EVA composite material for shoes and preparation method thereof

Abstract

The invention relates to an EVA composite material for shoes. The EVA composite material is prepared from the following raw materials in parts by weight: 60-65 parts of EVA, 10-15 parts of POE (Polyolefin Elastomer), 7-11 parts of filler modifier, 5-8 parts of modified clay agent, 5-8 parts of zinc oxide, 2-4 parts of foaming agent, 3-5 parts of cross-linking agent and 2-4 parts of calcium stearate. According to the EVA composite material disclosed by the invention, the EVA and the POE elastomer are used as base materials, the zinc oxide, the foaming agent, the cross-linking agent and the calcium stearate are added as functional aids, and the filler modifier and the modified clay agent are added as blending synergists, so that the EVA composite material and the POE elastomer are matched and coordinated to achieve a common synergistic effect; the obtained material product has excellent skid resistance, wear resistance and elasticity balance coordination improvement, and has remarkable scrubbing resistance and weather resistance stability effects.

Description

Technical Field

[0001] The present invention relates to the technical field of EVA materials, and particularly relates to an EVA composite material for shoes and a preparation method thereof. Background Art

[0002] The design and manufacture of footwear and sports equipment involve multiple factors, from aesthetics to comfort and feel, to performance and durability. Although designs and fashions may change rapidly, the demand for enhanced performance in the footwear and sports equipment market remains unchanged. The EVA materials currently used in soles have poor anti-slip performance, and at the same time, the wear resistance and elastic properties of the products are low. It is difficult to balance and coordinate the improvement of anti-slip, wear resistance, and elasticity of the products, and the products have poor washability and weather resistance stability, which limits the use efficiency of the products. Summary of the Invention

[0003] Aiming at the defects of the prior art, the purpose of the present invention is to provide an EVA composite material for shoes and a preparation method thereof to solve the problems raised in the above background art.

[0004] The present invention adopts the following technical solutions to solve the technical problems: The present invention provides an EVA composite material for shoes, and the EVA composite material comprises the following raw materials in parts by weight: 60 - 65 parts of EVA, 10 - 15 parts of POE elastomer, 7 - 11 parts of filler modifier, 5 - 8 parts of modified clay agent, 5 - 8 parts of zinc oxide, 2 - 4 parts of foaming agent, 3 - 5 parts of crosslinking agent, 2 - 4 parts of calcium stearate.

[0005] Preferably, the EVA composite material comprises the following raw materials in parts by weight: 62.5 parts of EVA, 12.5 parts of POE elastomer, 9 parts of filler modifier, 6.5 parts of modified clay agent, 6.5 parts of zinc oxide, 3 parts of foaming agent, 4 parts of crosslinking agent, 3 parts of calcium stearate.

[0006] Preferably, the foaming agent is AC foaming agent; the crosslinking agent is DCP; the VA content in the EVA is 18 - 20%, and the MFI is 1.5 - 2.5 g / min; the POE elastomer is ethylene - octene copolymer, and the melt index is 5 g / 10 min under the conditions of 190 °C and 2.16 Kg.

[0007] Preferably, the preparation method of the filler modifier is: S01: Mix nano - titanium dioxide, zirconium oxide, and sodium silicate solution evenly according to the weight ratio of (2 - 5):(1 - 3):(5 - 7) to obtain nano - titanium dioxide solution; 3-5 parts of nano titanium dioxide liquid and 1-3 parts of nano silica sol are added to 4-7 parts of dopamine hydrochloride solution, and then 1-2 parts of lanthanum oxide are added and stirred sufficiently to obtain a nano titanium dioxide modifier; S02: preheating barium carbonate at 60-65°C for 1 hour, immersing the preheated barium carbonate in a boron nitride solution with a volume of 3-5 times the total volume of barium carbonate, and subjecting the solution to ultrasonic treatment. After the ultrasonic treatment is completed, the solution is filtered and dried to obtain a barium carbonate polyvalent boron nitride agent. S03: Nano titanium dioxide modifier and barium carbonate polyboron nitride agent are mixed in a weight ratio of 5:3 and ball-milled at a speed of 1000 r / min for 1 h. After the ball milling is completed, the mixture is filtered and dried to obtain a filler modifier.

[0008] Preferably, the mass fraction of the sodium silicate solution is 4-7%; the mass fraction of the dopamine hydrochloride solution is 2-5%; the ultrasonic power of the immersion ultrasonic treatment is 450-500W, and the ultrasonic treatment is for 1 hour.

[0009] Preferably, the boron nitride solution comprises the following raw materials in parts by weight: 4 to 6 parts of boron nitride, 2 to 3 parts of barium sulfate, 3 to 5 parts of cordierite, 6 to 8 parts of 4% by mass sodium citrate solution, and 1 to 2 parts of 5% by mass urea solution.

[0010] Preferably, the preparation method of the modified clay agent is: S11: Stir the clay in a sufficient amount of acid solution, then wash, filter and dry. Treat the dried clay at 130-140°C for 1h. After the treatment, cool to 55°C and keep warm. S12: Preparation of modified composite liquid: S121: adding 3-5 parts of mica powder and 2-3 parts of magnesium oxide to 5-8 parts of sodium lignin sulfonate solution, and then adding 1-3 parts of silane coupling agent KH550, stirring evenly, to obtain a first modified solution; S122: adding 2-4 parts of silicon carbide and 3-5 parts of yttrium oxide to 5-8 parts of 4% by mass chitosan solution and mixing them thoroughly to obtain a second modified solution; S123: fully blending the first modified liquid and the second modified liquid in a weight ratio of (5-7):4 to obtain a modified composite liquid; S13: stirring the heat-insulated clay and the modified composite liquid at a weight ratio of 3:5 for modification treatment, filtering and drying after the stirring is completed to obtain a modified clay agent.

[0011] Preferably, the mass fraction of the acid solution is 2-5%; the mass fraction of the sodium lignin sulfonate solution is 5-8%.

[0012] Preferably, the stirring speed of the stirring modification treatment is 450-550 r / min, and the stirring time is 1 h.

[0013] The present invention also provides a method for preparing an EVA composite material for shoes, comprising the following steps: Weigh the raw materials according to parts by weight, mix the raw materials evenly in a kneader, knead them at 110-120 °C for 10 min, granulate them after open milling, and then mold them in a mold. The molding temperature is 215 °C, the molding pressure is 15 Mpa, and the molding time is 20 min to obtain the EVA composite material for shoes of the present invention.

[0014] Compared with the prior art, the present invention has the following beneficial effects: The EVA composite material of the present invention uses EVA and POE elastomer as matrix materials, adds zinc oxide, foaming agent, crosslinking agent and calcium stearate as functional additives, adds filler modifier and modified clay agent as blending synergistic agents, and uses the two raw materials to cooperate and coordinate with each other to achieve common synergistic effects. The obtained material product has excellent anti-slip, wear-resistant and elastic balance coordination improvement, and the product has remarkable effects of washing resistance and weather resistance stability; The filler modifier is made by mutually blending a nano-titanium dioxide modifier and a barium carbonate complexed boron nitride agent. The nano-titanium dioxide modifier is made by blending nano-titanium dioxide, zirconium oxide and sodium silicate solution to form a nano-titanium dioxide solution. Through the co-allocation and synergistic effect of the raw materials, and further through the co-allocation improvement of nano-silica sol, hydrochloric acid dopamine solution and lanthanum oxide, the obtained nano-titanium dioxide modifier optimizes the system performance in the system and better blends and coordinates with the barium carbonate complexed boron nitride agent. The barium carbonate complexed boron nitride agent is preheated with barium carbonate, and then immersed in a boron nitride solution for ultrasonic treatment. Boron nitride, barium sulfate and cordierite in the boron nitride solution are used as matrix materials, and then blended with a 4% sodium citrate solution and a 5% urea solution by mass fraction to further improve barium carbonate. Furthermore, the barium carbonate complexed boron nitride agent has a better synergistic effect with the nano-titanium dioxide modifier, and the performance of the product is further improved; The modified clay agent is prepared by stirring clay sufficiently in a sufficient amount of acid solution, then washing, filtering and drying. The dried clay is treated at 130-140 °C for 1 h, and after the treatment is completed, it is cooled to 55 °C to optimize the activity efficiency of the clay, and then further improved and optimized by a modified composite solution. The first modified solution and the second modified solution in the modified composite solution are blended and improved. At the same time, the first modified solution uses mica powder, magnesium oxide, lignosulfonate solution and silane coupling agent KH550. Through the coordination and optimization of the raw materials, and then blended with the second modified solution. Silicon carbide and yttrium oxide in the second modified solution are combined with a 4% chitosan solution by mass fraction. Through the co-allocation and synergistic effect of the raw materials, the coordination between the modified clay agent and the filler modifier is further enhanced, and thus the performance of the product is further improved. Specific embodiments

[0015] The following is a clear and complete description of the technical solutions in the embodiments of the present invention in conjunction with specific embodiments. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0016] The EVA composite material for shoes of this embodiment comprises the following raw materials in parts by weight: EVA 60-65 parts, POE elastomer 10-15 parts, filler modifier 7-11 parts, modified clay agent 5-8 parts, zinc oxide 5-8 parts, foaming agent 2-4 parts, cross-linking agent 3-5 parts, calcium stearate 2-4 parts.

[0017] The EVA composite material of the present embodiment comprises the following raw materials in parts by weight: EVA 62.5 parts, POE elastomer 12.5 parts, filler modifier 9 parts, modified clay agent 6.5 parts, zinc oxide 6.5 parts, foaming agent 3 parts, crosslinking agent 4 parts, calcium stearate 3 parts.

[0018] The foaming agent of this embodiment is AC foaming agent; the cross-linking agent is DCP; the VA content in the EVA is 18-20%, and the MFI is 1.5-2.5 g / min; the POE elastomer is ethylene-octene copolymer, and the melt index is 190°C, and 5g / 10min under 2.16Kg conditions.

[0019] The preparation method of the filler modifier of this embodiment is: S01: Evenly blend nano titanium dioxide, zirconium oxide and sodium silicate solution in a weight ratio of (2-5): (1-3): (5-7) to obtain nano titanium dioxide liquid; 3-5 parts of nano titanium dioxide liquid and 1-3 parts of nano silica sol are added to 4-7 parts of dopamine hydrochloride solution, and then 1-2 parts of lanthanum oxide are added and stirred sufficiently to obtain a nano titanium dioxide modifier; S02: preheating barium carbonate at 60-65°C for 1 hour, immersing the preheated barium carbonate in a boron nitride solution with a volume of 3-5 times the total volume of barium carbonate, and subjecting the solution to ultrasonic treatment. After the ultrasonic treatment is completed, the solution is filtered and dried to obtain a barium carbonate polyvalent boron nitride agent. S03: Nano titanium dioxide modifier and barium carbonate polyboron nitride agent are mixed in a weight ratio of 5:3 and ball-milled at a speed of 1000 r / min for 1 h. After the ball milling is completed, the mixture is filtered and dried to obtain a filler modifier.

[0020] The mass fraction of the sodium silicate solution in this embodiment is 4-7%; the mass fraction of the dopamine hydrochloride solution is 2-5%; the ultrasonic power of the immersion ultrasonic treatment is 450-500W, and the ultrasonic treatment is performed for 1 hour.

[0021] The boron nitride solution of this embodiment includes the following raw materials in parts by weight: 4-6 parts of boron nitride, 2-3 parts of barium sulfate, 3-5 parts of cordierite, 6-8 parts of 4% sodium citrate solution and 1-2 parts of 5% urea solution.

[0022] The preparation method of the modified clay agent of this embodiment is: S11: Stir the clay in a sufficient amount of acid solution, then wash, filter and dry. Treat the dried clay at 130-140°C for 1h. After the treatment, cool to 55°C and keep warm. S12: Preparation of modified composite liquid: S121: adding 3-5 parts of mica powder and 2-3 parts of magnesium oxide to 5-8 parts of sodium lignin sulfonate solution, and then adding 1-3 parts of silane coupling agent KH550, stirring evenly, to obtain a first modified solution; S122: adding 2-4 parts of silicon carbide and 3-5 parts of yttrium oxide to 5-8 parts of 4% by mass chitosan solution and mixing them thoroughly to obtain a second modified solution; S123: fully blending the first modified liquid and the second modified liquid in a weight ratio of (5-7):4 to obtain a modified composite liquid; S13: stirring the heat-insulated clay and the modified composite liquid at a weight ratio of 3:5 for modification treatment, filtering and drying after the stirring is completed to obtain a modified clay agent.

[0023] The mass fraction of the acid solution in this embodiment is 2-5%; the mass fraction of the sodium lignin sulfonate solution is 5-8%.

[0024] The stirring speed of the stirring modification treatment in this embodiment is 450-550 r / min, and the stirring time is 1 h.

[0025] A method for preparing an EVA composite material for shoes in this embodiment comprises the following steps: The raw materials are weighed according to weight parts, mixed uniformly in an internal mixer, and internally kneaded at 110-120° C. for 10 minutes, granulated after open kneading, and then molded in a mold at a molding temperature of 215° C., a molding pressure of 15 MPa, and molding for 20 minutes to obtain the EVA composite material for shoes of the present invention.

[0026] Example 1. The EVA composite material for shoes of this embodiment comprises the following raw materials in parts by weight: 60 parts of EVA, 10 parts of POE elastomer, 7 parts of filler modifier, 5 parts of modified clay agent, 5 parts of zinc oxide, 2 parts of foaming agent, 3 parts of crosslinking agent, 2 parts of calcium stearate.

[0027] The foaming agent in this example is AC foaming agent; the crosslinking agent is DCP; the VA content in the EVA is 18%, and the MFI is 1.5 g / min; the POE elastomer is ethylene-octene copolymer, and the melt index is 5 g / 10 min under the conditions of 190 °C and 2.16 Kg.

[0028] The preparation method of the filler modifier in this example is as follows: S01: Mix 2 parts of nano-titanium dioxide, 1 part of zirconium oxide and 5 parts of sodium silicate solution by weight to obtain nano-titanium dioxide solution; Add 3 parts of nano-titanium dioxide solution and 1 part of nano-silica sol to 4 parts of hydrochloric acid dopamine solution, and then add 1 part of lanthanum oxide, stir well to obtain nano-titanium dioxide modifier; S02: Preheat barium carbonate at 60 °C for 1 h, immerse the preheated barium carbonate into 3 times the total amount of boron nitride solution of barium carbonate and perform ultrasonic treatment. After the ultrasonic treatment, filter and dry to obtain barium carbonate complex boron nitride agent; S03: Mix and ball-mill the nano-titanium dioxide modifier and the barium carbonate complex boron nitride agent according to the weight ratio of 5:3. The ball-milling speed is 1000 r / min, and the ball-milling time is 1 h. After the ball-milling is completed, filter and dry to obtain the filler modifier.

[0029] The mass fraction of the sodium silicate solution in this example is 4%; the mass fraction of the hydrochloric acid dopamine solution is 2%; the ultrasonic power of the immersion ultrasonic treatment is 450 W, and the ultrasonic treatment is 1 h.

[0030] The boron nitride solution in this example includes the following raw materials in parts by weight: 4 parts of boron nitride, 2 parts of barium sulfate, 3 parts of cordierite, 6 parts of 4% sodium citrate solution and 1 part of 5% urea solution.

[0031] The preparation method of the modified clay agent in this example is as follows: S11: Stir the clay in a sufficient amount of acid solution, then wash with water, filter and dry. Treat the dried clay at 130 °C for 1 h, and after the treatment, cool to 55 °C and keep warm; S12: Preparation of modified composite liquid: S121: Add 3 parts of mica powder and 2 parts of magnesium oxide to 5 parts of sodium lignosulfonate solution, and then add 1-3 parts of silane coupling agent KH550, stir evenly to obtain the first modified liquid; S122: Add 2 parts of silicon carbide and 3 parts of yttrium oxide to 5 parts of 4% chitosan solution and mix well to obtain the second modified liquid; S123: fully blending the first modified liquid and the second modified liquid at a weight ratio of 5:4 to obtain a modified composite liquid; S13: stirring the heat-insulated clay and the modified composite liquid at a weight ratio of 3:5 for modification treatment, filtering and drying after the stirring is completed to obtain a modified clay agent.

[0032] The mass fraction of the acid solution in this embodiment is 2%; the mass fraction of the sodium lignin sulfonate solution is 5%.

[0033] The stirring speed of the stirring modification treatment in this embodiment is 450 r / min, and the stirring time is 1 hour.

[0034] A method for preparing an EVA composite material for shoes in this embodiment comprises the following steps: The raw materials are weighed according to weight parts, mixed uniformly in an internal mixer, and internally kneaded at 110° C. for 10 minutes, granulated after open kneading, and then molded in a mold at a molding temperature of 215° C., a molding pressure of 15 MPa, and molding for 20 minutes to obtain the EVA composite material for shoes of the present invention.

[0035] Example 2. The EVA composite material for shoes of this embodiment comprises the following raw materials in parts by weight: EVA 65 parts, POE elastomer 15 parts, filler modifier 11 parts, modified clay agent 8 parts, zinc oxide 8 parts, foaming agent 4 parts, crosslinking agent 5 parts, calcium stearate 4 parts.

[0036] The foaming agent of this embodiment is AC foaming agent; the cross-linking agent is DCP; the VA content in the EVA is 20%, and the MFI is 2.5g / min; the POE elastomer is ethylene-octene copolymer, and the melt index is 190°C, and 5g / 10min under 2.16Kg conditions.

[0037] The preparation method of the filler modifier of this embodiment is: S01: Evenly blend nano titanium dioxide, zirconium oxide and sodium silicate solution in a weight ratio of 5:3:7 to obtain nano titanium dioxide liquid; 5 parts of nano titanium dioxide liquid and 3 parts of nano silica sol are added to 7 parts of dopamine hydrochloride solution, and then 2 parts of lanthanum oxide are added and stirred sufficiently to obtain a nano titanium dioxide modifier; S02: preheating barium carbonate at 65°C for 1 hour, immersing the preheated barium carbonate in a boron nitride solution with a volume 5 times the total volume of barium carbonate, and subjecting the solution to ultrasonic treatment. After the ultrasonic treatment is completed, the solution is filtered and dried to obtain a barium carbonate polytonic boron nitride agent; S03: Mix the nano-titanium dioxide modifier and the barium carbonate compounded boron nitride agent in a weight ratio of 5:3, perform ball milling treatment at a ball milling speed of 1000 r / min for 1 h. After the ball milling is completed, perform suction filtration and drying to obtain the filler modifier.

[0038] In this embodiment, the mass fraction of the sodium silicate solution is 7%; the mass fraction of the dopamine hydrochloride solution is 5%; the ultrasonic power during the immersion ultrasonic treatment is 500 W, and ultrasonic treatment is performed for 1 h.

[0039] The boron nitride liquid in this embodiment includes the following raw materials in parts by weight: 6 parts of boron nitride, 3 parts of barium sulfate, 5 parts of cordierite, 8 parts of a 4% sodium citrate solution, and 2 parts of a 5% urea solution.

[0040] The preparation method of the modified clay agent in this embodiment is as follows: S11: Stir the clay sufficiently in a sufficient amount of acid solution, then wash with water, perform suction filtration and drying. Treat the dried clay at 140 °C for 1 h. After the treatment is completed, cool to 55 °C and keep warm. S12: Preparation of the modified composite liquid: S121: Add 5 parts of mica powder and 3 parts of magnesium oxide to 8 parts of a sodium lignosulfonate solution, and then add 3 parts of the silane coupling agent KH550, and stir evenly to obtain the first modified liquid. S122: Add 4 parts of silicon carbide and 5 parts of yttrium oxide to 8 parts of a 4% chitosan solution and mix well to obtain the second modified liquid. S123: Blend the first modified liquid and the second modified liquid in a weight ratio of 7:4 and mix well to obtain the modified composite liquid. S13: Stir and modify the heat-preserved clay and the modified composite liquid in a weight ratio of 3:5. After the stirring is completed, perform suction filtration and drying to obtain the modified clay agent.

[0041] In this embodiment, the mass fraction of the acid solution is 5%; the mass fraction of the sodium lignosulfonate solution is 8%.

[0042] In this embodiment, the stirring speed during the stirring and modification treatment is 550 r / min, and the stirring time is 1 h.

[0043] The preparation method of an EVA composite material for shoes in this embodiment includes the following steps: Weigh the raw materials according to the parts by weight, mix the raw materials evenly in a mixer, and knead at 120 °C for 10 min. Then, granulate after open rolling, and then mold and press in a mold at a molding temperature of 215 °C, a molding pressure of 15 Mpa, and mold and press for 20 min to obtain the EVA composite material for shoes of the present invention.

[0044] Example 3. The EVA composite material for shoes of this embodiment comprises the following raw materials in parts by weight: EVA 62.5 parts, POE elastomer 12.5 parts, filler modifier 9 parts, modified clay agent 6.5 parts, zinc oxide 6.5 parts, foaming agent 3 parts, crosslinking agent 4 parts, calcium stearate 3 parts.

[0045] The foaming agent of this embodiment is AC foaming agent; the cross-linking agent is DCP; the VA content in the EVA is 19%, and the MFI is 2.0 g / min; the POE elastomer is ethylene-octene copolymer, and the melt index is 190°C, and 5 g / 10 min under 2.16 kg.

[0046] The preparation method of the filler modifier of this embodiment is: S01: Evenly blend nano titanium dioxide, zirconium oxide and sodium silicate solution in a weight ratio of 3.5:2:6 to obtain nano titanium dioxide liquid; 4 parts of nano titanium dioxide liquid and 2 parts of nano silica sol are added to 5.5 parts of dopamine hydrochloride solution, and then 1.5 parts of lanthanum oxide are added and stirred sufficiently to obtain a nano titanium dioxide modifier; S02: preheating barium carbonate at 62.5°C for 1 hour, immersing the preheated barium carbonate in a boron nitride solution with a volume 4 times the total volume of barium carbonate, and subjecting the solution to ultrasonic treatment. After the ultrasonic treatment is completed, the solution is filtered and dried to obtain a barium carbonate polyvalent boron nitride agent. S03: Nano titanium dioxide modifier and barium carbonate polyboron nitride agent are mixed in a weight ratio of 5:3 and ball-milled at a speed of 1000 r / min for 1 h. After the ball milling is completed, the mixture is filtered and dried to obtain a filler modifier.

[0047] The mass fraction of the sodium silicate solution in this embodiment is 5.5%; the mass fraction of the dopamine hydrochloride solution is 3.5%; the ultrasonic power of the immersion ultrasonic treatment is 475W, and the ultrasonic treatment is performed for 1 hour.

[0048] The boron nitride liquid of this embodiment includes the following raw materials in parts by weight: 5 parts of boron nitride, 2.5 parts of barium sulfate, 4 parts of cordierite, 7 parts of 4% by mass sodium citrate solution, and 1.5 parts of 5% by mass urea solution.

[0049] The preparation method of the modified clay agent of this embodiment is: S11: Stir the clay in a sufficient amount of acid solution, then wash, filter and dry. Treat the dried clay at 135°C for 1 hour. After the treatment, cool to 55°C and keep warm. S12: Preparation of modified composite liquid: S121: adding 4 parts of mica powder and 2.5 parts of magnesium oxide to 6.5 parts of sodium lignin sulfonate solution, and then adding 2 parts of silane coupling agent KH550, stirring evenly to obtain a first modified solution; S122: adding 3 parts of silicon carbide and 4 parts of yttrium oxide to 6.5 parts of 4% chitosan solution by mass and mixing them thoroughly to obtain a second modified solution; S123: fully blending the first modified liquid and the second modified liquid in a weight ratio of 6:4 to obtain a modified composite liquid; S13: stirring the heat-insulated clay and the modified composite liquid at a weight ratio of 3:5 for modification treatment, filtering and drying after the stirring is completed to obtain a modified clay agent.

[0050] The mass fraction of the acid solution in this embodiment is 3.5%; the mass fraction of the sodium lignin sulfonate solution is 6.5%.

[0051] The stirring speed of the stirring modification treatment in this embodiment is 500 r / min, and the stirring time is 1 hour.

[0052] A method for preparing an EVA composite material for shoes in this embodiment comprises the following steps: The raw materials are weighed according to weight parts, mixed uniformly in an internal mixer, and internally kneaded at 115° C. for 10 minutes, granulated after open kneading, and then molded in a mold at a molding temperature of 215° C., a molding pressure of 15 MPa, and molding for 20 minutes to obtain the EVA composite material for shoes of the present invention.

[0053] Comparative Example 1. The difference from Example 3 is that no filler modifier is added.

[0054] Comparative Example 2. The difference from Example 3 is that no nano titanium dioxide modifier is added in the preparation of the filler modifier.

[0055] Comparative Example 3. The difference from Example 3 is that no nano titanium dioxide liquid is added to the nano titanium dioxide modifier.

[0056] Comparative Example 4. The difference from Example 3 is that no nano titanium dioxide or zirconium oxide is added to the nano titanium dioxide liquid.

[0057] Comparative Example 5. The difference from Example 3 is that no nano-silica sol and lanthanum oxide are added to the nano-titanium dioxide modifier.

[0058] Comparative Example 6. The difference from Example 3 is that no barium carbonate-recombined boron nitride agent is added in the preparation of the filler modifier.

[0059] Comparative Example 7. Different from Example 3, preheated barium carbonate was not added in the preparation of the barium carbonate complexed boron nitride agent.

[0060] Comparative Example 8. Different from Example 3, boron nitride liquid was not added in the preparation of the barium carbonate complexed boron nitride agent.

[0061] Comparative Example 9. Different from Example 3, the modified clay agent was not added.

[0062] Comparative Example 10. Different from Example 3, heat-insulated clay was not added in the preparation of the modified clay agent.

[0063] Comparative Example 11. Different from Example 3, the modified composite liquid was not added in the preparation of the modified clay agent.

[0064] Comparative Example 12. Different from Example 3, the first modified liquid was not added to the modified composite liquid.

[0065] Comparative Example 13. Different from Example 3, mica powder and magnesium oxide were not added to the first modified liquid.

[0066] Comparative Example 14. Different from Example 3, the second modified liquid was not added to the modified composite liquid.

[0067] Comparative Example 15. Different from Example 3, silicon carbide and yttrium oxide were not added to the second modified liquid.

[0068] For the conventional tests, the anti-slip, wear-resistant and elastic properties of Examples 1 - 3 and Comparative Examples 1 - 15, as well as the scrub resistance and weather resistance stability of the products (scrubbed 100 times with a commercially available shoe cleaner and then irradiated with ultraviolet light at an intensity of 100 w / m 2 , ultraviolet irradiation for 12 h), the test results are as follows;

[0069] It can be seen from Comparative Examples 1 - 15 and Examples 1 - 3 that; The products of Example 3 have excellent anti-slip, wear-resistant and elastic properties, and at the same time, the products have excellent scrub resistance and weather resistance stability; It can be seen from Comparative Examples 1 - 15 and Example 3 that when one of the filler modifiers or the modified clay agent is not added to the product, the performance of the product deteriorates significantly. By using the two in coordination and with a synergistic effect, the performance effect of the product is the most obvious; No nano-titanium dioxide modifier was added during the preparation of the filler modifier. No nano-titanium dioxide solution was added to the nano-titanium dioxide modifier. No nano-titanium dioxide, zirconia was added to the nano-titanium dioxide solution. No nano-silica sol and lanthanum oxide were added to the nano-titanium dioxide modifier. No barium carbonate complex boron nitride agent was added during the preparation of the filler modifier. No preheated barium carbonate was added during the preparation of the barium carbonate complex boron nitride agent. No boron nitride solution was added during the preparation of the barium carbonate complex boron nitride agent; The performance of the products shows a deteriorating trend to varying degrees. Only the filler modifier made of the barium carbonate complex boron nitride agent obtained by the method of the present invention in combination with a specific nano-titanium dioxide modifier has the most significant performance effect. At the same time, when no boron nitride solution is added during the preparation of the barium carbonate complex boron nitride agent, the performance of the products also shows a relatively obvious deteriorating trend; No heat-insulated clay was added during the preparation of the modified clay agent. No modified composite solution was added to the modified clay agent. No first modified solution was added to the modified composite solution. No mica powder and magnesium oxide were added to the first modified solution. No second modified solution was added to the modified composite solution. No silicon carbide and yttrium oxide were added to the second modified solution. The performance of the products shows a deteriorating trend to varying degrees. The modified composite solution made of the first modified solution and the second modified solution obtained by the specific method of the present invention, in combination with the heat-insulated clay to obtain the modified clay agent, has the most significant performance effect. Using other methods instead is not as obvious as the effect of the present invention.

[0070] Based on the fact that the boron nitride solution has a great influence on the performance of the products, further research is carried out on this: Experimental Example 1. The only difference from Example 3 is that no boron nitride was added to the boron nitride solution.

[0071] Experimental Example 2. The only difference from Example 3 is that no barium sulfate was added to the boron nitride solution.

[0072] Experimental Example 3. The only difference from Example 3 is that no cordierite was added to the boron nitride solution.

[0073] Experimental Example 4. The only difference from Example 3 is that no urea solution was added to the boron nitride solution, and water was used instead of the sodium citrate solution.

[0074]

[0075] As can be seen from Experimental Examples 1-4, when boron nitride is not added to the boron nitride solution, the performance change trend of the product is relatively large. At the same time, when cordierite, barium sulfate, urea solution are not added to the boron nitride solution, and the sodium citrate solution is replaced by water, the performance of the product shows a deteriorating trend to varying degrees. The performance effect of the product is the most significant when the boron nitride solution is obtained by combining boron nitride and cordierite with specific raw materials. Only the product prepared with the specific raw materials of the present invention has the most significant performance effect, and the effect of using other methods to replace is not as obvious as that of the present invention.

[0076] For those skilled in the art, it is obvious that the present invention is not limited to the details of the above exemplary embodiments, and the present invention can be implemented in other specific forms without departing from the spirit or basic characteristics of the present invention. Therefore, from any point of view, the embodiments should be regarded as exemplary and non-restrictive. The scope of the present invention is defined by the appended claims rather than the above description. Therefore, all changes falling within the meaning and scope of the equivalent elements of the claims are intended to be included in the present invention.

[0077] In addition, it should be understood that although this specification is described according to embodiments, not every embodiment only contains an independent technical solution. This narrative way of the specification is only for clarity. Those skilled in the art should regard the specification as a whole, and the technical solutions in each embodiment can also be appropriately combined to form other embodiments that can be understood by those skilled in the art.

Claims

1. An EVA composite material for shoes, characterized in that: The EVA composite material comprises the following raw materials in parts by weight: EVA 60-65 parts, POE elastomer 10-15 parts, filler modifier 7-11 parts, modified clay agent 5-8 parts, zinc oxide 5-8 parts, foaming agent 2-4 parts, cross-linking agent 3-5 parts, calcium stearate 2-4 parts.

2. The EVA composite material for shoes according to claim 1, characterized in that: The EVA composite material comprises the following raw materials in parts by weight: EVA 62.5 parts, POE elastomer 12.5 parts, filler modifier 9 parts, modified clay agent 6.5 parts, zinc oxide 6.5 parts, foaming agent 3 parts, crosslinking agent 4 parts, calcium stearate 3 parts.

3. The EVA composite material for shoes according to claim 1, characterized in that: The foaming agent is AC foaming agent; the crosslinking agent is DCP; the VA content in the EVA is 18-20%, and the MFI is 1.5-2.5 g / min; the POE elastomer is ethylene-octene copolymer, and the melt index is 190° C., and 5 g / 10 min under 2.16 kg.

4. The EVA composite material for shoes according to claim 1, characterized in that: The preparation method of the filler modifier is: S01: Evenly blend nano titanium dioxide, zirconium oxide and sodium silicate solution in a weight ratio of (2-5): (1-3): (5-7) to obtain nano titanium dioxide liquid; 3-5 parts of nano titanium dioxide liquid and 1-3 parts of nano silica sol are added to 4-7 parts of dopamine hydrochloride solution, and then 1-2 parts of lanthanum oxide are added and stirred sufficiently to obtain a nano titanium dioxide modifier; S02: preheating barium carbonate at 60-65°C for 1 hour, immersing the preheated barium carbonate in a boron nitride solution with a volume of 3-5 times the total volume of barium carbonate, and subjecting the solution to ultrasonic treatment. After the ultrasonic treatment is completed, the solution is filtered and dried to obtain a barium carbonate polyvalent boron nitride agent. S03: Nano titanium dioxide modifier and barium carbonate polyboron nitride agent are mixed in a weight ratio of 5:3 and ball-milled at a speed of 1000 r / min for 1 h. After the ball milling is completed, the mixture is filtered and dried to obtain a filler modifier.

5. The EVA composite material for shoes according to claim 4, characterized in that: The mass fraction of the sodium silicate solution is 4-7%; the mass fraction of the dopamine hydrochloride solution is 2-5%; the ultrasonic power of the immersion ultrasonic treatment is 450-500W, and the ultrasonic treatment is performed for 1 hour.

6. The EVA composite material for shoes according to claim 4, characterized in that: The boron nitride solution comprises the following raw materials in parts by weight: 4-6 parts of boron nitride, 2-3 parts of barium sulfate, 3-5 parts of cordierite, 6-8 parts of 4% by mass sodium citrate solution and 1-2 parts of 5% by mass urea solution.

7. The EVA composite material for shoes according to claim 1, characterized in that: The preparation method of the modified clay agent is: S11: Stir the clay in a sufficient amount of acid solution, then wash, filter and dry. Treat the dried clay at 130-140°C for 1h. After the treatment, cool to 55°C and keep warm. S12: Preparation of modified composite liquid: S121: adding 3-5 parts of mica powder and 2-3 parts of magnesium oxide to 5-8 parts of sodium lignin sulfonate solution, and then adding 1-3 parts of silane coupling agent KH550, stirring evenly, to obtain a first modified solution; S122: adding 2-4 parts of silicon carbide and 3-5 parts of yttrium oxide to 5-8 parts of 4% chitosan solution by mass and mixing them thoroughly to obtain a second modified solution; S123: fully blending the first modified liquid and the second modified liquid in a weight ratio of (5-7):4 to obtain a modified composite liquid; S13: stirring the heat-insulated clay and the modified composite liquid at a weight ratio of 3:5 for modification treatment, filtering and drying after the stirring is completed to obtain a modified clay agent.

8. The EVA composite material for shoes according to claim 7, characterized in that: The mass fraction of the acid solution is 2-5%; the mass fraction of the sodium lignin sulfonate solution is 5-8%.

9. The EVA composite material for shoes according to claim 7, characterized in that: The stirring speed of the stirring modification treatment is 450-550 r / min, and the stirring time is 1 h.

10. A method for preparing an EVA composite material for shoes according to any one of claims 1 to 9, characterized in that: The following steps are involved: The raw materials are weighed according to weight parts, mixed uniformly in an internal mixer, and internally kneaded at 110-120° C. for 10 minutes, granulated after open kneading, and then molded in a mold at a molding temperature of 215° C., a molding pressure of 15 MPa, and molding for 20 minutes to obtain the EVA composite material for shoes of the present invention.

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