were weighed at a molar ratio of about 1:10 between (polyether) polyorganosiloxane (HO-PS-OH) containing C-OH at both ends of the molecule and unsaturated carboxylic acid (VC). 1 =0, n 2 =40, R" = CH 3 α,ω-bis(hydroxy-terminated polyoxypropylene propyl) polymethylphenylsiloxane HO(C 3 H 6 O) 6 C 3 H 6 Si(CH 3 ) 2 [OSi(CH 3 )ph] 40 OSi(CH3 ) 2 C 3 H 6 (OC 3 H 6 ) 6 OH (HO-PS-OH-1, Zhejiang Runhe New Materials Co., Ltd., the same below), 0.1 mol (about 7.21 g) of acrylic acid (AA), and then add 0.3% (about 0.21 g) of hydroquinone inhibitor based on the total mass of HO-PS-OH-1 and AA, 0.1% (about 0.07 g) of aluminum acetylacetonate catalyst, and 100% (about 70.91 g) of cyclohexane solvent, stirred and mixed, heated to 90°C for reflux and water extraction reaction for 6 hours, the reaction was completed, the cyclohexane solvent was recovered by atmospheric distillation, and then at a pressure of P 表 =0.085MPa under reduced pressure to evaporate the residual AA, and then the product was successively treated with about 2% Na 2 CO 3 The solution was washed with deionized water for three times to remove the residual catalyst and inhibitor, and then 7.10 g of anhydrous magnesium sulfate was added to dry for 2 h, and filtered to obtain a colorless transparent liquid, which has the structure shown in formula (2). 1 =0, n 2 =40, R" = CH 3 , R"'=ph, a1=0, b1=6, M'=H oligosiloxane polyether acrylate diester - α, ω-bis(acrylate polyoxypropylene propyl) polymethylphenylsiloxane, denoted as PSDA-1.

[0033] 2) Synthesis of oligosiloxane polyether acrylate (PSMA-1)

[0034] In a three-necked flask equipped with a thermometer, a reflux condenser and an electric stirrer, 0.01 mol (44.60 g) of a single-ended (hydroxy-terminated polyoxypropylene propyl) polymethylphenylsiloxane (CH) having a structure shown in formula (3) with n=30, a=0 and b=3 were weighed at a molar ratio of about 1:10 between (polyether) polyorganosiloxane (PS-OH) containing C-OH at one end of the molecule and unsaturated carboxylic acid (VC). 3 ) 3 Si[OSi(CH 3 )ph] 30 OSi(CH 3 ) 2 C 3 H 6 (OC 3 H 6 ) 3OH (PS-OH-1, Anhui Aiyota Silicone Oil Co., Ltd., the same below), 0.1 mol (about 7.21 g) of acrylic acid (AA), and then add 0.3% (about 0.16 g) of hydroquinone inhibitor based on the total mass of PS-OH-1 and AA, 0.1% (about 0.05 g) of aluminum acetylacetonate catalyst, and 100% (about 51.81 g) of cyclohexane solvent, stirred and mixed, heated to 95°C for reflux and water extraction reaction for 4 hours, the reaction was completed, the cyclohexane solvent was recovered by atmospheric distillation, and then at a pressure of P 表 =0.085MPa under reduced pressure to evaporate the residual AA, and then the product was successively treated with a mass concentration of about 2% Na 2 CO 3 The mixture was washed with water and deionized water for three times to remove the residual catalyst and inhibitor, and then 5.20 g of anhydrous magnesium sulfate was added to dry for 2 hours. After filtering, a colorless transparent liquid was obtained, i.e., a low molecular weight siloxane polyether acrylate monoester having a structure as shown in formula (1) with n=30, a=0, b=3, and M'=H, namely, single-end acrylate-based polyoxypropylene propyl polymethylphenylsiloxane, denoted as PSMA-1.

[0035] 3) Preparation of moisture-curable adhesion-enhancing component aminosilane ring-opening epoxy resin (ASME-1)

[0036] Take 0.2 mol (about 44.27 g) of 3-aminopropyltriethoxysilane (KH-550) and 0.1 mol (about 45.45 g) of epoxy resin E44, stir and mix, heat to 60°C and stir to react for 1 hour to obtain a transparent liquid, which is the epoxy resin E44 modified by the moisture-curing viscosity-enhancing component aminosilane KH-550, recorded as ASME-1.

[0037] (2) Preparation of leather slurry (SPU-1)

[0038] According to mass parts, 30.0g α, ω-bis(acrylate-based polyoxypropylene propyl) polymethylphenylsiloxane PSDA-1, 5.0g single-end acrylate-based polyoxypropylene propyl polymethylphenylsiloxane PSMA-1, 25.0g polytetrahydrofuran ether polyurethane diacrylate with an average molecular weight of about 2500 (Zhongshan Qianyou Chemical Materials Co., Ltd., the same below), 30.0g tetrafunctional polyurethane acrylate HM6620 (Jiangxi Kunlong New Materials Co., Ltd., the same below), 10.0g isobornyl acrylate active diluent, 10.0g moisture-curable bottom adhesive component ASME-1, 1.0g Clariant oil-soluble black color paste Colanyl BlackN131-CN0030, 0.5g BYK-ATU dispersant and 5.0g free radical photoinitiator 1173 were stirred and dispersed for 30min using a dispersing disk at a speed of 1000r / min, and vacuum degassing was performed to obtain a leather slurry with a viscosity of about 5000mPa.s, which was recorded as SPU-1 and set aside.

[0039] (3) Preparation of silicone polyurethane leather (SPUL-1)

[0040] Take a polyester microfiber base cloth (Changshu Jinda Nonwoven Products Co., Ltd.) and lay it flat and fixed on the test bench. Use RDS-70 wire rod to evenly apply slurry SPU-1 on the surface of the base cloth. Control the amount of slurry so that the coating thickness formed after the SPU-1 slurry is cured is about 180μm. First, level it at room temperature for 5 minutes, then use a UV curing machine with a power of 1000W to cure it for 2 minutes, and then spray it with a leather feel agent DC-Q2-3238-ethanol solution with a mass concentration of about 0.5%, and bake it at 80℃ for 30 minutes. The resulting leather sample is light-cured silicone polyurethane leather, recorded as SPUL-1.

[0041] Example 2

[0042] 1) Synthesis of oligosiloxane polyether acrylate (PSDA-2)——α,ω-bis(methacrylate polyoxypropylene propyl)poly(dimethylsiloxane-co-diphenylsiloxane)

[0043] In a three-necked flask equipped with a thermometer, a reflux condenser and an electric stirrer, 0.01 mol (about 60.38 g) of the structure shown in formula (4) were weighed at a molar ratio of about 1:10 between polyether polyorganosiloxane (HO-PS-OH-2) containing C-OH at both ends of the molecule and unsaturated carboxylic acid (VC). 1 =20, n 2 =20, R = R' = CH 3 α,ω-bis(hydroxy-terminated polyoxypropylene propyl)poly(dimethylsiloxane-co-diphenylsiloxane) [HO(C 3 H 6 O) 3 C 3 H 6 Si(CH 3 ) 2 [OSi(CH 3 ) 2 ] 20 [OSi(Ph) 2 ] 20 OSi(CH 3 ) 2 C 3 H 6 (OC 3 H 6 ) 3OH], 0.1 mol (about 8.21 g) of methacrylic acid (MAA), and then add 0.5% (about 0.34 g) of hydroquinone inhibitor based on the total mass of HO-PS-OH-2 and MAA, 0.2% (about 0.14 g) of aluminum acetylacetonate catalyst, and 80% (about 54.87 g) of cyclohexane solvent, stirred and mixed, heated to 95°C for reflux and water extraction reaction for 4 hours, the reaction was completed, the cyclohexane solvent was recovered by atmospheric distillation, and then at a pressure of P 表 =0.09MPa under reduced pressure to evaporate the residual MAA, and then the product was successively treated with a mass concentration of about 2% Na 2 CO 3 The solution was washed with deionized water for three times to remove the residual catalyst and inhibitor, and then 6.90 g of anhydrous magnesium sulfate was added to dry for 2 h, and filtered to obtain a colorless transparent liquid, which has the structure shown in formula (2). 1 =20, n 2 =20, R = R' = CH 3 , R”=R”'=ph, a1=0, b1=3, M'=CH 3 α,ω-bis(methacrylate polyoxypropylene propyl)poly(dimethylsiloxane-co-diphenylsiloxane) is denoted as PSDA-2.

[0044] 2) Synthesis of oligosiloxane polyether acrylate (PSMA-2)

[0045] The synthesis method and the amount of raw materials used were the same as those in Example 1, except that the single-terminal (hydroxyl-terminated polyoxypropylene propyl) polymethylphenylsiloxane PS-OH-2[(CH 3 ) 3 Si[OSi(CH 3 )ph] 30 OSi(CH 3 ) 2 C 3 H 6 (OC 3 H 6 ) 5 OH] was substituted for the raw material PS-OH-1 of Example 1 to carry out the reaction. The obtained product, i.e., the single-terminal (acrylate-based polyoxypropylene propyl) polymethylphenylsiloxane synthesized in Example 2, having a structure shown in formula (1) with n=30, a=0, b=5, and M=H, was denoted as PSMA-2.

[0046] 3) Preparation of moisture-curable tackifier (ASME-2): The preparation method and dosage were the same as those in Example 1, except that KH-550 was replaced with 3-aminopropylmethyldimethoxysilane in equal moles. The resulting product, 3-aminopropylmethyldimethoxysilane ring-opening modified epoxy resin E44, was the moisture-curable primer component ASME-2 obtained in Example 2.

[0047] (2) Preparation of leather slurry (SPU-2)

[0048] According to mass parts, weigh 25.0g α, ω-bis(methacrylate polyoxypropylene propyl) poly(dimethylsiloxane-co-diphenylsiloxane) PSDA-2, 10.0g single-end (acrylate polyoxypropylene propyl) polymethylphenylsiloxane PSMA-2, 25.0g polytetrahydrofuran ether polyurethane diacrylate with an average molecular weight of about 2500, 30.0g pentaerythritol triacrylate, 10.0g isobornyl acrylate active diluent, 30.0g moisture-curable primer component ASME-2, 2.0g DF616 permanent red F5, 1.0g BYK-163 dispersant and 5.0 g of a free radical photoinitiator composed of 1173 / 184 (1:1, wt / wt) were stirred and dispersed for 30 minutes using a dispersing disk at a speed of 1000 r / min, and vacuum degassing was performed to obtain a leather slurry with a consistency of about 10000 mPa.s, which was recorded as SPU-2 and set aside.

[0049] (3) Preparation of silicone polyurethane leather SPUL-2

[0050] Take a spandex microfiber base cloth (Changshu Jinda Nonwoven Products Co., Ltd.) and lay it flat and fixed it on the test bench. Use RDS-70 wire rod to evenly apply SPU-2 slurry on the surface of the base cloth. Control the amount of slurry so that the coating thickness formed after the SPU-2 slurry is cured is about 220μm. First, level it at room temperature for 5 minutes, then use a UV curing machine with a power of 1000W to cure it for 4 minutes, and then spray it with a leather feel agent DC-Q2-3238-ethanol solution with a mass concentration of about 0.5%, and bake it at 90℃ for 30 minutes. The resulting leather sample is light-cured silicone polyurethane leather, recorded as SPUL-2.

[0051] Example 3

[0052] 1) Synthesis of oligosiloxane polyether acrylate (PSDA-3)——α,ω-bis(methacrylate polyoxypropylene propyl)poly(dimethylsiloxane-co-methylphenylsiloxane)

[0053] In a three-necked flask equipped with a thermometer, a reflux condenser and an electric stirrer, 0.01 mol (about 29.04 g) of the structure shown in formula (4) were weighed at a molar ratio of about 1:5 between polyether polyorganosiloxane (HO-PS-OH-3) containing C-OH at both ends of the molecule and unsaturated carboxylic acid (VC). 1 =10, n 2 =10, R = R' = R" = CH 3α,ω-bis(hydroxy-terminated polyoxyethylene polyoxypropylene propyl)poly(dimethylsiloxane-co-methylphenylsiloxane) [HO(C 2 H 4 O) 3 (C 3 H 6 O) 7 C 3 H 6 Si(CH 3 ) 2 [OSi(CH 3 ) 2 ] 10 [OSi(CH 3 )Ph] 10 OSi(CH 3 ) 2 C 3 H 6 (OC 3 H 6 ) 7 (OC 2 H 4 ) 3 OH], 0.05 mol (about 4.10 g) of methacrylic acid (MAA), and then add 0.6% (about 0.20 g) of hydroquinone inhibitor based on the total mass of HO-PS-OH-3 and MAA, 0.2% (about 0.066 g) of acetylacetonate aluminum catalyst, and 100% (33.14 g) of methylcyclohexane solvent, stirred and mixed, heated to 110°C for reflux and water extraction reaction for 4.5 hours, the reaction was completed, the methylcyclohexane solvent was recovered by atmospheric distillation, and then at a pressure of P 表 =0.09MPa under reduced pressure to evaporate the residual MAA, and then the product was successively treated with a mass concentration of about 2% Na 2 CO 3 The solution was washed with water and saturated brine three times to remove the residual catalyst and inhibitor, and then 4.30 g of anhydrous magnesium sulfate was added to dry for 2 h, and filtered to obtain a colorless transparent liquid, which has the structure shown in formula (2). 1 =10, n 2 =10, R = R' = R" = CH 3 , R"'=ph, a1=3, b1=7, M'=CH 3 α,ω-bis(methacrylate polyoxyethylene polyoxypropylene propyl) poly(dimethylsiloxane-co-methylphenylsiloxane), denoted as PSDA-3.

[0054] 2) Synthesis of oligosiloxane polyether acrylate (PSMA-3)

[0055] The synthesis method and the amount of raw materials used were the same as those in Example 1, except that single-terminated (hydroxyethyloxypropyl) polymethylphenylsiloxane PS-OH-3[(CH 3 ) 3 Si[OSi(CH 3 )ph] 20 OSi(CH 3 ) 2 C 3 H 6 OC 2 H 4 OH] is substituted for PS-OH-1 in Example 1 to react to obtain a single-terminal (acrylate ethoxypropyl) polymethylphenylsiloxane having a structure as shown in formula (1) with n=20, a=1, b=0, and M=H, which is used as the oligosiloxane polyether acrylate monoester in Example 3 and is recorded as PSMA-3.

[0056] 3) Preparation of moisture-curable tackifier (ASME-3): The preparation method and dosage were the same as those in Example 1, except that KH-550 was replaced with 3-aminopropylmethyldiethoxysilane in equal moles. The resulting product, 3-aminopropylmethyldiethoxysilane ring-opening modified epoxy resin E44, was the moisture-curable tackifier ASME-3 prepared in Example 3.

[0057] (2) Preparation of leather slurry SPU-3

[0058] According to mass parts, weigh 20.0g α, ω-bis(methacrylate polyoxyethylene polyoxypropylene propyl) block poly(dimethylsiloxane-co-methylphenylsiloxane) PSDA-3, 15.0g single-end (acrylate ethoxypropyl) polymethylphenylsiloxane PSMA-3, 25.0g polypropylene glycol ether polyurethane diacrylate with an average molecular weight of about 1600, 20.0g trimethylolpropane triacrylate, 20.0g cyclohexyl methacrylate active diluent, 15.0g moisture-curable primer component ASME-3, 1.0g Clariant oil-soluble black color paste Colanyl Black N131-CN0030, 0.5g BYK-ATU dispersant and 3.0 g of free radical photoinitiator composed of 1173 / 184 (1:1, wt / wt) were stirred and dispersed for 30 minutes using a dispersing disk at a speed of 1000 r / min, and vacuum degassing was performed to obtain a leather slurry with a consistency of about 6000 mPa.s, which was recorded as SPU-3 and set aside.

[0059] (3) Preparation of silicone polyurethane leather SPUL-3

[0060] Take a polyester microfiber base cloth (Changshu Jinda Nonwoven Products Co., Ltd.) and lay it flat and fixed on the test bench. Use RDS-70 wire rod to evenly apply SPU-3 slurry on the surface of the base cloth. Control the amount of slurry so that the coating thickness formed after the SPU-3 slurry is cured is about 202μm. First, level it at room temperature for 5min, then use a UV curing machine with a power of 1000W to cure it for 4min, and then spray it with a leather feel agent DC-Q2-3238-ethanol solution with a mass concentration of about 0.5%, and bake it at 90℃ for 30min. The resulting leather sample is light-cured silicone polyurethane leather, recorded as SPUL-3.

[0061] Example 4

[0062] 1) Synthesis of oligosiloxane polyether acrylate diester (PSDA-4)——α,ω-bis(acrylate ethoxypropyl) polydiphenylsiloxane

[0063] In a dry three-necked flask equipped with a thermometer, a reflux condenser and an electric stirrer, 0.01 mol (about 72.68 g) of the structure shown in formula (4) were weighed at a molar ratio of about 1:10 between polyether polyorganosiloxane (HO-PS-OH-4) containing C-OH at both ends of the molecule and unsaturated carboxylic acid (VC). 1 =0, n 2 =35, R" = R"' = ph, a1 = 1, b1 = 0 α, ω-bis (hydroxyethyloxypropyl) polydiphenylsiloxane [HOC 2 H 4 OC 3 H 6 Si(CH 3 ) 2 [OSi(Ph) 2 ] 35 OSi(CH 3 ) 2 C 3 H 6 OC 2 H 4 OH], 0.1 mol (about 7.21 g) of acrylic acid (AA), and then add 0.5% (0.4 g) of hydroquinone inhibitor based on the total mass of HO-PS-OH-4 and AA, 0.2% (0.16 g) of aluminum acetylacetonate catalyst, and 50% (40.0 g) of cyclohexane solvent, stirred and mixed, heated to 90°C for reflux and water extraction reaction for 6 hours, the reaction was completed, the cyclohexane solvent was recovered by atmospheric distillation, and then at a pressure of P 表 =0.09MPa under reduced pressure to evaporate the residual AA, and then the product was successively treated with a mass concentration of about 2% Na 2 CO 3The solution was washed with deionized water for three times to remove the residual catalyst and inhibitor, and then 8.0 g of anhydrous magnesium sulfate was added to dry for 2 h, and filtered to obtain a colorless transparent liquid, which has the structure shown in formula (2). 1 =0, n 2 =35, R"=R"'=ph, a1=1, b1=0, M'=H α,ω-bis(acrylate ethoxypropyl)polydiphenylsiloxane is denoted as PSDA-4.

[0064] 2) Synthesis of oligosiloxane polyether acrylate (PSMA-4)

[0065] The synthesis method and the amount of raw materials used were the same as those in Example 1, except that a=3, b=7, and n=40 were used for the single-terminal (hydroxyl-terminated polyoxyethylene polyoxypropylene propyl) polymethylphenylsiloxane PS-OH-4[(CH 3 ) 3 Si[OSi(CH 3 )ph] 40 OSi(CH 3 ) 2 C 3 H 6 (OC 3 H 6 ) 7 (OC 2 H 4 ) 3 OH] was used to replace the raw material PS-OH-1 in Example 1 to react to obtain a single-terminal (acrylate-based polyoxyethylene polyoxypropylene propyl) polymethylphenylsiloxane with a structure as shown in formula (1) with n=40, a=3, b=7, and M=H, which was recorded as PSMA-4.

[0066] 3) Preparation of moisture-curable tackifier ASME-4: The preparation method and dosage are the same as those in Example 1, except that KH-550 is replaced with 3-aminopropyltrimethoxysilane in equal moles. The resulting product, 3-aminopropyltrimethoxysilane ring-opening modified epoxy resin E44, is the moisture-curable base adhesive component ASME-4 prepared in Example 4.

[0067] (2) Preparation of leather slurry SPU-4

[0068] According to mass parts, 25.0g α, ω-bis (acrylate ethoxypropyl) polydiphenylsiloxane PSDA-4, 10.0g single-end (acrylate polyoxyethylene polyoxypropylene propyl) polymethylphenylsiloxane PSMA-4, 32.0g polytetrahydrofuran ether polyurethane diacrylate with an average molecular weight of about 2500, 18.0g tetrafunctional polyurethane acrylate HM6620 (Jiangxi Kunlong New Materials Co., Ltd.), 15.0g methacrylate isobornyl active diluent, 30.0g moisture-curable bottom adhesive component ASME-4, 5.0g F-5629 fluorescent yellow (Guangzhou Moke Chemical Co., Ltd.), 1.0g BYK-110 dispersant and 4.0 g of a free radical photoinitiator composed of 1173 / 184 (1:1, wt / wt) were stirred and dispersed for 30 minutes using a dispersing disk at a speed of 1000 r / min, and vacuum degassing was performed to obtain a leather slurry with a consistency of about 10000 mPa.s, which was recorded as SPU-4 and set aside.

[0069] (3) Preparation of silicone polyurethane leather SPUL-4

[0070] Take a polyester microfiber base cloth (Changshu Jinda Nonwoven Products Co., Ltd.) and lay it flat and fixed on the test bench. Use RDS-70 wire rod to evenly apply SPU-4 slurry on the surface of the base cloth. Control the amount of slurry so that the average thickness of the coating formed after the SPU-4 slurry is cured is about 220μm. First, level it at room temperature for 5 minutes, then use a UV curing machine with a power of 1000W to cure it for 4 minutes, and then spray it with a leather feel agent DC-Q2-3238-ethanol solution with a mass concentration of about 0.5%, and bake it at 90℃ for 30min. The resulting leather sample is light-cured silicone polyurethane leather, recorded as SPUL-4.

[0071] Example 5

[0072] 1) Synthesis of oligosiloxane polyether acrylate diester (PSDA-5)——α,ω-bis(acrylate polyoxypropylene propyl) polymethylphenylsiloxane

[0073] In a dry three-necked flask equipped with a thermometer, a reflux condenser and an electric stirrer, 0.02 mol (39.16 g) of the structure shown in formula (4) were weighed in a molar ratio of about 1:6 between polyether polyorganosiloxane (HO-PS-OH-5) containing C-OH at both ends of the molecule and unsaturated carboxylic acid (VC). 1 =0, n 2 =10, R" = CH 3 α,ω-bis(hydroxy-terminated polyoxypropylene propyl)polymethylphenylsiloxane [HO(C 3 H 6 O) 3 C3 H 6 Si(CH 3 ) 2 [OSi(CH 3 )Ph] 10 OSi(CH 3 ) 2 C 3 H 6 (OC 3 H 6 ) 3 OH], 0.12 mol (about 8.71 g) of acrylic acid (AA), and then add 0.5% (about 0.24 g) of hydroquinone inhibitor based on the total mass of HO-PS-OH-5 and AA, 0.1% (about 0.05 g) of aluminum acetylacetonate catalyst, and 100% (about 47.87 g) of cyclohexane solvent, stirred and mixed, heated to 95°C for reflux and water extraction reaction for 4 hours, the reaction was completed, the cyclohexane solvent was recovered by atmospheric distillation, and then at a pressure of P 表 =0.09MPa under reduced pressure to evaporate the residual AA, and then the product was successively treated with a mass concentration of about 2% Na 2 CO 3 The solution was washed with water and deionized water for three times to remove the residual catalyst and inhibitor, and then 4.79 g of anhydrous magnesium sulfate was added to dry for 2 h, and filtered to obtain a colorless transparent liquid, which has the structure shown in formula (2). 1 =0, n 2 =10, R" = CH 3 α,ω-bis(acrylate polyoxypropylene propyl) polymethylphenylsiloxane wherein R''=ph, a1=0, b1=3, and M'=H is referred to as PSDA-5.

[0074] 2) Preparation of moisture curable tackifier: same as ASME-2 in Example 2.

[0075] (2) Preparation of leather slurry SPU-5

[0076] 30.0 g of α, ω-bis(acrylate-based polyoxypropylene propyl) polymethylphenylsiloxane PSDA-5, 32.0 g of polytetramethylene ether polyurethane diacrylate with an average molecular weight of about 2500, 10.0 g of tetrafunctional polyurethane acrylate HM6620 (Jiangxi Kunlong New Materials Co., Ltd.), 28.0 g of polypropylene glycol diacrylate reactive diluent with an average molecular weight of about 200, 30.0 g of moisture-curable base adhesive component ASME-2, 3.0 g of Clariant oil-soluble black color paste Colanyl Black N131-CN0030, 0.6 g of BYK-ATU dispersant, and 2.8 g of a free radical photoinitiator composed of 1173 / TPO (2:1, wt / wt) were weighed by mass, and the mixture was dispersed with a dispersion disk at a speed of 1000 r / min for 30 min. The mixture was vacuumed and degassed to obtain a leather slurry with a consistency of about 7500 mPa.s, which was recorded as SPU-5 and set aside.

[0077] (3) Preparation of silicone polyurethane leather (SPUL-5)

[0078] Take a spandex microfiber base cloth (Changshu Jinda Nonwoven Products Co., Ltd.) and lay it flat and fixed it on the test bench. Use RDS-70 wire rod to evenly apply SPU-5 slurry on the surface of the base cloth. Control the amount of slurry so that the coating thickness formed after the SPU-5 slurry is cured is about 206μm. First, level it at room temperature for 5 minutes, then use a UV curing machine with a power of 1000W to cure it for 4 minutes, and then spray it with a leather feel agent DC-Q2-3238-ethanol solution with a mass concentration of about 0.5%, and bake it at 80℃ for 30 minutes. The resulting leather sample is light-cured silicone polyurethane leather, recorded as SPUL-5.

[0079] Example 6

[0080] The synthesis process and the amount of raw materials used are the same as in Example 1, but the structure shown in formula (4) is used. 1 =50, n 2 =0, R = R' = CH 3 α,ω-bis(hydroxy-terminated polyoxypropylene propyl) polydimethylsiloxane HO(C 3 H 6 O) 6 C 3 H 6 Si(CH 3 ) 2 [OSi(CH 3 ) 2 ] 50 OSi(CH 3 ) 2 C 3 H 6 (C 3 H6 O) 6 OH(HO-PS-OH-6) was used to replace HO-PS-OH-1 in Example 1 in an equal molar amount and the reaction was carried out in the same manner. The obtained structure is shown in formula (2). 1 =50, n 2 =0, R = R' = CH 3 , a1=0, b1=6, M'=H, that is, the oligosiloxane polyether acrylate diester synthesized in Example 6, denoted as PSDA-6.

[0081] PSDA-6 was used instead of PSDA-1, and then the slurry was prepared and the light-cured silicone polyurethane leather was prepared in the same way as in Example 1. The leather sample obtained was recorded as SPUL-6 and used as the reference-1 of the present invention.

[0082] Example 7

[0083] The synthesis process and the amount of raw materials used were the same as in Example 1, except that 30.0 g of commercially available α, ω-(diacrylated propyl) polydimethylsiloxane was used in place of PSDA-1, and an equal amount of commercially available single-end acrylated propyl polydimethylsiloxane was used in place of PSMA-1. Then, the slurry (SPUL-7) was prepared in the same manner as in Example 1 and photocured, which was used as a reference sample of the present invention. The results showed that the system was turbid, phase-separated after standing, and could not be photocured.

[0084] Example 8

[0085] The synthesis process and the amount of raw materials used are the same as those in Example 1, but the tetrafunctional polyurethane acrylate HM6620 is not added. Instead, HM6620 is replaced by polytetramethylene ether polyurethane diacrylate with an equal mass average molecular weight of about 2500. The obtained leather slurry (SPU-8) is then photocured in the same manner as in Example 1 and used as a reference for the present invention. The result is that the system cannot be effectively cured.

[0086] Example 9

[0087] The synthesis process and the amount of raw materials used are the same as those in Example 1, but the difunctional polytetramethylene ether polyurethane diacrylate is not added, and the ester is replaced by an equal mass of tetrafunctional polyurethane acrylate HM6620. Then, the slurry is prepared and the light-cured silicone polyurethane leather is prepared as in Example 1. The obtained leather sample is recorded as SPUL-9 and used as a reference for the present invention.

[0088] The SPUL samples and reference samples of the light-cured silicone polyurethane leather prepared in Examples 1-9 were taken and balanced for 48 hours at room temperature of 25±2° C. and relative humidity RH of about 60%, and then performance tests were performed:

[0089] Tensile strength and elongation at break: refer to GB / T528-2009 standard, use dumbbell-shaped I-type test specimens as test specimens and use a universal testing machine to test. Leather surface hydrophobicity: the static contact angle (θ H2O ) is indicated by JC-2000C1 static contact angle measuring instrument, and the water drop size is 5μL; aging resistance (1000h×85℃×RH85%): measured by KK-SN-150 xenon lamp aging test box in accordance with GB / T2423.24-1995 standard. Wear resistance test: cut a circular leather sample with a die cutter in accordance with GB / T13775 standard, and measure it with HD-P306-2 Martindale wear tester (Guangdong Haida Instrument Co., Ltd.) under a load of 200g, with a measuring stroke of 60.5±0.5 (mm), and observe the degree of coating wear with a magnifying glass. The maximum friction number measured when the substrate is not exposed is used as the friction resistance number of this experiment. All measurement results are shown in Table 1.

[0090] As can be seen from Table 1, SPUL-1-5 has good compatibility and solubility with components such as polymethylphenylsiloxane, polydiphenylsiloxane, poly(dimethylsiloxane-co-diphenylsiloxane) containing polyether acrylate groups and non-silicon 2-6 functional (polyether) polyurethane acrylate resins and aminosilane-modified bisphenol A epoxy resins. The photocurable resin composition of the present invention not only overcomes the phase separation, stratification and turbidity that are easily produced when traditional organic silicon (such as polydimethylsiloxane) meets resins such as polyurethane acrylate, but also makes the composition present a homogeneous and transparent appearance. Therefore, under UV light conditions, the composition of the present invention can not only effectively realize The present invention cures at room temperature, and due to the hydrogen bonds and intermolecular forces between the polyether groups CO, phenylsiloxane, ester bonds -COO- on the main chains of PSDA and PSMA and the -NHCOO-, benzene rings or alicyclic hydrocarbons in the structures of polyurethane acrylates, etc., it is also helpful to enhance the interaction between the polymer chain segments after curing, so that the synthetic leather prepared based on the photocurable resin of the present invention can not only achieve an adhesion of 0-1 and a friction resistance of 12000-15000 times, but also because the single-end polymethylphenylsiloxane chain segments migrate out of the directional arrangement of the leather surface and have a good waterproof and dustproof effect, the contact angle of water on the leather surface of the present invention can reach 96.7-113.8°, thereby showing a better water resistance.

[0091] Table 1 Performance test results of light-cured silicone polyurethane leather SPUL-1~9

[0092]

[0093] ★: Good aging resistance, 1000h×85℃×RH85% without yellowing

[0094] 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 photocurable silicone polyurethane leather tanning slurry, characterized in that: The composition comprises, by mass, 10-35 parts of oligosiloxane acrylate, 35-80 parts of a mixture of difunctional polyurethane acrylate and multifunctional acrylate, 10-30 parts of acrylate reactive diluent, 10-30 parts of aminosilane ring-opening modified epoxy resin, 1-5 parts of oil-soluble color paste, 0.5-1 parts of wetting dispersant, and 1-5 parts of free radical photoinitiator; The oligosiloxane acrylate has a main component as shown in formula (I) and / or formula (II): Wherein, n=4-40, a=0-3, b=0-10, a+b=0-10, M=H or CH3; n1, n2=0-40, n1+n2=4-40, R, R', R", R''=CH3 or phenyl Ph, a1=0-3, b1=0-10, a1+b1=0-10, M'=H or CH3; The difunctional polyurethane acrylate is a polyether polyurethane diacrylate containing two acrylate groups or a polyester polyurethane diacrylate containing two acrylate groups, and the number average molecular weight Mn is 2000-20000; The multifunctional acrylate is a free radical copolymerization monomer containing 3-6 acrylate groups or a polyurethane acrylate prepolymer containing 3-6 acrylate groups; The acrylate reactive diluent is a free radical copolymerization monomer or a diol oligomer containing 1-2 acrylate groups; The aminosilane ring-opening modified epoxy resin is an aminosilane modified epoxy resin obtained by reacting epoxy resin with aminosilane.

2. The leather slurry according to claim 1, characterized in that The oligosiloxane acrylate is a mixture of a single-end polyether acrylate-based polyorganosiloxane of formula (I) and a double-end polyether acrylate-based polyorganosiloxane of formula (II); wherein the single-end polyether acrylate-based polyorganosiloxane of formula (I) is used in an amount of less than or equal to 15 parts, and the double-end polyether acrylate-based polyorganosiloxane of formula (II) is used in an amount of 10-35 parts; in the mixture of 35-80 parts of difunctional polyurethane acrylate and multifunctional acrylate, the difunctional polyurethane acrylate is 30-75 parts and the multifunctional acrylate is 5-30 parts.

3. The leather slurry according to claim 1, characterized in that: The oligosiloxane acrylate is obtained by reacting a terminal hydroxyl polyorganosiloxane having a structure of formula (III) and / or formula (IV) as the main component with an unsaturated carboxylic acid; the structures of formula (III) and formula (IV) are: In the formula, n=4-40, a=0-3, b=0-10, a+b=0-10; n1, n2=0-40, n1+n2=4-40, R, R', R", R''=CH3 or phenyl Ph, a1=0-3, b1=0-10, a1+b1=0-10.

4. The leather slurry according to claim 3, characterized in that: The molar ratio of the terminal hydroxyl polyorganosiloxane to the unsaturated carboxylic acid is 1:(5-10), the reaction temperature is 80-110° C., and the reaction time is 4-10 hours.

5. The leather slurry according to claim 3, characterized in that: The unsaturated carboxylic acid is one or more of acrylic acid, methacrylic acid and 2-butenoic acid.

6. The leather slurry according to claim 1, characterized in that: The multifunctional acrylate is one or more of pentaerythritol triacrylate, pentaerythritol tetraacrylate, polydipentaerythritol hexaacrylate, glycerol triacrylate, trimethylolpropane triacrylate, and polyurethane acrylate with a functionality of 4-6; The acrylate reactive diluent is acrylic acid C 1-12 One or more of alkyl esters, cyclohexyl acrylate, isobornyl acrylate, ethylene glycol diacrylate, propylene glycol diacrylate, diethylene glycol diacrylate, dipropylene glycol diacrylate, triethylene glycol diacrylate, tripropylene glycol diacrylate, polypropylene glycol diacrylate with Mn=200-600, and polyethylene glycol diacrylate with Mn=200-400.

7. The leather slurry according to claim 1, characterized in that: The aminosilane ring-opening modified epoxy resin is prepared by reacting epoxy resin and aminosilane at a molar ratio of 1: (2-2.2) at 60-70°C for 30-60 minutes; the epoxy resin is one or more of bisphenol A epoxy resins E51 and E44, and the aminosilane is one or more of 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, and 3-aminopropylmethyldiethoxysilane.

8. The leather slurry according to claim 1, characterized in that: The wetting and dispersing agent is one or more of BYK-ATU, BYK-110, BYK-163; the substrate is fluorine release paper, non-woven fabric made of polyester or spandex, or ultrafine fiber base fabric.

9. The method for making leather using the leather making slurry according to any one of claims 1 to 8, characterized in that: The steps include: 1) Preparation of leather slurry: weigh 10-35 parts of oligosiloxane acrylate, 35-80 parts of a mixture of difunctional polyurethane acrylate and multifunctional acrylate, 10-30 parts of acrylate reactive diluent, 10-30 parts of aminosilane ring-opening modified epoxy resin, 1-5 parts of oil-soluble color paste, 0.5-1 parts of dispersant, and 1-5 parts of free radical photoinitiator, by mass, and stir and mix to obtain leather slurry; 2) Preparation of photocurable silicone polyurethane leather: Fix the substrate on the laboratory table, evenly apply the slurry on the surface of the substrate, control the amount of slurry so that the coating thickness after curing is 150-300μm, cure with UV light, spray leather feel agent, and obtain photocurable silicone polyurethane leather.

10. The light-cured organosilicon polyurethane leather prepared by the method according to claim 9.

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