Rubber imitation leather material and preparation method thereof

Abstract

The invention relates to the technical field of rubber simulation materials, in particular to a rubber simulation leather material and a preparation method thereof.The rubber simulation leather material is characterized in that raw materials such as modified transparent rubber are used for preparing a calendering upper sheet so that a transparent and smooth sheet layer can be formed after follow-up mold pressing, and the sheet layer is excellent in high and low temperature resistance, wear resistance and tear resistance and good in rebound resilience; the TPR material, the coloring agent, the filling agent, the plasticizer and the stabilizer are mixed and then extruded and granulated to obtain the TPR blend, so that the TPR blend is more uniformly mixed, the coloring effect of the TPR blend is facilitated, and foaming lines with obvious color and luster can be subsequently presented; adding a foaming expanding agent, modified transparent rubber and other raw materials into the TPR blending material to prepare a calendering bottom sheet; then the calendering upper piece and the calendering bottom piece are compounded under the conditions of high temperature and high pressure, the calendering bottom piece is subjected to micro-foaming while vulcanization is performed, the rubber imitated leather material with a smooth surface and foaming lines inside is obtained, the overall high and low temperature resistance is kept, the wear resistance and tear resistance are excellent, the rebound resilience is good, and the rubber imitated leather material is suitable for the fields of furniture, bags, automotive interiors and the like.

Description

Technical Field

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

[0002] Simulated leather is a material with a similar appearance to real leather. It is usually made of plastics such as polyvinyl chloride (PVC), polyurethane (PU), polyethylene (PE) through special processing. Although these materials can be processed to produce plastic simulated leather with texture, color and gloss close to real leather, they are often hard to the touch and lack the softness and elasticity of real leather. In addition, plastic simulated leather may harden or crack after long-term use. It is not resistant to high and low temperatures, wear resistance and toughness / tear resistance, and is not suitable for 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, wherein a calendered upper sheet is prepared using raw materials such as modified transparent rubber, and a calendered bottom sheet is prepared using raw materials such as TPR material, colorant, foaming expansion agent and modified transparent rubber, and then the calendered bottom sheet and the calendered upper sheet are placed 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, and the inside of the calendered bottom sheet is micro-foamed to obtain a rubber simulation leather material with a smooth surface and foamed lines inside. The rubber simulation leather material has excellent high and low temperature resistance, wear resistance and tear resistance, good resilience, and is suitable for the fields of furniture, luggage and automobile interiors. The preparation method is simple to operate, convenient to control, high in production efficiency, low in 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 genuine leather and has excellent high and low temperature resistance, wear resistance and tear resistance, and good resilience, and is suitable for 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), taking 1.8-2.5 parts of vulcanizing agent A, 1-3 parts of vulcanization accelerator and 100 parts of modified transparent rubber by weight, mixing at 90-110° C. and calendering into a sheet, and cutting to obtain a calendered upper sheet;

[0007] (S2), taking 80 parts 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 by weight, mixing at a temperature of 180-230° C., and extruding and granulating through a twin-screw extruder to obtain a TPR blend;

[0008] (S3), adding 10-15 parts of foaming expansion 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 to the TPR blend by weight, kneading at a temperature of 60-90° C. and calendering into sheets, and cutting to obtain a calendered bottom sheet;

[0009] (S4) adding a calendered bottom sheet into a molding device, covering the surface of the calendered top sheet on the calendered bottom sheet, and vulcanizing at a high temperature of 155-170° C. and 10-20 MPa for 240-600 seconds to obtain a rubber simulation leather material with a smooth surface and foamed texture inside.

[0010] The preparation method of the rubber simulation leather material comprises the following steps: mixing vulcanizing agent A, a vulcanization accelerator and a modified transparent rubber at 90-110 DEG C and then calendering to form a calendered upper sheet, so as to form a transparent and smooth sheet layer after subsequent molding, and the sheet layer has excellent high and low temperature resistance, abrasion resistance and tear resistance, and good resilience; then mixing TPR material, a colorant, a filler, a plasticizer and a stabilizer at 180-230 DEG C and then extruding and granulating to obtain a TPR blend, which is more evenly mixed, is conducive to the coloring effect of the TPR blend, is convenient for the subsequent presentation of foaming lines with obvious colors, improves the flexibility and ductility of the TPR material, and maintains good weather resistance, high and low temperature resistance and tear resistance; adding a foaming expansion agent, a vulcanizing agent B, The vulcanization accelerator and the modified transparent rubber are kneaded at 60-90°C and then calendered to form a calendered bottom sheet, which is beneficial to avoid premature and rapid foaming of the foaming expansion agent and fully mix the raw materials. The small amount of modified transparent rubber mixed in the calendered bottom sheet can improve the high and low temperature resistance and tear resistance of the calendered bottom sheet, and can promote its integrated molding with the calendered upper sheet. Then, the calendered bottom sheet and the calendered upper sheet are placed in the molding equipment. During the molding process, the calendered upper sheet and the calendered bottom sheet are compounded and vulcanized under high temperature and high pressure conditions, and the calendered bottom sheet is micro-foamed at the same time, so as to obtain a rubber simulation leather material with a smooth surface and foaming patterns inside, which maintains the overall high and low temperature resistance, excellent wear resistance and tear resistance, and good resilience, and is suitable for furniture, luggage, and automotive interiors. In step (S4), the molding conditions are controlled at 155-170°C, 10-20Mpa, and maintained for 240-600s, which ensures complete vulcanization of the rubber simulation leather material and improves its wear resistance, and promotes the foaming and expansion of the calendered bottom sheet to present a foaming pattern similar to the appearance of genuine leather, meeting the application requirements. The processing temperatures of each section of the twin-screw extruder are: 150-160°C, 160-170°C, 170-180°C, 170-180°C, the die head temperature is 170-175°C, and the screw aspect 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] By adopting the above technical scheme, 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 beneficial to the formation of foaming lines on the calendered bottom sheet during the molding process. The rubber simulation leather with foaming lines inside can be more intuitively 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 diisopropylbenzene peroxide and sulfur in a weight ratio of 2-2.5:0.5.

[0014] By adopting the above technical solution, the calendered upper sheet uses the above vulcanizing agent A and vulcanization accelerator, which has a better vulcanization effect and is more beneficial to the transparency and mechanical properties of the transparent and smooth sheet layer.

[0015] Preferably, 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 activator and 0.3-1.5 parts of antioxidant.

[0016] The above technical scheme is adopted, with special rubber raw materials as the main body, maintaining basic transparency, high and low temperature resistance, wear resistance, tear resistance and elasticity; the doping of composite reinforcing agents is synergistically beneficial to improving the transparency of the modified transparent rubber, and the reinforcement effect is good, which can significantly improve the tensile strength, tear strength and wear resistance of the rubber, and improve the heat resistance effect; the added plasticizer is beneficial to improving the plasticity of the rubber, so that the rubber products show 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 calendered upper sheet after molding and vulcanization smoother and brighter; the added activator is beneficial to promoting the vulcanization of the modified transparent rubber, and is beneficial to improving the wear resistance, while avoiding the influence on the transparency.

[0017] Preferably, 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 poly(phenylene ether sulfone) (SPPBES).

[0018] More preferably, the rubber raw material is ethylene propylene rubber, isoprene rubber and styrene butadiene rubber mixed in a weight ratio of 3-4:3-4:1, with the above-mentioned specially compounded rubber raw materials as the main body, maintaining basic transparency, high and low temperature resistance, wear resistance, tear resistance and elasticity; the composite reinforcing agent is transparent white carbon black, basic magnesium carbonate and sulfonated polyphenylene ether sulfone (SPPBES) mixed in a weight ratio of 5:2-3:1, and the composite reinforcing agent is soaked in silane coupling agent KH550 and then dried for use to improve the compatibility and dispersibility of the composite reinforcing agent in rubber. The doping of the above-mentioned composite reinforcing agent is synergistically beneficial 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 effect. Further, the average particle size of the composite reinforcing agent is 15-30μm.

[0019] Preferably, 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.

[0020] By adopting the above technical solution, adding the above plasticizer is conducive to improving the plasticity of rubber, so that rubber products show better elasticity and toughness during processing and use, and is conducive to improving the heat resistance and cold resistance of rubber, so that it can still maintain stable performance under extreme temperature conditions, and is also conducive to making the surface of the calendered upper sheet smoother and brighter after molding and vulcanization; adding the above active agent is conducive to promoting the vulcanization of modified transparent rubber, and is conducive to improving wear resistance while avoiding the impact on transparency. The above antioxidant is conducive to improving the anti-oxidation and anti-aging effect of modified transparent rubber, extending the service life, and avoiding the impact on transparency.

[0021] Preferably, the TPR material is selected from at least one of 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; the plasticizer is a mixture of trioctyl trimellitate and dodecenyl succinic anhydride in a weight ratio of 1:1.

[0022] By adopting the above technical solution, the above TPR material has the characteristics of both rubber and thermoplastics, has excellent elasticity, weather resistance and processing performance, has a bright surface, has good reflective performance, is easy to color, and the foaming texture presented by the foaming agent after molding in the calendered film is similar to the appearance of leather, meeting the application requirements. The above-mentioned compound filler is used to improve its compatibility and dispersibility in the TPR material, which can not only improve the mechanical properties of the TPR material such as tensile strength and tear strength, but also improve its weather resistance, wear resistance and fatigue resistance, effectively share the load of the TPR material during the stress process, thereby improving the overall performance of the composite material. Furthermore, the length of the silane coupling agent modified glass fiber is 3mm. The plasticizer is a mixture of trioctyl trimellitate and dodecenyl succinic anhydride in a weight ratio of 1:1, which increases the plasticity of the TPR material, makes it easier to process, enhances its flexibility and ductility, and reasonably controls the amount of the plasticizer to avoid an adverse effect on the strength of the material due to increased brittleness caused by excessive amounts of the plasticizer.

[0023] Preferably, the colorant is at least one of titanium dioxide, lithopone, red iron oxide, permanent yellow, cyanine 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 benzenesulfonyl hydrazide in a weight ratio of 5-8:1.

[0025] By adopting the above technical solution, the foaming texture of the TPR material in the calendered bottom sheet after molding and the reaction with the foaming agent is similar to the appearance of genuine leather, which meets the application requirements.

[0026] Another object of the present invention is achieved through the following technical solution: a rubber simulation leather material is prepared by the preparation method of the rubber simulation leather material as described above.

[0027] The beneficial effects of the present invention are as follows: the preparation method of the rubber simulation leather material of the present invention uses modified transparent rubber and other raw materials to prepare a calendered upper sheet, and then uses TPR material, colorant, foaming expansion agent and modified transparent rubber and other raw materials to prepare a calendered bottom sheet, and then puts the calendered bottom sheet and the calendered upper sheet into a molding device, and during the molding process, the calendered upper sheet and the calendered bottom sheet are compounded and vulcanized under high temperature and high pressure conditions, and the calendered bottom sheet is micro-foamed inside to obtain a rubber simulation leather material with a smooth surface and foamed lines inside, which has excellent high and low temperature resistance, wear resistance and tear resistance, good resilience, and is suitable for the fields of furniture, luggage and automobile interiors; the preparation method is simple to operate, convenient to control, high in production efficiency, low in production cost, and can be used for large-scale production.

[0028] The rubber simulated leather material of the present invention can simulate the appearance of genuine leather and has excellent high and low temperature resistance, wear resistance and tear resistance, as well as good resilience, and is suitable for the fields of furniture, luggage, and automobile interiors. BRIEF DESCRIPTION OF THE DRAWINGS

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

[0030] In order to facilitate the understanding of those skilled in the art, the present invention is further described below in conjunction with embodiments and drawings. The contents mentioned in the implementation modes are not intended to limit the present invention.

[0031] Example 1

[0032] A method for preparing a rubber simulation leather material comprises the following steps:

[0033] (S1), taking 2 parts of vulcanizing agent A, 2 parts of vulcanization accelerator and 100 parts of modified transparent rubber by weight, kneading at 100° C. and calendering into a sheet, and 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°C, and extruding and granulating through a twin-screw extruder to obtain a TPR blend;

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

[0036] (S4) Add a calendered bottom sheet to a molding device, cover the surface of the calendered top sheet on the calendered bottom sheet, and vulcanize at the same time by high temperature molding at 160° C. and 15 MPa for 420 seconds to obtain a rubber simulation leather material with a smooth surface and foamed texture inside.

[0037] Wherein, in the step (S2), the processing temperatures of each section of the twin-screw extruder are: 155°C, 165°C, 170°C, 180°C, the die head temperature is 175°C, and the screw aspect ratio is 16:1.

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

[0039] 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 2.5:1; and the vulcanizing agent B is a mixture of diisopropylbenzene peroxide and sulfur at a weight ratio of 2.3:0.5.

[0040] The modified transparent rubber comprises the following raw materials in parts by weight: 100 parts of rubber raw materials, 22 parts of composite reinforcing agent, 4 parts of plasticizer, 4 parts of activator 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 poly(phenylene ether sulfone) (SPPBES) in a weight ratio of 5:2.5:1, 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 20 μm.

[0042] The plasticizer is diethylene glycol dibenzoate; the activator 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 wollastonite powder modified by silane coupling agent KH550 and glass fiber modified by silane coupling agent KH550 in a weight ratio of 10:1, and the length of the glass fiber modified by silane coupling agent KH550 is 3 mm; 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; the stabilizer is a mixture of antioxidant SP and antioxidant CA in a weight ratio of 4:1.

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

[0046] Example 2

[0047] A method for preparing a rubber simulation leather material comprises 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, kneading at 90°C and calendering into a sheet, and cutting to obtain a calendered upper 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 185°C, and extruding and granulating through a twin-screw extruder to obtain a TPR blend;

[0050] (S3), adding 10 parts of foaming expansion 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, kneading at 60° C. and calendering into sheets, and cutting to obtain a calendered bottom sheet;

[0051] (S4) adding a calendered bottom sheet into 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° C. and 10 MPa and vulcanization at the same time, and maintaining the temperature for 600 seconds, thereby obtaining a rubber simulation leather material with a smooth surface and foamed texture inside.

[0052] Wherein, in the step (S2), the processing temperatures of each section of the twin-screw extruder are: 155°C, 165°C, 170°C, 180°C, the die head temperature is 175°C, and the screw aspect ratio is 16:1.

[0053] The ratio of the thickness of the calendered bottom sheet to the thickness of 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 in a weight ratio of 2:1; and the vulcanizing agent B is a mixture of diisopropylbenzene peroxide and sulfur in a weight ratio of 2:0.5.

[0055] The modified transparent rubber comprises the following raw materials in parts by weight: 100 parts of rubber raw materials, 15 parts of composite reinforcing agent, 2 parts of plasticizer, 2 parts of activator and 0.3 parts of antioxidant.

[0056] The rubber raw material is a mixture of ethylene propylene rubber, isoprene rubber and styrene butadiene rubber in a weight ratio of 3:3:1; the composite reinforcing agent is a mixture of transparent white carbon black, basic magnesium carbonate and sulfonated poly(phenylene ether sulfone) (SPPBES) in 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 activator is activated zinc oxide; and the antioxidant is a mixture of antioxidant SP and antioxidant MB in a weight ratio of 4:1.

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

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

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

[0061] Example 3

[0062] A method for preparing a rubber simulation leather material 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, kneading at 100° C. and calendering into a sheet, and 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, mixing at 230°C, and extruding and granulating through a twin-screw extruder to obtain a TPR blend;

[0065] (S3), adding 15 parts of foaming expansion 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, kneading at 90° C. and calendering into sheets, and cutting to obtain a calendered bottom sheet;

[0066] (S4) Add a calendered bottom sheet to a molding device, cover the surface of the calendered top sheet on the calendered bottom sheet, and vulcanize at the same time by high temperature molding at 170° C. and 20 MPa for 240 seconds to obtain a rubber simulation leather material with a smooth surface and foamed texture inside.

[0067] Wherein, in the step (S2), the processing temperatures of each section of the twin-screw extruder are: 155°C, 165°C, 170°C, 180°C, the die head temperature is 175°C, and the screw aspect ratio is 16:1.

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

[0069] 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 3:1; and the vulcanizing agent B is a mixture of diisopropylbenzene peroxide and sulfur in a weight ratio of 2.5:0.5.

[0070] The modified transparent rubber comprises the following raw materials in parts by weight: 100 parts of rubber raw materials, 30 parts of composite reinforcing agent, 5 parts of plasticizer, 5 parts of activator 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 poly(phenylene ether sulfone) (SPPBES) in a weight ratio of 5:3:1, 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 30 μm.

[0072] The plasticizer is diethylene glycol dibenzoate; the activator 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 wollastonite powder modified by silane coupling agent KH550 and glass fiber modified by silane coupling agent KH550 in a weight ratio of 15:1, and the length of the glass fiber modified by silane coupling agent KH550 is 3 mm; 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 expansion agent is a mixture of sodium bicarbonate and benzenesulfonyl hydrazide in a weight ratio of 8:1.

[0076] Example 4

[0077] A method for preparing a rubber simulation leather material comprises the following steps:

[0078] (S1), taking 2.2 parts of vulcanizing agent A, 2 parts of vulcanization accelerator and 100 parts of modified transparent rubber by weight, kneading at 100° C. and calendering into a sheet, and 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 200° C., and extruding and granulating through a twin-screw extruder to obtain a TPR blend;

[0080] (S3), adding 13 parts of foaming expansion agent, 0.35 parts of vulcanizing agent B, 0.4 parts of vulcanization accelerator and 28 parts of modified transparent rubber to the TPR blend by weight, kneading at 80° C. and calendering into sheets, and cutting to obtain a calendered bottom sheet;

[0081] (S4) adding a calendered bottom sheet into 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 160° C. and 18 MPa and vulcanization at the same time, and maintaining the temperature for 300 seconds, thereby obtaining a rubber simulation leather material with a smooth surface and foamed texture inside.

[0082] Wherein, in the step (S2), the processing temperatures of each section of the twin-screw extruder are: 155°C, 165°C, 170°C, 180°C, the die head temperature is 175°C, and the screw aspect ratio is 16:1.

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

[0084] 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 2.5:1; and the vulcanizing agent B is a mixture of diisopropylbenzene peroxide and sulfur at a weight ratio of 2.2:0.5.

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

[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 poly(phenylene ether sulfone) (SPPBES) in a weight ratio of 5:2.3:1, 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 20 μm.

[0087] The plasticizer is diethylene glycol dibenzoate; the activator 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 wollastonite powder modified by silane coupling agent KH550 and glass fiber modified by silane coupling agent KH550 in a weight ratio of 12:1, and the length of the glass fiber modified by silane coupling agent KH550 is 3 mm; 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; the stabilizer is a mixture of antioxidant SP and antioxidant CA in a weight ratio of 4:1.

[0090] The foaming expansion 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 this comparative example and Example 1 is:

[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 this comparative example and Example 1 is:

[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 this comparative example and Example 1 is:

[0099] In the step (S4), the molding conditions are 160° C., normal pressure, and maintained for 420 seconds.

[0100] Comparative Example 4

[0101] The difference between this comparative example and Example 1 is:

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

[0103] Example 5

[0104] Performance Testing

[0105] 1. The rubber simulation leather material sample of Example 2 is as follows Figure 1 As shown by Figure 1 It can be seen that the rubber simulated leather sample has the characteristics of a smooth and transparent surface and obvious foaming lines inside.

[0106] II. Take the rubber simulation leather materials of Examples 1-4 and Comparative Examples 1-4, observe and record the product appearance, and test their resilience, abrasion resistance, tear strength, heat resistance and low temperature resistance respectively. The test methods are as follows:

[0107] Rebound resilience: According to GBT 1681-2009, the rebound resilience of vulcanized rubber is measured. The sample thickness is 2±0.1mm. The rebound value is recorded and converted into a rebound value expressed in percentage form. The median value is taken in %.

[0108] Wear resistance: According to GB / T 9867-2008 Determination of wear resistance of vulcanized rubber or thermoplastic rubber, the relative volume wear loss is tested in mm. 3 .

[0109] Tear strength: According to GB / T 529 Determination of tear strength of vulcanized rubber or thermoplastic rubber, the right-angle tear strength is tested, and the unit is kN / m.

[0110] Heat resistance, 85℃, 72h. According to GB / T 3512-2014 “Hot air accelerated aging and heat resistance test for vulcanized rubber or thermoplastic rubber”, a heat aging test was carried out at 85℃, 72h. The change rate of tear strength before and after the test was calculated in %.

[0111] Low temperature resistance: According to GB / T 15256-2014 Determination of low temperature brittleness of vulcanized rubber or thermoplastic rubber (multiple specimen method), prepare type A specimens, test and record the limit temperature of low temperature brittleness in °C.

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

[0113]

[0114] As can be seen from Table 1 above, the preparation method of the rubber simulation leather material of the present invention prepares a rubber simulation leather material with a smooth and transparent surface and foaming patterns inside, which maintains excellent overall high and low temperature resistance, wear resistance and tear resistance, and good resilience, and is suitable for furniture, luggage, and automotive interiors.

[0115] The above embodiments are preferred implementation schemes of the present invention. In addition, the present invention may also be implemented in other ways. Any obvious replacement without departing from the concept of the present invention is within the protection scope of the present invention.

Claims

1. A method for preparing a rubber simulation leather material, characterized in that: The steps include: (S1), taking 1.8-2.5 parts of vulcanizing agent A, 1-3 parts of vulcanization accelerator and 100 parts of modified transparent rubber by weight, mixing at 90-110° C. and calendering into a sheet, and cutting to obtain a calendered upper sheet; (S2), taking 80 parts 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 by weight, mixing at a temperature of 180-230° C., and extruding and granulating through a twin-screw extruder to obtain a TPR blend; (S3), adding 10-15 parts of foaming expansion 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 to the TPR blend by weight, kneading at a temperature of 60-90° C. and calendering into sheets, and cutting to obtain a calendered bottom sheet; (S4) adding a calendered bottom sheet into a molding device, covering the surface of the calendered top sheet on the calendered bottom sheet, and vulcanizing at a high temperature of 155-170° C. and 10-20 MPa for 240-600 seconds to obtain a rubber simulation leather material with a smooth surface and foamed texture inside.

2. The method for preparing a rubber simulation leather material according to claim 1, characterized in that: 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 simulation leather material according to claim 1, characterized in that: 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 diisopropylbenzene peroxide and sulfur in a weight ratio of 2-2.5:0.

5.

4. The method for preparing a rubber simulation leather material according to claim 1, characterized in that: The modified transparent rubber comprises the following raw materials in parts by weight: 100 parts of rubber raw materials, 15-30 parts of composite reinforcing agent, 2-5 parts of plasticizer, 2-5 parts of activator and 0.3-1.5 parts of antioxidant.

5. The method for preparing a rubber simulation leather material according to claim 4, characterized in that: 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 poly(phenylene ether sulfone) (SPPBES).

6. The method for preparing a rubber simulation leather material according to claim 4, characterized in that: 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.

7. The method for preparing a rubber simulation leather material according to claim 1, characterized in that: The TPR material is selected from at least one of TPRXT7025, 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; the plasticizer is a mixture of trioctyl trimellitate and dodecenyl succinic anhydride in a weight ratio of 1:

1.

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

9. 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.

10. A rubber imitation leather material, characterized in that: The rubber simulation leather material is prepared by the preparation method of any one of claims 1 to 9.

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