Rubber imitation leather and method for producing the same

Abstract

The present application relates to the technical field of rubber simulation material, in particular to a rubber simulation leather and a preparation method thereof, modified transparent rubber and other raw materials are used to prepare a calendered top piece, so that a transparent and smooth piece layer is formed after subsequent mold pressing, and the rubber simulation leather has excellent high and low temperature resistance, wear resistance and tear resistance, good resilience; TPR material, colorant, filler, plasticizer and stabilizer are mixed and extruded and granulated to obtain TPR blend, the mixing is more uniform, which is beneficial to the coloring effect of the TPR blend and facilitates the subsequent formation of obvious color and foaming lines; a foaming and expanding agent and modified transparent rubber and other raw materials are added to the TPR blend to prepare a calendered bottom piece; then the calendered top piece and the calendered bottom piece are compounded and vulcanized under high temperature and high pressure, and the calendered bottom piece is micro-foamed at the same time, so that the rubber simulation leather with a smooth surface and foaming lines in the interior is obtained, the rubber simulation leather has excellent high and low temperature resistance, wear resistance and tear resistance, good resilience, and is suitable for furniture, luggage and automotive interior and the like.

Description

Technical Field

[0001] The present invention relates to the technical field of rubber simulation materials, in particular to a rubber simulation leather material and a preparation method thereof. Background Art

[0002] Simulated leather is a material that resembles genuine leather. It's typically made from plastics like polyvinyl chloride (PVC), polyurethane (PU), and polyethylene (PE) through specialized processing techniques. While these materials can create a texture, color, and sheen that mimics genuine leather, they often feel hard and lack the softness and elasticity of genuine leather. Furthermore, after prolonged use, simulated leather may harden or crack on the surface. Its resistance to high and low temperatures, wear resistance, and toughness / tear resistance are insufficient, making it unsuitable for applications such as furniture, luggage, and automotive interiors. Summary of the Invention

[0003] In order to overcome the shortcomings and deficiencies in the prior art, the purpose of the present invention is to provide a method for preparing a rubber simulation leather material, which comprises preparing a calendered upper sheet using raw materials such as modified transparent rubber, and preparing a calendered bottom sheet using raw materials such as TPR material, colorant, foaming expansion agent and modified transparent rubber, and then placing the calendered bottom sheet and the calendered upper sheet in a molding device. During the molding process, the calendered upper sheet and the calendered bottom sheet are compounded and vulcanized under high temperature and high pressure conditions, while the interior of the calendered bottom sheet is micro-foamed, thereby obtaining a rubber simulation leather material with a smooth surface and foamed texture inside. The rubber simulation leather material has excellent high and low temperature resistance, wear resistance and tear resistance, and good resilience, and is suitable for use in the fields of furniture, luggage, and automotive interiors. The preparation method is simple to operate, convenient to control, has high production efficiency, low production cost, and can be used for large-scale production.

[0004] Another object of the present invention is to provide a rubber simulated leather material that can simulate the appearance of real leather and has excellent high and low temperature resistance, wear resistance and tear resistance, and good resilience, and is suitable for use in furniture, luggage, and automotive interiors.

[0005] The purpose of the present invention is achieved through the following technical solution: A method for preparing a rubber simulation leather material comprises the following steps:

[0006] (S1) 1.8-2.5 parts of vulcanizing agent A, 1-3 parts of vulcanization accelerator and 100 parts of modified transparent rubber are mixed at 90-110° C. and then calendered into a sheet, which is then cut to obtain a calendered upper sheet;

[0007] (S2) taking 80 parts by weight of TPR material, 0.1-20 parts of colorant, 5-20 parts of filler, 3-5 parts of plasticizer and 1-3 parts of stabilizer, mixing them at a temperature of 180-230° C., and extruding and granulating them through a twin-screw extruder to obtain a TPR blend;

[0008] (S3), 10-15 parts of foaming expanding agent, 0.3-0.4 parts of vulcanizing agent B, 0.2-0.6 parts of vulcanization accelerator and 20-30 parts of modified transparent rubber are added to the TPR blend by weight parts, and after mixing at 60-90℃, the rubber sheet is obtained by calendering and cutting;

[0009] (S4), the calendered bottom sheet is added to the molding equipment, and the calendered top sheet is covered on the surface of the calendered bottom sheet, and the rubber leather is obtained by high-temperature molding at 155-170℃ and 10-20Mpa, and vulcanizing at the same time, and keeping for 240-600s, and the rubber leather has smooth surface and foaming lines inside.

[0010] The preparation method of the rubber leather, the vulcanizing agent A, the vulcanization accelerator and the modified transparent rubber are mixed at 90-110℃ to form the calendered top sheet, so as to form a transparent and smooth sheet layer after subsequent molding, and the rubber leather has excellent high and low temperature resistance, wear resistance and tear resistance, good resilience; the TPR material, the coloring agent, the filler, the plasticizer and the stabilizer are mixed at 180-230℃ to obtain the TPR blend by extruding and granulating, the mixture is more uniform, which is beneficial to the coloring effect of the TPR blend, the foaming lines with obvious color are easily obtained, the flexibility and ductility of the TPR material are improved, and the good weather resistance, high and low temperature resistance and tear resistance are maintained; the foaming expanding agent, the vulcanizing agent B, the vulcanization accelerator and the modified transparent rubber are added to the TPR blend, and the TPR blend is mixed at 60-90℃ to form the calendered bottom sheet, which is beneficial to avoiding the foaming expanding agent foaming too early and too fast, and the raw materials are fully mixed, and a small amount of modified transparent rubber is mixed in the calendered bottom sheet to improve the high and low temperature resistance and tear resistance, and promote the molding of the calendered top sheet; then the calendered bottom sheet and the calendered top sheet are put into the molding equipment, and the calendered top sheet and the calendered bottom sheet are compounded and vulcanized under high temperature and high pressure in the molding process, and the calendered bottom sheet is slightly foamed, and the rubber leather with smooth surface and foaming lines inside is obtained, which has excellent high and low temperature resistance, wear resistance and tear resistance, and good resilience, and is suitable for furniture, luggage and automotive interior and the like. In step (S4), the molding conditions are controlled at 155-170℃, 10-20Mpa and keeping for 240-600s, which ensures the complete vulcanization of the rubber leather, improves the wear resistance of the rubber leather, promotes the foaming expansion of the calendered bottom sheet to form the foaming lines similar to the appearance of leather, and meets the application requirements. The processing temperature of each section of the twin-screw extruder is 150-160℃, 160-170℃, 170-180℃ and 170-180℃, the die temperature is 170-175℃, and the screw length-diameter ratio is 16-18:1.

[0011] Preferably, the ratio of the thickness of the calendered bottom sheet to the thickness of the calendered top sheet is 1-6:0.6-2.

[0012] The transparent and smooth sheet layer formed after the calendering upper sheet is molded plays an important role in the resilience, high and low temperature resistance, wear resistance and tear resistance of the rubber simulation leather, and is conducive to the formation of foaming lines on the calendering bottom sheet during the molding process, and the rubber simulation leather with foaming lines inside is more directly displayed through the transparent and smooth sheet layer.

[0013] Preferably, the vulcanizing agent A is di-tert-butyl peroxide; the vulcanization accelerator is a mixture of accelerator DM and accelerator H in a weight ratio of 2-3:1; and the vulcanizing agent B is a mixture of dicumyl peroxide and sulfur in a weight ratio of 2-2.5:0.5.

[0014] The above technical scheme is adopted, the calendering upper sheet uses the above-mentioned vulcanizing agent A and vulcanization accelerator, and the vulcanization effect is better, which is more conducive to the transparency and mechanical properties of the transparent and smooth sheet layer.

[0015] Preferably, the modified transparent rubber comprises the following raw materials by weight: 100 parts of rubber raw material, 15-30 parts of composite reinforcing agent, 2-5 parts of plasticizer, 2-5 parts of active agent, and 0.3-1.5 parts of anti-aging agent.

[0016] The above technical scheme is adopted, and the special rubber raw material is used as the main body to maintain the basic transparency, high and low temperature resistance, wear resistance, tear resistance and elasticity; the composite reinforcing agent is doped to improve the transparency of the modified transparent rubber, and the reinforcing effect is good, which can significantly improve the tensile strength, tear strength and wear resistance of the rubber, and improve the heat resistance; the plasticizer is added to improve the plasticity of the rubber, so that the rubber product exhibits better elasticity and toughness during processing and use, and is conducive to improving the heat resistance and cold resistance of the rubber, so that it can still maintain stable performance under extreme temperature conditions, and is also conducive to making the surface of the calendering upper sheet after molding and vulcanization more smooth and bright; the active agent is added to promote the vulcanization of the modified transparent rubber, and is conducive to improving the wear resistance while avoiding affecting the transparency.

[0017] Preferably, the rubber raw material is at least one of ethylene-propylene rubber, isoprene rubber, butyl rubber and styrene-butadiene rubber; and the composite reinforcing agent is a mixture of at least two of transparent white carbon black, basic magnesium carbonate and sulfonated hetero-naphthalene biphenyl copolymer arylether sulfone (SPPBES).

[0018] More preferably, the rubber raw material is a mixture of ethylene-propylene rubber, isoprene rubber and styrene-butadiene rubber in a weight ratio of 3-4:3-4:1, and the above-mentioned specially compounded rubber raw material is used as the main body to maintain the basic transparency, high and low temperature resistance, wear resistance, tear resistance and elasticity; the composite reinforcing agent is a mixture of transparent white carbon black, basic magnesium carbonate and sulfonated heteronaphthalene biphenyl copolymer aryl ether sulfone (SPPBES) in a weight ratio of 5:2-3:1, and the composite reinforcing agent is soaked with silane coupling agent KH550 and then dried for use to improve the compatibility and dispersibility of the composite reinforcing agent in the rubber, and the doping of the above-mentioned composite reinforcing agent is beneficial to improving the transparency of the modified transparent rubber, and the reinforcing effect is good, which can significantly improve the tensile strength, tear strength and wear resistance of the rubber, and improve the heat resistance. Further, the average particle size of the composite reinforcing agent is 15-30 μm.

[0019] Preferably, the plasticizer is alkyl phenyl sulfonate and / or diethylene glycol dibenzoate; the active agent is transparent zinc oxide or activated zinc oxide; and the antioxidant is antioxidant SP and / or antioxidant MB.

[0020] By using the above technical solution, the addition of the above-mentioned plasticizer is beneficial to improving the plasticity of the rubber, making the rubber products exhibit better elasticity and toughness during processing and use, and is beneficial to improving the heat resistance and cold resistance of the rubber, so that it can still maintain stable performance under extreme temperature conditions, and is also beneficial to making the surface of the calendering sheet mold vulcanization more smooth and bright; the addition of the above-mentioned active agent is beneficial to promoting the vulcanization of the modified transparent rubber, and is beneficial to improving the wear resistance while avoiding affecting the transparency. The above-mentioned antioxidant is beneficial to improving the antioxidant and anti-aging effect of the modified transparent rubber, prolonging the service life, and avoiding affecting the transparency.

[0021] Preferably, the TPR material is at least one selected from TPR XT7025, TPR55A, TPR60A or TPR65A; the filler is a mixture of silane coupling agent modified wollastonite powder and silane coupling agent modified glass fiber in a weight ratio of 8-15:1; and the plasticizer is a mixture of trioctyl trimellitate and dodecenyl succinic anhydride in a weight ratio of 1:1.

[0022] The TPR material has the characteristics of rubber and thermoplastic plastic, has excellent elasticity, weather resistance and processing performance, the surface is bright, has good light reflection performance, is easy to color, and after being molded in a rolling base sheet, the foaming lines presented by the TPR material in cooperation with a foaming expansion agent are similar to the appearance of real leather, and meet the application requirements. The above-mentioned filler is compounded, the compatibility and dispersibility of the filler in the TPR material are improved, the mechanical properties such as tensile strength and tear strength of the TPR material are improved, the weather resistance, wear resistance and fatigue resistance of the TPR material are improved, the load of the TPR material in the stress process is effectively shared, and the overall performance of the composite material is improved. Further, the length of the silane coupling agent modified glass fiber is 3 mm. The above-mentioned plasticizer is mixed by using trioctyl trimellitate and dodecenyl succinic anhydride at a weight ratio of 1:1, the plasticity of the TPR material is increased, the TPR material is more easy to process, the flexibility and ductility of the TPR material are enhanced, the amount of the plasticizer is reasonably controlled, the brittleness of the TPR material is avoided to be increased due to too much amount of the plasticizer, and the adverse effect of the plasticizer on the strength of the TPR material is avoided.

[0023] Preferably, the colorant is at least one of titanium dioxide, zinc sulfide, red iron oxide, permanent yellow, china blue and phthalocyanine green; and the stabilizer is at least one of antioxidant SP, antioxidant CA, antioxidant DLTP and antioxidant 264.

[0024] Preferably, the foaming expansion agent is a mixture of sodium bicarbonate and phenylsulfonyl hydrazine at a weight ratio of 5-8:1.

[0025] According to the above technical scheme, the foaming lines presented by the TPR material in cooperation with the foaming expansion agent after being molded in the rolling base sheet are similar to the appearance of real leather, and meet the application requirements.

[0026] Another object of the present application is achieved by the following technical scheme: a rubber imitation leather is prepared by the above-mentioned method.

[0027] The rubber imitation leather prepared by the method has the advantages that: the modified transparent rubber and other raw materials are used to prepare a rolling upper sheet, and the TPR material, the colorant, the foaming expansion agent and the modified transparent rubber and other raw materials are used to prepare a rolling base sheet, then the rolling base sheet and the rolling upper sheet are put into a molding equipment, the rolling upper sheet and the rolling base sheet are compounded and vulcanized under high temperature and high pressure in the molding process, and the rolling base sheet is internally foamed at the same time, so that the rubber imitation leather with smooth surface and internal foaming lines is obtained, the rubber imitation leather has excellent high and low temperature resistance, wear resistance and tear resistance, good resilience, and is suitable for furniture, luggage and automotive interiors and the like; the preparation method is simple in operation, convenient to control, high in production efficiency and low in production cost, and can be used for large-scale production.

[0028] The rubber artificial leather of the present application can simulate the appearance similar to the leather, has excellent high and low temperature resistance, wear resistance and tear resistance, good resilience, and is suitable for the fields of furniture, luggage and automotive interior decoration. BRIEF DESCRIPTION OF DRAWINGS

[0029] Figure 1 is a product schematic diagram of embodiment 2 of the present application. DETAILED DESCRIPTION

[0030] In order to facilitate the understanding of those skilled in the art, the present application will be further described below in conjunction with the embodiments and drawings, and the content mentioned in the embodiments is not a limitation on the present application.

[0031] Embodiment 1

[0032] A preparation method of a rubber artificial leather, comprising the following steps:

[0033] (S1), taking 2 parts of vulcanizing agent A, 2 parts of vulcanizing accelerator and 100 parts of modified transparent rubber by weight, mixing at 100℃ and then calendering into a sheet, cutting to obtain a calendered upper sheet;

[0034] (S2), taking 80 parts of TPR material, 10 parts of colorant, 15 parts of filler, 4 parts of plasticizer and 2 parts of stabilizer by weight, mixing at 220℃, then extruding and granulating by a double screw extruder to obtain a TPR blend;

[0035] (S3), adding 13 parts of foaming agent, 0.35 parts of vulcanizing agent B, 0.4 parts of vulcanizing accelerator and 25 parts of modified transparent rubber to the TPR blend by weight, mixing at 75℃ and then calendering into a sheet, cutting to obtain a calendered bottom sheet;

[0036] (S4), adding the calendered bottom sheet to a molding equipment, covering the calendered upper sheet on the surface of the calendered bottom sheet, high temperature molding at 160℃ and 15Mpa while vulcanizing, keeping for 420s to obtain a rubber artificial leather with smooth surface and foaming lines inside.

[0037] In the step (S2), the processing temperature of each section of the double screw extruder is 155℃, 165℃, 170℃ and 180℃, the die temperature is 175℃, and the screw length-diameter ratio is 16:1.

[0038] The ratio of the thickness of the calendered bottom sheet to the thickness of the calendered upper sheet is 3:1.

[0039] The vulcanizing agent A is di-t-butyl peroxide; the vulcanizing accelerator is a mixture of accelerator DM and accelerator H in a weight ratio of 2.5:1; and the vulcanizing agent B is a mixture of dicumyl peroxide and sulfur in a weight ratio of 2.3:0.5.

[0040] The modified transparent rubber comprises raw materials in the following weight parts: 100 parts of rubber raw material, 22 parts of composite reinforcing agent, 4 parts of plasticizer, 4 parts of active agent and 1 part of antioxidant.

[0041] The rubber raw material is a mixture of ethylene-propylene rubber, isoprene rubber and styrene-butadiene rubber in a weight ratio of 3.5:3.5:1; the composite reinforcing agent is a mixture of transparent white carbon black, basic magnesium carbonate and sulfonated heteronaphthalene-biphenyl copolymer aryl ether sulfone (SPPBES) in a weight ratio of 5:2.5:1, and the composite reinforcing agent is soaked with silane coupling agent KH550 and then dried for use, and the average particle size of the composite reinforcing agent is 20 μm.

[0042] The plasticizer is diethylene glycol dibenzoate; the active agent is activated zinc oxide; and the antioxidant is a mixture of antioxidant SP and antioxidant MB in a weight ratio of 4:1.

[0043] The TPR material is selected from TPR XT7025; the filler is a mixture of silane coupling agent KH550 modified wollastonite powder and silane coupling agent KH550 modified glass fiber in a weight ratio of 10:1, the length of the silane coupling agent KH550 modified glass fiber is 3 mm; and the plasticizer is a mixture of trioctyl trimellitate and dodecenyl succinic anhydride in a weight ratio of 1:1.

[0044] The colorant is permanent yellow; and the stabilizer is a mixture of antioxidant SP and antioxidant CA in a weight ratio of 4:1.

[0045] The foaming and expanding agent is a mixture of sodium bicarbonate and benzenesulfonyl hydrazide in a weight ratio of 7:1.

[0046] Example 2

[0047] A preparation method of a rubber artificial leather, comprising the following steps:

[0048] (S1), taking 1.8 parts of vulcanizing agent A, 3 parts of vulcanization accelerator and 100 parts of modified transparent rubber by weight, mixing at a temperature of 90℃, calendering into a sheet, cutting to obtain a calendered top sheet;

[0049] (S2), taking 80 parts of TPR material, 18 parts of colorant, 5 parts of filler, 3 parts of plasticizer and 1 part of stabilizer by weight, mixing at a temperature of 185℃, then extruding and granulating by a double screw extruder to obtain a TPR blend;

[0050] (S3), adding 10 parts of foaming and expanding agent, 0.3 parts of vulcanizing agent B, 0.6 parts of vulcanization accelerator and 20 parts of modified transparent rubber to the TPR blend by weight, mixing at a temperature of 60℃, calendering into a sheet, cutting to obtain a calendered bottom sheet;

[0051] (S4), adding the calendered bottom sheet into the molding equipment, covering the calendered top sheet on the surface of the calendered bottom sheet, high-temperature molding and vulcanization at 155 DEG C, 10Mpa, keeping for 600s, to obtain the rubber artificial leather with smooth surface and foaming lines inside.

[0052] In the step (S2), the processing temperature of each section of the double-screw extruder is 155 DEG C, 165 DEG C, 170 DEG C, 180 DEG C, the die temperature is 175 DEG C, and the screw length-diameter ratio is 16:1.

[0053] The thickness ratio of the calendered bottom sheet to the calendered top sheet is 3:1.

[0054] The vulcanizing agent A is di-tert-butyl peroxide; the vulcanization accelerator is a mixture of accelerator DM and accelerator H at a weight ratio of 2:1; and the vulcanizing agent B is a mixture of dicumyl peroxide and sulfur at a weight ratio of 2:0.5.

[0055] The modified transparent rubber comprises the following raw materials by weight: 100 parts of rubber raw material, 15 parts of composite reinforcing agent, 2 parts of plasticizer, 2 parts of active agent, and 0.3 parts of anti-aging agent.

[0056] The rubber raw material is a mixture of ethylene-propylene rubber, isoprene rubber, and styrene-butadiene rubber at a weight ratio of 3:3:1; the composite reinforcing agent is a mixture of transparent white carbon black, basic magnesium carbonate, and sulfonated hetero-naphthalene biphenyl copolymer arylether sulfone (SPPBES) at a weight ratio of 5:2:1, and the composite reinforcing agent is soaked in silane coupling agent KH550 and then dried for use; and the average particle size of the composite reinforcing agent is 15 μm.

[0057] The plasticizer is diethylene glycol dibenzoate; the active agent is activated zinc oxide; and the anti-aging agent is a mixture of anti-aging agent SP and anti-aging agent MB at a weight ratio of 4:1.

[0058] The TPR material is selected from TPR XT7025; the filler is a mixture of silane coupling agent KH550 modified wollastonite powder and silane coupling agent KH550 modified glass fiber at a weight ratio of 8:1, the length of the silane coupling agent KH550 modified glass fiber is 3 mm; and the plasticizer is a mixture of trioctyl trimellitate and dodecenyl succinic anhydride at a weight ratio of 1:1.

[0059] The colorant is permanent yellow; and the stabilizer is a mixture of anti-aging agent SP and antioxidant CA at a weight ratio of 4:1.

[0060] The foaming expansion agent is a mixture of sodium bicarbonate and benzenesulfonyl hydrazide at a weight ratio of 5:1.

[0061] Example 3

[0062] A method for preparing a rubber artificial leather comprises the following steps:

[0063] (S1), taking 2.5 parts of vulcanizing agent A, 1 part of vulcanization accelerator and 100 parts of modified transparent rubber by weight, after mixing at 100℃, calendering into a sheet, cutting to obtain a calendered upper sheet;

[0064] (S2), taking 80 parts of TPR material, 1 part of colorant, 20 parts of filler, 5 parts of plasticizer and 3 parts of stabilizer by weight, after mixing at 230℃, extruding and granulating through a double screw extruder, to obtain a TPR blend;

[0065] (S3), adding 15 parts of foaming agent, 0.4 parts of vulcanizing agent B, 0.2 parts of vulcanization accelerator and 30 parts of modified transparent rubber to the TPR blend by weight, after mixing at 90℃, calendering into a sheet, cutting to obtain a calendered bottom sheet;

[0066] (S4), adding the calendered bottom sheet to the molding equipment, covering the calendered upper sheet on the surface of the calendered bottom sheet, high temperature molding at 170℃, 20Mpa, simultaneous vulcanization, keeping for 240s, to obtain a rubber simulation leather with smooth surface and internal foaming lines.

[0067] In the step (S2), the processing temperature of each section of the double screw extruder is 155℃, 165℃, 170℃, 180℃, the die temperature is 175℃, and the screw length-diameter ratio is 16:1.

[0068] The ratio of the thickness of the calendered bottom sheet to the thickness of the calendered upper sheet is 3:1.

[0069] The vulcanizing agent A is di-t-butyl peroxide; the vulcanization accelerator is a mixture of accelerator DM and accelerator H in a weight ratio of 3:1; the vulcanizing agent B is a mixture of dicumyl peroxide and sulfur in a weight ratio of 2.5:0.5.

[0070] The modified transparent rubber includes the following raw materials by weight: 100 parts of rubber raw material, 30 parts of composite reinforcing agent, 5 parts of plasticizer, 5 parts of active agent and 1.5 parts of antioxidant.

[0071] The rubber raw material is a mixture of ethylene-propylene rubber, isoprene rubber and styrene-butadiene rubber in a weight ratio of 4:4:1; the composite reinforcing agent is a mixture of transparent white carbon black, basic magnesium carbonate and sulfonated hetero-naphthalene biphenyl copolymer aryl ether sulfone (SPPBES) in a weight ratio of 5:3:1, and the composite reinforcing agent is soaked with silane coupling agent KH550 and dried for use, and the average particle size of the composite reinforcing agent is 30μm.

[0072] The plasticizer is diethylene glycol dibenzoate; the active agent is activated zinc oxide; and the antioxidant is a mixture of antioxidant SP and antioxidant MB in a weight ratio of 4:1.

[0073] The TPR material is selected from TPR XT7025; the filler is a mixture of silane coupling agent KH550 modified wollastonite powder and silane coupling agent KH550 modified glass fiber in a weight ratio of 15:1, the length of the silane coupling agent KH550 modified glass fiber is 3mm; the plasticizer is a mixture of trioctyl trimellitate and dodecenyl succinic anhydride in a weight ratio of 1:1.

[0074] The colorant is permanent yellow; the stabilizer is a mixture of antioxidant SP and antioxidant CA in a weight ratio of 4:1.

[0075] The foaming agent is a mixture of sodium bicarbonate and phenylsulfonyl hydrazine in a weight ratio of 8:1.

[0076] Example 4

[0077] A method for preparing a rubber artificial leather material, comprising the following steps:

[0078] (S1), taking 2.2 parts of vulcanizing agent A, 2 parts of vulcanizing accelerator and 100 parts of modified transparent rubber by weight, mixing at a temperature of 100℃, calendering into a sheet, cutting to obtain a calendered upper sheet;

[0079] (S2), taking 80 parts of TPR material, 10 parts of colorant, 10 parts of filler, 5 parts of plasticizer and 2 parts of stabilizer by weight, mixing at a temperature of 200℃, then extruding and granulating by a twin-screw extruder to obtain a TPR blend;

[0080] (S3), adding 13 parts of foaming agent, 0.35 parts of vulcanizing agent B, 0.4 parts of vulcanizing accelerator and 28 parts of modified transparent rubber to the TPR blend by weight, mixing at a temperature of 80℃, calendering into a sheet, cutting to obtain a calendered lower sheet;

[0081] (S4), adding the calendered lower sheet to a molding device, covering the calendered upper sheet on the surface of the calendered lower sheet, high-temperature molding and vulcanizing at 160℃ and 18Mpa at the same time, keeping for 300s to obtain a rubber artificial leather material with smooth surface and foaming lines inside.

[0082] In the step (S2), the processing temperature of each section of the twin-screw extruder is 155℃, 165℃, 170℃ and 180℃, the die temperature is 175℃, and the screw length-diameter ratio is 16:1.

[0083] The ratio of the thickness of the calendered lower sheet to the thickness of the calendered upper sheet is 3:1.

[0084] The vulcanizing agent A is di-t-butyl peroxide; the vulcanizing accelerator is a mixture of accelerator DM and accelerator H in a weight ratio of 2.5:1; the vulcanizing agent B is a mixture of dicumyl peroxide and sulfur in a weight ratio of 2.2:0.5.

[0085] The modified transparent rubber comprises raw materials in the following weight parts: rubber raw material 100 parts, composite reinforcing agent 25 parts, plasticizer 3 parts, active agent 3 parts and antioxidant 0.5 parts.

[0086] The rubber raw material is a mixture of ethylene-propylene rubber, isoprene rubber and styrene-butadiene rubber in a weight ratio of 3.4:3.4:1; the composite reinforcing agent is a mixture of transparent white carbon black, basic magnesium carbonate and sulfonated heteronaphthalene-biphenyl copolymer aryl ether sulfone (SPPBES) in a weight ratio of 5:2.3:1, and the composite reinforcing agent is soaked with silane coupling agent KH550 and then dried for use, and the average particle size of the composite reinforcing agent is 20 μm.

[0087] The plasticizer is diethylene glycol dibenzoate; the active agent is activated zinc oxide; and the antioxidant is a mixture of antioxidant SP and antioxidant MB in a weight ratio of 4:1.

[0088] The TPR material is selected from TPR XT7025; the filler is a mixture of silane coupling agent KH550 modified wollastonite powder and silane coupling agent KH550 modified glass fiber in a weight ratio of 12:1, the length of the silane coupling agent KH550 modified glass fiber is 3 mm; and the plasticizer is a mixture of trioctyl trimellitate and dodecenyl succinic anhydride in a weight ratio of 1:1.

[0089] The colorant is permanent yellow; and the stabilizer is a mixture of antioxidant SP and antioxidant CA in a weight ratio of 4:1.

[0090] The foaming and expanding agent is a mixture of sodium bicarbonate and benzenesulfonyl hydrazide in a weight ratio of 6:1.

[0091] Comparative Example 1

[0092] The difference between the present comparative example and Example 1 is that:

[0093] The composite reinforcing agent is a mixture of transparent white carbon black and basic magnesium carbonate in a weight ratio of 5.5:3.

[0094] Comparative Example 2

[0095] The difference between the present comparative example and Example 1 is that:

[0096] The rubber raw material is a mixture of butyl rubber and styrene-butadiene rubber in a weight ratio of 7:1.

[0097] Comparative Example 3

[0098] The difference between the present comparative example and Example 1 is that:

[0099] In the step (S4), the molding conditions are 160℃, normal pressure and 420s of holding.

[0100] Comparative Example 4

[0101] The difference between the present comparative example and Example 1 is that:

[0102] The filler is talc powder modified by silane coupling agent KH550.

[0103] Example 5

[0104] Performance test

[0105] I, the rubber imitation leather sample of Example 2 is as shown in Figure 1 It can be seen that the rubber imitation leather sample has the characteristics of smooth and transparent surface and obvious foaming lines inside. Figure 1

[0106] II, take the rubber imitation leather of Examples 1-4 and Comparative Examples 1-4, observe and record the appearance of the product, and test its resilience, wear resistance, tear strength, heat resistance and low temperature resistance respectively, and the test methods are as follows:

[0107] Resilience: according to the determination of resilience of vulcanized rubber in GBT 1681-2009, the thickness of the sample is 2±0.1mm, the resilience value is recorded and converted into resilience value expressed in percentage form, the median value is taken, and the unit is %.

[0108] Wear resistance: according to the determination of wear resistance of vulcanized rubber or thermoplastic rubber in GB / T 9867-2008, test its relative volume wear amount, unit is mm 3 .

[0109] Tear strength: according to the determination of tear strength of vulcanized rubber or thermoplastic rubber in GB / T 529, test its straight angle tear strength, unit is kN / m.

[0110] Heat resistance, 85℃, 72h, according to GB / T 3512-2014 "determination of heat resistance of vulcanized rubber or thermoplastic rubber", 85℃, 72h heat aging test, calculate the change rate of tear strength before and after test, unit is %.

[0111] Low temperature resistance: according to the determination of low temperature brittleness of vulcanized rubber or thermoplastic rubber in GB / T 15256-2014 (multi sample method), prepare type A sample, test and record the limit temperature of low temperature brittleness, unit is ℃.

[0112] The test results are shown in Table 1 below:

[0113]

[0114] ​As shown in Table 1, the rubber simulation leather prepared by the preparation method of the rubber simulation leather has a smooth and transparent surface, foaming lines in the interior, excellent high and low temperature resistance, wear resistance and tear resistance, good resilience, and is suitable for furniture, luggage, automobile interior and the like.

[0115] The above embodiments are the preferred implementation of the present application, in addition to this, the present application can be implemented in other ways, without departing from the concept of the present application, any obvious replacement within the protection scope of the present application.

Claims

1. A method for preparing a rubber simulation leather material, characterized in that: The steps include: (S1) 1.8-2.5 parts of vulcanizing agent A, 1-3 parts of vulcanization accelerator and 100 parts of modified transparent rubber are mixed at 90-110° C. and then calendered into a sheet, which is then cut to obtain a calendered upper sheet; (S2) taking 80 parts by weight of TPR material, 0.1-20 parts of colorant, 5-20 parts of filler, 3-5 parts of plasticizer and 1-3 parts of stabilizer, mixing them at a temperature of 180-230° C., and extruding and granulating them through a twin-screw extruder to obtain a TPR blend; (S3), adding 10-15 parts of a foaming expansion agent, 0.3-0.4 parts of a vulcanizing agent B, 0.2-0.6 parts of a vulcanization accelerator, and 20-30 parts of a modified transparent rubber to the TPR blend by weight, kneading the mixture at a temperature of 60-90° C., and calendering the mixture into a sheet, which is then cut to obtain a calendered bottom sheet; (S4) adding a calendered bottom sheet to a molding device, covering the surface of the calendered bottom sheet with a calendered top sheet, and subjecting the calendered bottom sheet to high temperature molding at 155-170° C. and 10-20 MPa and vulcanization simultaneously, maintaining the temperature for 240-600 seconds to obtain a rubber simulation leather material with a smooth surface and foamed lines inside; The modified transparent rubber comprises the following raw materials in parts by weight: 100 parts of rubber raw material, 15-30 parts of composite reinforcing agent, 2-5 parts of plasticizer, 2-5 parts of active agent and 0.3-1.5 parts of antioxidant; The rubber raw material is at least one of ethylene propylene rubber, isoprene rubber, butyl rubber and styrene butadiene rubber; the composite reinforcing agent is a mixture of at least two of transparent white carbon black, basic magnesium carbonate and sulfonated naphthalene biphenyl copolyarylethersulfone (SPPBES); The filler is a mixture of silane coupling agent modified wollastonite powder and silane coupling agent modified glass fiber in a weight ratio of 8-15:

1.

2. The method for preparing a rubber simulation leather material according to claim 1, wherein: The ratio of the thickness of the calendered bottom sheet to the thickness of the calendered top sheet is 1-6:0.6-2.

3. The method for preparing a rubber imitation leather material according to claim 1, wherein: The vulcanizing agent A is di-tert-butyl peroxide; the vulcanization accelerator is a mixture of accelerator DM and accelerator H in a weight ratio of 2-3:1; and the vulcanizing agent B is a mixture of dicumyl peroxide and sulfur in a weight ratio of 2-2.5:0.

5.

4. The method for preparing a rubber imitation leather material according to claim 1, wherein: The plasticizer is alkylphenyl sulfonate and / or diethylene glycol dibenzoate; the active agent is transparent zinc oxide or activated zinc oxide; and the antioxidant is antioxidant SP and / or antioxidant MB.

5. The method for preparing a rubber simulation leather material according to claim 1, wherein: The TPR material is selected from at least one of TPRXT7025, TPR55A, TPR60A or TPR65A; the plasticizer is a mixture of trioctyl trimellitate and dodecenylsuccinic anhydride in a weight ratio of 1:

1.

6. The method for preparing a rubber imitation leather material according to claim 1, characterized in that: The colorant is at least one of titanium dioxide, lithopone, red iron oxide, permanent yellow, Chinese blue, and phthalocyanine green; the stabilizer is at least one of antioxidant SP, antioxidant CA, antioxidant DLTP, and antioxidant 264.

7. The method for preparing a rubber simulation leather material according to claim 1, characterized in that: The foaming expansion agent is a mixture of sodium bicarbonate and benzenesulfonyl hydrazide in a weight ratio of 5-8:

1.

8. A rubber imitation leather material, characterized by: The rubber imitation leather is prepared by the preparation method of any one of claims 1 to 7.

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