CN113881130A - High-wear-resistance EVA (ethylene-vinyl acetate) foam material for shoes and preparation method thereof - Google Patents

High-wear-resistance EVA (ethylene-vinyl acetate) foam material for shoes and preparation method thereof Download PDF

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CN113881130A
CN113881130A CN202111315317.0A CN202111315317A CN113881130A CN 113881130 A CN113881130 A CN 113881130A CN 202111315317 A CN202111315317 A CN 202111315317A CN 113881130 A CN113881130 A CN 113881130A
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foaming
parts
eva
wear
shoes
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CN113881130B (en
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党明江
秦培新
贺金林
吴志诚
罗小傅
梁志新
王瑞龙
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Anta China Co Ltd
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Anta China Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
    • C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
    • C08J9/102—Azo-compounds
    • C08J9/103—Azodicarbonamide
    • A—HUMAN NECESSITIES
    • A43—FOOTWEAR
    • A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
    • A43B13/00—Soles; Sole-and-heel integral units
    • A43B13/02—Soles; Sole-and-heel integral units characterised by the material
    • A43B13/04—Plastics, rubber or vulcanised fibre
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0014—Use of organic additives
    • C08J9/0023—Use of organic additives containing oxygen
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0066—Use of inorganic compounding ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0095—Mixtures of at least two compounding ingredients belonging to different one-dot groups
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    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/04—N2 releasing, ex azodicarbonamide or nitroso compound
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    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/08—Copolymers of ethene
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    • C08J2353/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2409/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08J2409/06—Copolymers with styrene
    • C—CHEMISTRY; METALLURGY
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    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
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    • C—CHEMISTRY; METALLURGY
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    • C08J2427/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2427/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2427/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08J2427/18—Homopolymers or copolymers of tetrafluoroethylene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2451/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2453/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
    • Y02P70/62—Manufacturing or production processes characterised by the final manufactured product related technologies for production or treatment of textile or flexible materials or products thereof, including footwear

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Emergency Medicine (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Footwear And Its Accessory, Manufacturing Method And Apparatuses (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention belongs to the technical field of foaming materials for shoes, and discloses a high-wear-resistance EVA foaming material for shoes and a preparation method thereof, wherein the foaming material is prepared by mixing and foaming formula materials, and the formula materials comprise the following raw materials in parts by weight: 40-60 parts of ethylene-vinyl acetate copolymer; 20-30 parts of a polyolefin elastomer; 5-10 parts of maleic anhydride grafted; 10-15 parts of a wear-resisting agent, wherein the wear-resisting agent is a polytetrafluoroethylene and styrene butadiene rubber composite solid material; 0.2-1 part of stearic acid; 0.2-1 part of zinc stearate; 0.3-2 parts of zinc oxide; 2-5 parts of talcum powder; 0.3-1.5 parts of bridging agent; 1.5-5 parts of foaming agent. The invention improves the wear resistance, the compression resistance, the resilience and the softness of the EVA foaming material, does not influence the slip resistance of the foaming material, and has important practical significance for expanding the contact-ground EVA foaming shoe sole.

Description

High-wear-resistance EVA (ethylene-vinyl acetate) foam material for shoes and preparation method thereof
Technical Field
The application relates to the technical field of foaming materials for shoes, in particular to a high-wear-resistance EVA foaming material for shoes and a preparation method thereof.
Background
Along with the improvement of living standard and the continuous popularization of exercise, people have higher and higher requirements on the comfort of shoes and the functionality of the shoes. The EVA foamed shoe sole is improved towards the properties of light, soft, elastic and pressure-resistant deformation, but the comprehensive properties of the EVA foamed shoe sole are generally difficult to combine, for example, the comfort and the wear resistance of the EVA foamed shoe sole are generally difficult to reach the standard under the condition of ensuring the properties of light, soft, elastic and pressure-resistant deformation. In the market, in order to pursue comfort, the hardness of the sole material is generally very low, but the sole is neglected to be too soft, so that the foot is easy to sprain, and fatigue is easy to bring after the sole stands for too long time. In addition, the low-hardness lightweight foamed shoe sole cannot directly touch the ground due to poor wear resistance, and a layer of rubber sole needs to be attached, so that the weight of the whole shoe is difficult to reduce.
On the other hand, in order to improve the wear resistance of the EVA foam material, a means of adding wear-resistant powder is generally adopted in the industry to improve the wear resistance of the material. For example, chinese patent publication No. CN 107936360 a discloses a wear-resistant EVA injection-crosslinked foam material, which comprises the following raw materials: 5-30 parts of vinyl copolymer, 40-60 parts of EVA (ethylene-vinyl acetate), 1-15 parts of MAH (maleic anhydride), 0.1-3 parts of dispersant, 0.1-1.5 parts of initiator, 0-1 part of inhibitor, 0-1.5 parts of second monomer, 5-20 parts of toughener, 0-15 parts of foaming promoter, 1-10 parts of foaming agent, 0.5-1.5 parts of cross-linking agent, 5-15 parts of superfine ultrahigh molecular weight polyethylene (the average particle size is 80-150 mu m) and 0.5-3 parts of filler.
In the prior art, the wear resistance of the EVA foam material is realized mainly by adding the ultra-high molecular weight polyethylene with excellent wear resistance and strong comprehensive performance. However, the combination properties of abrasion resistance and resistance to pressure change are still to be improved.
Disclosure of Invention
In view of the above, the application provides a high-wear-resistance EVA foaming material for shoes and a preparation method thereof.
The invention provides a high-wear-resistance EVA (ethylene vinyl acetate) foaming material for shoes, which is prepared by mixing and foaming formula materials, wherein the formula materials comprise the following raw materials in parts by weight:
Figure BDA0003343432600000021
the wear-resisting agent is a polytetrafluoroethylene and styrene butadiene rubber composite solid material.
Preferably, the ethylene-vinyl acetate copolymer has a vinyl acetate content of between 18% and 40%.
Preferably, the wear-resisting agent is a composite solid material obtained by emulsion blending and physical precipitation of polytetrafluoroethylene emulsion and styrene-butadiene rubber emulsion.
Further preferably, the anti-wear agent is obtained in the following specific manner: mixing the polytetrafluoroethylene emulsion and the styrene butadiene rubber emulsion under stirring, continuously stirring for a certain time, adding saturated salt solution until solid is separated out, crushing the obtained solid, placing the crushed solid in clear water, soaking for at least 12 hours, and then drying in vacuum to obtain the polytetrafluoroethylene and styrene butadiene rubber composite solid material.
Preferably, the emulsion particle size of the polytetrafluoroethylene emulsion is 0.1-1 μm, and the solid content is 50-65%.
Preferably, the solid content of the styrene-butadiene rubber emulsion is 50-65%, and the mass ratio of the polytetrafluoroethylene emulsion to the styrene-butadiene rubber emulsion is 1: (1-3).
Preferably, the bridging agent is 1, 4-di-tert-butylperoxydiisopropylbenzene; the foaming agent is azodicarbonamide.
The invention provides a preparation method of the EVA foaming material for shoes, which comprises the following steps:
s1, mixing all the raw materials except the bridging agent and the foaming agent in the weighed raw materials;
s2, adding the bridging agent and the foaming agent into the material mixed in the step S1, and mixing;
s3, granulating the mixture obtained in the step S2, and standing for cooling;
and S4, carrying out an IP (Internet protocol) primary forming process or an MD secondary die pressing process on the cooled particles obtained in the step S3 to obtain the high-wear-resistance EVA foaming material for the shoes.
In the embodiment of the present invention, the IP one-shot forming process specifically includes: and (5) injecting the particles cooled in the step (S3) by an EVA injection machine, vulcanizing and foaming to obtain the EVA foaming material for shoes.
In the embodiment of the invention, the MD secondary molding process specifically comprises the following steps: weighing the particles cooled in the step S3 according to the mould body, and carrying out small foaming; and carrying out hot pressing, cooling and shaping on the rough blank obtained by small foaming to obtain the EVA foaming material for the shoes.
Compared with the prior art, in the EVA foaming formula material system, the polytetrafluoroethylene and styrene butadiene rubber composite solid material is used as a wear-resisting agent; the system comprises, by weight, 40-60 parts of EVA (ethylene-vinyl acetate), 20-30 parts of polyolefin elastomer, 5-10 parts of maleic anhydride grafted polyethylene, 10-15 parts of the wear-resisting agent and a corresponding functional additive. In the invention, the material can be endowed with better wear resistance and can also keep good mechanical property by adopting smaller filling amount of the wear-resisting agent; meanwhile, the flexibility and elasticity of the EVA foaming material can be improved by introducing the styrene butadiene rubber; the ethylene-based polymer grafted maleic anhydride is used as a compatilizer, so that the compatibility of polytetrafluoroethylene and an EVA (ethylene-vinyl acetate copolymer) base material is improved, the polytetrafluoroethylene plays a certain role in enhancing the base material, and the EVA foaming material for the shoes has good support property and compression property. Therefore, the invention improves the wear resistance, the pressure change resistance, the resilience and the softness of the EVA foaming material, does not influence the slip resistance of the foaming material, and has important practical significance for expanding the contact-ground EVA foaming shoe sole.
Detailed Description
The technical solutions in the embodiments of the present application are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present application, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
The application provides a high wear-resistant EVA (ethylene-vinyl acetate copolymer) foaming material for shoes, which is prepared by mixing and foaming formula materials, wherein the formula materials comprise the following raw materials in parts by weight:
Figure BDA0003343432600000041
the wear-resisting agent is a polytetrafluoroethylene and styrene butadiene rubber composite solid material.
The EVA foaming material provided by the invention has higher wear resistance, good compression deformation resistance and good comfort, and can be used for preparing EVA foaming soles with excellent comprehensive performance.
The EVA foaming formula provided by the embodiment of the invention comprises the following raw materials in parts by weight: 40-60 parts of ethylene-vinyl acetate copolymer; 20-30 parts of a polyolefin elastomer; 5-10 parts of maleic anhydride grafted polyethylene. The ethylene-vinyl acetate copolymer is EVA for short, and is formed by copolymerizing monomer ethylene and Vinyl Acetate (VA). Further, the mass content of vinyl acetate in the ethylene-vinyl acetate copolymer is between 18 and 40 percent. The ethylene-vinyl acetate copolymer can be one or more of EVA7350M, EVA7360M, EVA7470M and EVA 40W. EVA is copolymer of ethylene and vinyl acetate, the content of vinyl acetate is different in different types, the VA content of EVA7350M is 18%, the EVA7350, 7360, 7470 are produced by Taiwan plastics, the EVA40W is produced by DuPont in the United states, and the VA content is 40%
Further, the polyolefin elastomer can be one or more of Infuse9100, Infuse9107, Infuse9500 and Infuse9507 (the INFUSE series is a Dow's OBCs polyolefin block copolymer).
Further, the type of the maleic anhydride grafted polyethylene can be
Figure BDA0003343432600000042
E588 (DuPont, USA), the present application is not limited to any particular type of starting product.
In some embodiments of the invention, the ethylene-vinyl acetate copolymer: 40 parts by weight; polyolefin thermoplastic elastomer: 30 parts by weight; maleic anhydride grafted polyethylene: 10 parts by weight. In other embodiments, the ethylene-vinyl acetate copolymer may be 50 parts by weight or 60 parts by weight.
The formula material provided by the embodiment of the invention comprises 10-15 parts by mass of a wear-resisting agent, wherein the wear-resisting agent is a polytetrafluoroethylene and styrene butadiene rubber composite solid material, and the dosage of the wear-resisting agent can be 10 parts, 11 parts, 12 parts, 13 parts, 15 parts and the like.
The polytetrafluoroethylene is commonly called as 'plastic king', is almost insoluble in all solvents, has heat resistance and cold resistance, can be used at minus 180-260 ℃ for a long time, has excellent self-lubricating property due to small friction coefficient, and can be used as an abrasion-resistant filler of engineering plastics. However, the powder filler generally has a large particle size and a small specific surface area, and needs to be added in a relatively large amount to achieve the wear-resistant effect, and the application of the powder filler to shoe materials such as EVA and the like causes the problems of poor material performance and the like.
The problem of the wear resistance of the EVA foaming material is solved, and the difficulty of preparing the EVA foaming material with excellent comprehensive properties such as light, soft, elastic and pressure-change resistance in the industry is always solved. The polytetrafluoroethylene and the styrene butadiene rubber are introduced to form the composite wear-resisting agent (which can be called as polytetrafluoroethylene/styrene butadiene rubber composite material), so that the wear-resisting effect is achieved, and the resilience, softness and the like of the material can be improved.
In a preferred embodiment of the invention, the anti-wear agent is a composite solid material obtained by emulsion blending and physical precipitation of polytetrafluoroethylene emulsion and styrene-butadiene rubber emulsion. According to the method, the polytetrafluoroethylene is dispersed in the rubber matrix in an emulsion blending mode, so that the composite wear-resistant agent with small particle size and good dispersion can be obtained. In addition, the composite wear-resistant agent is a solid material, and is convenient to operate and apply.
Further, the specific preparation method of the polytetrafluoroethylene/styrene butadiene rubber composite wear-resistant agent is as follows:
(1) weighing a certain amount of polytetrafluoroethylene emulsion in a beaker, and mechanically stirring at a certain stirring speed;
(2) weighing styrene butadiene rubber emulsion according to a certain proportion, slowly adding the styrene butadiene rubber emulsion into the beaker, and continuously stirring for a certain time;
(3) stopping stirring, and slowly adding saturated salt solution until solid is separated out and the solution is transparent;
(4) cutting the obtained solid into small pieces or granules, and soaking in clear water overnight;
(5) taking out the soaked solid, and preferably drying the solid in vacuum at 50-60 ℃ to obtain the polytetrafluoroethylene/styrene butadiene rubber composite solid material.
Wherein, the latex particle diameter of the polytetrafluoroethylene emulsion can be 0.1-1 μm, and the solid content is generally 50-65% (mass). The solid content of the styrene-butadiene rubber emulsion is 50-65%, such as 60%; the certain proportion is omega (polytetrafluoroethylene emulsion): ω (styrene butadiene rubber emulsion) ═ 1: (1 to 3), preferably 1: 2.
the embodiment of the invention utilizes the self-lubricating property of the polytetrafluoroethylene to improve the wear resistance of the EVA foaming material in a composite mode, and adopts an emulsion mixing mode to disperse smaller-particle polytetrafluoroethylene in a matrix material, so that compared with micro powder filling, the invention can provide larger specific surface area and increase interaction force, and thus the invention can endow the material with better wear resistance by smaller filling amount.
In addition, the polytetrafluoroethylene serving as engineering plastic can keep good mechanical properties within a wide temperature range, and the compatibility of the polytetrafluoroethylene and an EVA matrix material is improved by grafting maleic anhydride and the like on the vinyl polymer, so that the polytetrafluoroethylene has a certain reinforcing effect on the matrix material, and the foaming material has good support property and compression property. Meanwhile, the styrene butadiene rubber is introduced, so that the flexibility and elasticity of the EVA foaming material can be improved. In addition, the emulsion mixing mode in the embodiment of the invention is easy to disperse and simple to operate.
The preparation raw materials of the EVA foam material with high wear resistance and compression deformation resistance obtained by the embodiment of the invention also comprise the following components in parts by weight: 0.2-1 part of stearic acid; 0.2-1 part of zinc stearate; 0.3-2 parts of zinc oxide (ZnO); 2-5 parts of talcum powder.
In the embodiment of the invention, 0.3-1.5 parts of bridging agent and 1.5-5 parts of foaming agent are adopted to enable the material system in the formula to be crosslinked and foamed to form the EVA foaming material for shoes with excellent comprehensive performance (for example, the EVA foaming material can be called as an EVA composite foaming material for shoes with light weight, pressure deformation resistance, high wear resistance and extremely good foot feeling, or an EVA foaming material with super-comfortable feeling of high wear resistance and compression deformation resistance, an EVA foaming material with high wear resistance and compression deformation resistance, and the like). The bridging agent is also called a cross-linking agent, and is preferably 1, 4-di-tert-butylperoxydiisopropylbenzene; the blowing agent is preferably azodicarbonamide. In the embodiment of the present invention, other additives such as a crosslinking agent, a foaming agent, and an activator are not particularly limited, and may be those commonly used in the art. In the specific embodiment of the invention, the EVA foaming material for shoes has the hardness of 42-52C, the rebound resilience of over 58 percent and the density of 0.185g/cm3And the wear resistance and compression deformation are better.
The embodiment of the invention provides a preparation method of the EVA foaming material for shoes, which comprises the following steps:
s1, mixing all the raw materials except the bridging agent and the foaming agent in the weighed raw materials;
s2, adding the bridging agent and the foaming agent into the material mixed in the step S1, and mixing;
s3, granulating the mixture obtained in the step S2, and standing for cooling;
and S4, carrying out an IP (Internet protocol) primary forming process or an MD secondary die pressing process on the cooled particles obtained in the step S3 to obtain the high-wear-resistance EVA foaming material for the shoes.
Specifically, the preparation method of the EVA foam material for the shoes with high wear resistance and compressive deformation resistance provided by the embodiment of the invention comprises the following steps:
step 1: weighing the raw materials according to the mass parts of the components in the defined composition for preparing the EVA foaming material with high wear resistance and compression deformation resistance;
step 2: mixing all the components except the cross-linking agent and the foaming agent;
and step 3: adding the weighed cross-linking agent and foaming agent into the mixed materials and then mixing;
and 4, step 4: the resulting mixture was granulated, and the resulting granules were left to cool.
In order to enable the formula materials to be used in a wider range, the following steps adopt an IP one-step forming or MD two-step molding process to prepare the EVA foaming material sole and the test piece with high wear resistance and high compression deformation resistance.
In some embodiments of the present invention, the IP one-shot forming process comprises the following steps:
and 5: and (4) injecting the particles obtained in the step (4) by an EVA injection machine, vulcanizing and foaming to obtain the EVA foaming material sole and the test piece with high wear resistance and high compression deformation resistance.
In other embodiments of the present invention, the MD overmolding process follows the following steps:
and 5: weighing a certain mass of the particles obtained in the step 4 according to the mould body, and carrying out small foaming to obtain a coarse blank;
step 6: and (5) carrying out hot pressing, cooling and shaping on the small foamed coarse blank in the step (5) to obtain the EVA foamed material sole and the test piece with high wear resistance and high compression deformation resistance.
The embodiment of the invention has no special limitation on the preparation process; all data of the prepared product can reach the national physical property standard of the EVA foamed sole material, and the prepared product is a high-wear-resistance and compression-deformation-resistant EVA foamed material with super-comfort, and has important practical significance for expanding contact with the ground of the EVA foamed sole.
In order to better understand the technical content of the invention, specific examples are provided below to further illustrate the invention. In the present invention, the amounts referred to in the present invention are all mass percentages unless otherwise specified.
Example 1
The EVA foam material with high wear resistance and compression deformation resistance and super-comfortable feeling comprises the following raw materials in parts by weight:
ethylene-vinyl acetate copolymer: 40 parts of a mixture;
polyolefin thermoplastic elastomer: 30 parts of (1);
maleic anhydride grafted polyethylene: 10 parts of (A);
wear-resisting agent: 10 parts of (A);
stearic acid: 0.5 part;
zinc stearate: 1 part;
zinc oxide: 1.5 parts;
talc powder: 4 parts of a mixture;
a bridging agent: 0.8 part;
foaming agent: 2.5 parts;
wherein the ethylene-vinyl acetate copolymer is EVA7470M, produced by Taiwan plastic company; the polyolefin block copolymer is the type infuse9507, manufactured by the Dow company; maleic anhydride grafted polyethylene as
Figure BDA0003343432600000081
E588, manufactured by DuPont corporation; the wear-resisting agent is a polytetrafluoroethylene/styrene butadiene rubber composite material prepared by an emulsion method; the cross-linking agent is 1, 4-di-tert-butylperoxy diisopropylbenzene; the foaming agent is azodicarbonamide. The polytetrafluoroethylene emulsion is selected from Japanese gold D-210C, the particle size is 0.15-0.35 μm, and the solid content is 60%; chemical engineering of styrene-butadiene rubber emulsionThe solids content is 60%, the viscosity is 1300-2000 mPas.
A preparation method of EVA foaming material with high wear resistance and compression deformation resistance and super comfortable feeling comprises the following steps of adding raw materials according to the mixing ratio as described above:
(1) preparing a polytetrafluoroethylene/styrene butadiene rubber composite material:
1) weighing 100g of polytetrafluoroethylene emulsion in a beaker, and mechanically stirring at the stirring speed of 2000 rpm;
2) weighing 200g of styrene-butadiene rubber emulsion, slowly adding into the beaker in the step 1), and continuously stirring for 2 hours;
3) stopping stirring, and slowly adding saturated salt solution until solid is separated out and the solution is transparent;
4) cutting the solid obtained in the step 3) into small pieces, and soaking in clear water overnight;
5) and (4) taking out the solid obtained in the step (4), and drying the solid in vacuum at the temperature of 60 ℃ to obtain the polytetrafluoroethylene/styrene butadiene rubber composite material wear-resistant agent.
(2) Pouring the ethylene-vinyl acetate copolymer, the polyolefin elastomer, the maleic anhydride grafted polyethylene, the wear-resistant agent, the stearic acid, the zinc stearate, the zinc oxide and the talcum powder into an internal mixer for internal mixing according to the raw material proportion, turning the materials for 4-5 times, controlling the internal mixing temperature at 115 ℃ and 120 ℃ and keeping the internal mixing time for 12-15 minutes;
(3) adding a bridging agent and a foaming agent into the step (2), and continuously carrying out banburying, wherein the banburying temperature is controlled at 110-115 ℃ and the time is about 3-5 minutes;
(4) conveying the material uniformly mixed in the open mill in the step (3) to a granulator for granulation, and cooling the granulated particles to room temperature;
(5) and (4) injecting the particles in the step (4) by an injection machine, vulcanizing and foaming, wherein the vulcanizing time is 320-182 seconds, and the vulcanizing temperature is controlled at 178-182 ℃, so as to obtain the EVA foaming material sole and the test piece with high wear resistance and compression deformation resistance and super-comfort.
Example 2:
the EVA foam material with high wear resistance and compression deformation resistance and super-comfortable feeling comprises the following raw materials in parts by weight:
ethylene-vinyl acetate copolymer: 40 parts of a mixture;
polyolefin thermoplastic elastomer: 30 parts of (1);
maleic anhydride grafted polyethylene: 10 parts of (A);
wear-resisting agent: 15 parts of (1);
stearic acid: 0.5 part;
zinc stearate: 1 part;
zinc oxide: 1.6 parts;
talc powder: 4 parts of a mixture;
a bridging agent: 1.2 parts;
foaming agent: 3.2 parts of a mixture;
wherein the ethylene-vinyl acetate copolymer is prepared from EVA7470M and EVA40W in a mass ratio of 2:1, the EVA7470M is prepared by Taiwan plastic company, and the EVA40W is prepared by DuPont company; the polyolefin block copolymer is the model number infuse9107, manufactured by the Dow company; maleic anhydride grafted polyethylene as
Figure BDA0003343432600000091
E588, manufactured by DuPont corporation; the wear-resisting agent is a polytetrafluoroethylene/styrene butadiene rubber composite material prepared by an emulsion method; the cross-linking agent is 1, 4-di-tert-butylperoxy diisopropylbenzene; the foaming agent is azodicarbonamide.
A preparation method of EVA foaming material with high wear resistance and compression deformation resistance and super comfortable feeling comprises the following steps of adding raw materials according to the mixing ratio as described above:
(1) preparation of polytetrafluoroethylene/styrene butadiene rubber composite (in the examples, the preparation of the wear resistant agent was the same as in example 1):
1) weighing 100g of polytetrafluoroethylene emulsion in a beaker, and mechanically stirring at the stirring speed of 2000 rpm;
2) weighing 200g of styrene-butadiene rubber emulsion, slowly adding into the beaker in the step 1), and continuously stirring for 2 hours;
3) stopping stirring, and slowly adding saturated salt solution until solid is separated out and the solution is transparent;
4) cutting the solid obtained in the step 3) into small pieces, and soaking in clear water overnight;
5) and (4) drying the solid obtained in the step (4) in vacuum at the temperature of 60 ℃ to obtain the polytetrafluoroethylene/styrene butadiene rubber composite material wear-resistant agent.
(2) Pouring ethylene-vinyl acetate copolymer, polyolefin elastomer, maleic anhydride grafted polyethylene, wear-resisting agent, stearic acid, zinc stearate, zinc oxide and talcum powder into an internal mixer for internal mixing according to the raw material proportion, turning for 4-5 times, controlling the internal mixing temperature at 115-120 ℃ and the time at 12-15 minutes;
(3) adding a bridging agent and a foaming agent into the step (2), and continuously carrying out banburying, wherein the banburying temperature is controlled at 110-115 ℃ and the time is about 3-5 minutes;
(4) conveying the material uniformly mixed in the open mill in the step (3) to a granulator for granulation, and cooling the granulated particles to room temperature;
(5) and (4) injecting the particles in the step (4) by an injection machine, vulcanizing and foaming, wherein the vulcanizing time is 320-182 seconds, and the vulcanizing temperature is controlled at 178-182 ℃, so as to obtain the EVA foaming material sole and the test piece with high wear resistance and compression deformation resistance and super-comfort.
Comparative example 1:
the comparative example comprises the following raw materials in parts by weight:
ethylene-vinyl acetate copolymer: 40 parts of a mixture;
polyolefin thermoplastic elastomer: 30 parts of (1);
maleic anhydride grafted polyethylene: 10 parts of (A);
wear-resisting agent: 15 parts of (1);
stearic acid: 0.5 part;
zinc stearate: 1 part;
zinc oxide: 1.6 parts;
talc powder: 4 parts of a mixture;
a bridging agent: 1.2 parts;
foaming agent: 3.2 parts of a mixture;
wherein the ethylene-vinyl acetate copolymer is prepared from EVA7470M and EVA40W in a mass ratio of 2:1, the EVA7470M is prepared by Taiwan plastic company, and the EVA40W is prepared by DuPont company; the polyolefin block copolymer is the model number infuse9107, manufactured by the Dow company; maleic anhydride grafted polyethylene as
Figure BDA0003343432600000101
E588, manufactured by DuPont corporation; the wear-resisting agent is silicone master batch, the model is CMB1502, and is produced by Saito high polymer material (Shanghai) Co., Ltd; the cross-linking agent is an odorless bridging agent 1, 4-di-tert-butylperoxy diisopropylbenzene; the foaming agent is azodicarbonamide.
The method for producing the EVA foamed material of the comparative example, in which the raw materials are added in the mixing ratio as described above, comprises the steps of:
(1) pouring ethylene-vinyl acetate copolymer, polyolefin elastomer, maleic anhydride grafted polyethylene, wear-resisting agent, stearic acid, zinc stearate, zinc oxide and talcum powder into an internal mixer for internal mixing according to the raw material proportion, turning for 4-5 times, controlling the internal mixing temperature at 115-120 ℃ and the time at 12-15 minutes;
(2) adding a bridging agent and a foaming agent into the step (1), and continuously carrying out banburying, wherein the banburying temperature is controlled at 110-115 ℃ and the time is about 3-5 minutes;
(3) conveying the material uniformly mixed in the open mill in the step (2) to a granulator for granulation, and cooling the granulated particles to room temperature;
(4) injecting the particles in the step (3) by an injection machine, vulcanizing and foaming, wherein the vulcanizing time is 320-400 seconds, and the vulcanizing temperature is controlled at 178-182 ℃, so as to obtain the EVA foaming material sole and the test piece.
TABLE 1 one-shot forming example and comparative example formulation
Figure BDA0003343432600000111
Example 3:
the EVA foam material with high wear resistance and compression deformation resistance and super-comfortable feeling comprises the following raw materials in parts by weight:
ethylene-vinyl acetate copolymer: 40 parts of a mixture;
polyolefin thermoplastic elastomer: 30 parts of (1);
maleic anhydride grafted polyethylene: 10 parts of (A);
wear-resisting agent: 10 parts of (A);
stearic acid: 0.5 part;
zinc stearate: 1 part;
zinc oxide: 1.5 parts;
talc powder: 4 parts of a mixture;
a bridging agent: 0.6 part;
foaming agent: 3.5 parts;
wherein the ethylene-vinyl acetate copolymer is EVA7470M, produced by Taiwan plastic company; the polyolefin block copolymer is the type infuse9507, manufactured by the Dow company; maleic anhydride grafted polyethylene as
Figure BDA0003343432600000121
E588, manufactured by DuPont corporation; the wear-resisting agent is a polytetrafluoroethylene/styrene butadiene rubber composite material prepared by an emulsion method; the cross-linking agent is 1, 4-di-tert-butylperoxy diisopropylbenzene; the foaming agent is azodicarbonamide.
A preparation method of EVA foaming material with high wear resistance and compression deformation resistance and super comfortable feeling comprises the following steps of adding raw materials according to the mixing ratio as described above:
(1) preparing a polytetrafluoroethylene/styrene butadiene rubber composite material:
1) weighing 100g of polytetrafluoroethylene emulsion in a beaker, and mechanically stirring at the stirring speed of 2000 rpm;
2) weighing 200g of styrene-butadiene rubber emulsion, slowly adding into the beaker in the step 1), and continuously stirring for 2 hours;
3) stopping stirring, and slowly adding saturated salt solution until solid is separated out and the solution is transparent;
4) cutting the solid obtained in the step 3) into small pieces, and soaking in clear water overnight;
5) and (4) drying the solid obtained in the step (4) in vacuum at the temperature of 60 ℃ to obtain the polytetrafluoroethylene/styrene butadiene rubber composite material wear-resistant agent.
(2) Pouring ethylene-vinyl acetate copolymer, polyolefin elastomer, maleic anhydride grafted polyethylene, wear-resisting agent, stearic acid, zinc stearate, zinc oxide and talcum powder into an internal mixer for internal mixing according to the raw material proportion, turning for 4-5 times, controlling the internal mixing temperature at 115-120 ℃ and the time at 12-15 minutes;
(3) adding a bridging agent and a foaming agent into the step (2), and continuously carrying out banburying, wherein the banburying temperature is controlled at 110-115 ℃ and the time is about 3-5 minutes;
(4) conveying the material uniformly mixed in the open mill in the step (3) to a granulator for granulation, and cooling the granulated particles to room temperature;
(5) and (4) carrying out small foaming on the particles in the step (4), wherein the mold temperature is about 155 ℃ and 160 ℃, and the vulcanization time is about 500 ℃ and 600 seconds, so as to obtain a small foamed coarse blank.
(6) And (3) carrying out hot pressing and cooling setting on the small foamed coarse blank in the step (5), wherein the hot pressing temperature is 150 ℃, and the hot pressing and cooling setting time is 450 seconds, so as to obtain the EVA foamed material sole and the test piece with high wear resistance and compression deformation resistance and super-comfort.
Example 4:
the EVA foam material with high wear resistance and compression deformation resistance and super-comfortable feeling comprises the following raw materials in parts by weight:
ethylene-vinyl acetate copolymer: 40 parts of a mixture;
polyolefin thermoplastic elastomer: 30 parts of (1);
maleic anhydride grafted polyethylene: 10 parts of (A);
wear-resisting agent: 15 parts of (1);
stearic acid: 0.5 part;
zinc stearate: 1 part;
zinc oxide: 1.5 parts;
talc powder: 4 parts of a mixture;
a bridging agent: 1 part;
foaming agent: 5 parts of a mixture;
wherein the ethylene-vinyl acetate copolymer is prepared from EVA7470M and EVA40W in a mass ratio of 2:1, the EVA7470M is prepared by Taiwan plastic company, and the EVA40W is prepared by DuPont company; the polyolefin block copolymer is the model number infuse9107, manufactured by the Dow company; maleic anhydride grafted polyethylene as
Figure BDA0003343432600000131
E588, manufactured by DuPont corporation; the wear-resisting agent is a polytetrafluoroethylene/styrene butadiene rubber composite material prepared by an emulsion method; crosslinking agentIs 1, 4-di-tert-butylperoxy-diisopropylbenzene; the foaming agent is azodicarbonamide.
A preparation method of EVA foaming material with high wear resistance and compression deformation resistance and super comfortable feeling comprises the following steps of adding raw materials according to the mixing ratio as described above:
(1) preparing a polytetrafluoroethylene/styrene butadiene rubber composite material:
1) weighing 100g of polytetrafluoroethylene emulsion in a beaker, and mechanically stirring at the stirring speed of 2000 rpm;
2) weighing 200g of styrene-butadiene rubber emulsion, slowly adding into the beaker in the step 1), and continuously stirring for 2 hours;
3) stopping stirring, and slowly adding saturated salt solution until solid is separated out and the solution is transparent;
4) cutting the solid obtained in the step 3) into small pieces, and soaking in clear water overnight;
5) and (4) taking out the solid obtained in the step (4), and drying the solid in vacuum at the temperature of 60 ℃ to obtain the polytetrafluoroethylene/styrene butadiene rubber composite material wear-resistant agent.
(2) Pouring ethylene-vinyl acetate copolymer, polyolefin elastomer, maleic anhydride grafted polyethylene, wear-resisting agent, stearic acid, zinc stearate, zinc oxide and talcum powder into an internal mixer for internal mixing according to the raw material proportion, turning for 4-5 times, controlling the internal mixing temperature at 115-120 ℃ and the time at 12-15 minutes;
(3) adding a bridging agent and a foaming agent into the step (2), and continuously carrying out banburying, wherein the banburying temperature is controlled at 110-115 ℃ and the time is about 3-5 minutes;
(4) conveying the material uniformly mixed in the open mill in the step (3) to a granulator for granulation, and cooling the granulated particles to room temperature;
(5) and (4) carrying out small foaming on the particles in the step (4), wherein the mold temperature is about 155 ℃ and 160 ℃, and the vulcanization time is about 500 ℃ and 600 seconds, so as to obtain the small foamed coarse blank.
(6) And (3) carrying out hot pressing and cooling setting on the small foamed coarse blank in the step (5), wherein the hot pressing temperature is 150 ℃, and the hot pressing and cooling setting time is 450 seconds, so that the high-wear-resistance and compression-deformation-resistance ultrahigh-comfort EVA foamed material sole and test piece can be obtained.
Comparative example 2:
the comparative example comprises the following raw materials in parts by weight:
ethylene-vinyl acetate copolymer: 40 parts of a mixture;
polyolefin thermoplastic elastomer: 30 parts of (1);
maleic anhydride grafted polyethylene: 10 parts of (A);
wear-resisting agent: 15 parts of (1);
stearic acid: 0.5 part;
zinc stearate: 1 part;
zinc oxide: 1.5 parts;
talc powder: 4 parts of a mixture;
a bridging agent: 1 part;
foaming agent: 5 parts of a mixture;
wherein the ethylene-vinyl acetate copolymer is prepared from EVA7470M and EVA40W in a mass ratio of 2:1, the EVA7470M is prepared by Taiwan plastic company, and the EVA40W is prepared by DuPont company; the polyolefin block copolymer is the model number infuse9107, produced by the Dow company; maleic anhydride grafted polyethylene as
Figure BDA0003343432600000151
E588, manufactured by DuPont corporation; the wear-resisting agent is silicone master batch, the model is CMB1502, and is produced by Saito high polymer material (Shanghai) Co., Ltd; the cross-linking agent is 1, 4-di-tert-butylperoxy diisopropylbenzene; the foaming agent is azodicarbonamide.
Comparative example the mixing ratio of the added raw materials is as described above, comprising the steps of:
(1) pouring ethylene-vinyl acetate copolymer, polyolefin elastomer, maleic anhydride grafted polyethylene, wear-resisting agent, stearic acid, zinc stearate, zinc oxide and talcum powder into an internal mixer for internal mixing according to the raw material proportion, turning for 4-5 times, controlling the internal mixing temperature at 115-120 ℃ and the time at 12-15 minutes;
(2) adding a bridging agent and a foaming agent into the step (1), and continuously carrying out banburying, wherein the banburying temperature is controlled at 110-115 ℃ and the time is about 3-5 minutes;
(3) conveying the material uniformly mixed in the open mill in the step (2) to a granulator for granulation, and cooling the granulated particles to room temperature;
(4) and (4) carrying out small foaming on the particles in the step (3), wherein the mold temperature is about 155 ℃ and 160 ℃, and the vulcanization time is about 500 ℃ and 600 seconds, so as to obtain the small foamed coarse blank.
(5) And (4) carrying out hot pressing and cooling setting on the small foamed coarse blank in the step (4), wherein the hot pressing temperature is 150 ℃, and the hot pressing and cooling setting time is 450 seconds, so as to obtain the EVA foamed material sole and the test piece.
Table 2: formula of two-time molding process examples and comparative examples
Figure BDA0003343432600000152
Figure BDA0003343432600000161
The EVA foams obtained in examples 1 to 4 and comparative examples 1 to 2 were subjected to physical property tests as shown in Table 3 under conditions of a temperature of 23. + -. 3 ℃ and a humidity of 65. + -. 5%.
Table 3: physical Properties of EVA foam of examples and comparative examples
Figure BDA0003343432600000162
The wear-resisting agents added in the embodiments of the invention are all polytetrafluoroethylene/styrene butadiene rubber composite materials, the wear-resisting agents added in the comparative examples are common silicone master batches, wherein the embodiments 1-2 and the comparative example 1 are primary injection processes, and the embodiments 3-4 and the comparative example 2 are secondary die pressing processes. As can be seen from the data in Table 3, the wear resistance and compression deformation of each example are obviously better than those of the comparative examples no matter the primary process or the secondary process, and the data of each example can reach the national physical property standard of the EVA foamed sole material, wherein the examples 2 and 4 can meet the performance requirements of high resilience and light weight.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (10)

1. The EVA foaming material for the shoes is characterized by being prepared by mixing and foaming formula materials, wherein the formula materials comprise the following raw materials in parts by weight:
Figure FDA0003343432590000011
the wear-resisting agent is a polytetrafluoroethylene and styrene butadiene rubber composite solid material.
2. EVA foam for shoes according to claim 1, characterized in that the vinyl acetate content of the ethylene-vinyl acetate copolymer is between 18% and 40%.
3. The EVA foaming material for shoes according to claim 1, wherein the wear-resistant agent is a composite solid material obtained by emulsion blending and physical precipitation of polytetrafluoroethylene emulsion and styrene-butadiene rubber emulsion.
4. EVA foam for shoes according to claim 3, characterized in that the abrasion-resistant agent is obtained in the following specific manner: mixing the polytetrafluoroethylene emulsion and the styrene butadiene rubber emulsion under stirring, continuously stirring for a certain time, adding saturated salt solution until solid is separated out, crushing the obtained solid, placing the crushed solid in clear water, soaking for at least 12 hours, and then drying in vacuum to obtain the polytetrafluoroethylene and styrene butadiene rubber composite solid material.
5. The EVA foam material for shoes as claimed in claim 4, wherein the polytetrafluoroethylene emulsion has latex particles of 0.1-1 μm in diameter and 50-65% of solid content.
6. The EVA foaming material for shoes as claimed in claim 4, wherein the styrene-butadiene rubber emulsion has a solid content of 50-65%, and the mass ratio of the polytetrafluoroethylene emulsion to the styrene-butadiene rubber emulsion is 1: (1-3).
7. The EVA foam for shoes according to any one of claims 1 to 6, wherein the bridging agent is 1, 4-di-tert-butylperoxydiisopropylbenzene; the foaming agent is azodicarbonamide.
8. A method of preparing EVA foam for shoes as claimed in any one of claims 1 to 7, comprising the steps of:
s1, mixing all the raw materials except the bridging agent and the foaming agent in the weighed raw materials in the formula;
s2, adding the bridging agent and the foaming agent into the material mixed in the step S1, and mixing;
s3, granulating the mixture obtained in the step S2, and standing for cooling;
and S4, carrying out an IP (Internet protocol) primary forming process or an MD secondary die pressing process on the cooled particles obtained in the step S3 to obtain the high-wear-resistance EVA foaming material for the shoes.
9. The preparation method according to claim 8, wherein the IP one-step molding process specifically comprises the following steps: and (5) injecting the particles cooled in the step (S3) by an EVA injection machine, vulcanizing and foaming to obtain the EVA foaming material for shoes.
10. The method for preparing the composite material according to claim 8, wherein the MD secondary molding process is specifically as follows: weighing the particles cooled in the step S3 according to the mould body, and carrying out small foaming; and carrying out hot pressing, cooling and shaping on the rough blank obtained by small foaming to obtain the EVA foaming material for the shoes.
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CN114213745A (en) * 2022-01-19 2022-03-22 安徽佳宾新材料科技有限公司 EVA (ethylene-vinyl acetate) foaming material and preparation method thereof
CN114736417A (en) * 2022-05-23 2022-07-12 安踏（中国）有限公司 EVA foamed sole with starry appearance and preparation method thereof
CN115028921A (en) * 2022-06-22 2022-09-09 福建嘉怡塑胶有限公司 One-step formed environment-friendly EVA supercritical foaming sole and preparation method thereof
CN115746440A (en) * 2022-11-23 2023-03-07 莆田市百合鞋业有限公司 EVA wear-resistant sole and preparation method thereof
CN115746440B (en) * 2022-11-23 2024-02-09 莆田市百合鞋业有限公司 EVA wear-resistant sole and preparation method thereof

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