WO2024026920A1 - Composite hot melt adhesive film for soles and preparation method therefor - Google Patents

Composite hot melt adhesive film for soles and preparation method therefor Download PDF

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Publication number
WO2024026920A1
WO2024026920A1 PCT/CN2022/112254 CN2022112254W WO2024026920A1 WO 2024026920 A1 WO2024026920 A1 WO 2024026920A1 CN 2022112254 W CN2022112254 W CN 2022112254W WO 2024026920 A1 WO2024026920 A1 WO 2024026920A1
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parts
eva
adhesive film
layer
melt adhesive
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PCT/CN2022/112254
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French (fr)
Chinese (zh)
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宾家荃
宾家齐
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广东汇齐新材料有限公司
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Publication of WO2024026920A1 publication Critical patent/WO2024026920A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/24—Plastics; Metallised plastics based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/241—Polyolefin, e.g.rubber
    • C09J7/243—Ethylene or propylene polymers
    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J123/04—Homopolymers or copolymers of ethene
    • C09J123/08—Copolymers of ethene
    • C09J123/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C09J123/0853—Vinylacetate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J151/06—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/35—Heat-activated
    • 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
    • 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
    • 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
    • C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2475/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
    • C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
    • C09J2301/122—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present only on one side of the carrier, e.g. single-sided adhesive tape
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/304—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being heat-activatable, i.e. not tacky at temperatures inferior to 30°C
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2423/00—Presence of polyolefin
    • C09J2423/04—Presence of homo or copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2423/00—Presence of polyolefin
    • C09J2423/04—Presence of homo or copolymers of ethene
    • C09J2423/046—Presence of homo or copolymers of ethene in the substrate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2451/00—Presence of graft polymer

Definitions

  • the invention relates to the field of shoe sole materials, and in particular to a composite hot melt adhesive film for shoe soles and a preparation method thereof.
  • the sole is generally mainly composed of the midsole and the outsole.
  • the outsole is in contact with the ground and has good wear resistance and anti-slip properties. Therefore, the outsole is made of carbon rubber, which has wear resistance.
  • the midsole is glued to the top surface of the outsole through a coated and formed adhesive layer.
  • the midsole serves as the support body of the shoe to absorb and buffer the reaction force during movement. Therefore, the midsole is made of polyurethane, which can provide cushioning properties.
  • the outsole and midsole are made of different materials, and the contact force between the adhesive layer and different materials is different; therefore, the contact force between the adhesive layer and the outsole is often And there is a gap in the contact force between the adhesive layer and the midsole, making it difficult for the midsole and the outsole to be firmly integrated into one through the adhesive layer and easily separated. Therefore, the shoe soles of the prior art have the problem of being easily disintegrated due to insufficient gluing strength.
  • the purpose of the present invention is to provide a composite hot melt adhesive film for shoe soles and a preparation method thereof, so as to solve the problem that the outsole and midsole are easily disintegrated due to insufficient adhesive force of the composite adhesive film for shoe soles. .
  • a composite hot melt adhesive film for shoe soles including:
  • the EVA adhesive film layer and the EVA/rubber elastomer composite layer are bonded to the TPU/EVA alloy base layer through thermal bonding to form the composite hot melt adhesive film for shoe soles.
  • the TPU/EVA alloy base layer includes the following raw materials by weight: 50-70 parts of EVA resin, 15-30 parts of TPU, 0.1-1 part of zinc stearate, 0.5-1.5 parts of azodicarbonamide, acrylic acid 5-15 parts of glycidyl ester, 0.1-0.5 parts of antioxidant, 0.5-1.5 parts of stearic acid, 0.5-1.5 parts of anti-UV additive, 0.1-0.5 parts of cumene peroxide, and 1-5 parts of talc.
  • the EVA film layer includes the following raw materials by weight: 60-80 parts of EVA grafted maleic anhydride, 15-30 parts of polyether polyol, 1-5 parts of microcrystalline wax, and 2-6 parts of terpene resin. parts, antioxidant 0.5-1.5 parts, vinyl trichlorosilane 0.2-0.5 parts, cumene peroxide 0.5-1.5 parts.
  • the molecular weight of the polyether polyol is 400-4000.
  • VA content in the EVA-grafted maleic anhydride is 28%, and the grafting rate of maleic anhydride is 1.2%.
  • the EVA/rubber elastomer composite layer includes the following raw materials in parts by weight: 50-80 parts by weight of EVA main resin, 1-5 parts by styrene-butadiene block copolymer, and amino acid-modified maleic anhydride grafted polyethylene. 10-15 parts, terpene resin 3-10 parts, cumene peroxide 0.1-1 part, antioxidant 0.1-1 part.
  • the above-mentioned preparation method of composite hot-melt adhesive film for shoe soles includes the following steps:
  • Graft EVA with 60-80 parts of maleic anhydride, 15-30 parts of polyether polyol, 1-5 parts of microcrystalline wax, 2-6 parts of terpene resin, 0.5-1.5 parts of antioxidant, and vinyl trichlorosilane 0.2-0.5 parts and 0.5-1.5 parts of cumene peroxide are added to the mixer for premixing, and then put into a screw extruder for melt extrusion, granulation, and casting to form a film to obtain an EVA film layer;
  • EVA main resin 1-5 parts of styrene-butadiene block copolymer, 10-15 parts of amino acid-modified maleic anhydride grafted polyethylene, 3-10 parts of terpene resin, and isoperoxide 0.1-1 part of propylbenzene and 0.1-1 part of antioxidant are added to the mixer for premixing, and then put into a screw extruder for melt extrusion, granulation, and casting to form a film to obtain an EVA/rubber elastomer composite layer;
  • the EVA adhesive film layer and the EVA/rubber elastomer composite layer are respectively bonded to the upper surface and lower surface of the TPU/EVA alloy base layer through thermal bonding to form the composite hot melt adhesive film for shoe soles.
  • the premixing temperature is 120-150°C
  • the stirring speed is 250-500r/min
  • the stirring time is 4-10 minutes.
  • the extrusion temperature of the screw extruder is 160-200°C
  • the stirring speed is 300-600r/min.
  • the casting temperature in the film forming process is 160-200°C.
  • the composite hot-melt adhesive film for shoe soles of the present invention is a three-layer composite adhesive film material.
  • the surface layer is a graft-modified EVA adhesive film layer, which is used to bond the EVA midsole.
  • the middle layer is a high-strength TPU/EVA alloy layer, and the bottom layer is EVA.
  • Rubber elastomer composite layer uses a three-layer thermal bonding method to make a composite film, which is then used for sole bonding. Through the multi-layer composite film method, the poor bonding strength of the sole is solved, and it can adapt to different midsoles and outsole
  • the sole is heat-resistant, hydrolysis-resistant and washable.
  • the manufacturer of the reagents or instruments used in the present invention is not indicated, they are all conventional products that can be purchased on the market.
  • EVA main resin 60 parts of EVA main resin, 3 parts of styrene-butadiene block copolymer, 12 parts of amino acid-modified maleic anhydride grafted polyethylene, 8 parts of terpene resin, 0.5 parts of cumene peroxide, and 0.5 parts of antioxidant.
  • the extrusion temperature of the screw extruder is 180°C and the stirring speed is 450r/min, extruded by a screw extruder, granulated, and cast into a film at 180°C to obtain an EVA/rubber elastomer composite layer;
  • the EVA adhesive film layer and the EVA/rubber elastomer composite layer are respectively bonded to the upper surface and lower surface of the TPU/EVA alloy base layer through thermal bonding to form the composite hot melt adhesive film for shoe soles.
  • the EVA adhesive film layer and the EVA/rubber elastomer composite layer are respectively bonded to the upper surface and lower surface of the TPU/EVA alloy base layer through thermal bonding to form the composite hot melt adhesive film for shoe soles.
  • EVA main resin 1 part of styrene-butadiene block copolymer, 15 parts of amino acid-modified maleic anhydride-grafted polyethylene, 3 parts of terpene resin, 0.1 part of cumene peroxide, and 0.1 part of antioxidant.
  • the extrusion temperature of the screw extruder is 180°C and the stirring speed is 450r/min, extruded by a screw extruder, granulated, and cast into a film at 180°C to obtain an EVA/rubber elastomer composite layer;
  • the EVA adhesive film layer and the EVA/rubber elastomer composite layer are respectively bonded to the upper surface and lower surface of the TPU/EVA alloy base layer through thermal bonding to form the composite hot melt adhesive film for shoe soles.
  • Polyethylene-ethyl acrylate copolymer is the toughest and most flexible group of polyolefins. It is a random copolymer of ethylene and ethyl acrylate. Compared with ethylene-vinyl acetate, polyethylene-ethyl acrylate The copolymer has higher thermal stability and excellent adhesion to non-polar substrates, and is a non-corrosive degradation product.
  • Maleic anhydride-grafted EVA is produced by reaction extrusion and grafting of maleic anhydride. Strongly polar side groups are introduced into the main chain of the EVA molecule. The grafted EVA becomes a material that improves the adhesion and adhesion between polar materials and non-polar materials. Compatible bridges, the bonding strength is significantly improved.
  • Thermoplastic polyurethane (TPU) is increasingly popular because of its superior performance and environmental protection concept. It has good mechanical properties, durability and durability. The advantages of abrasion, low-temperature compliance and adhesion can form complementary advantages with ethylene-vinyl acetate copolymer, especially for shoe sole materials.
  • Styrene-butadiene block copolymer is referred to as SBS.
  • SBS thermoplastic elastomer is a tri-block copolymer with styrene and butadiene as monomers. It has the solubility and thermoplasticity of polystyrene (PS) and the It has the flexibility and resilience of butadiene rubber (PB), and has the dual characteristics of thermoplastics and vulcanized rubber.
  • PS polystyrene
  • PB butadiene rubber
  • SBS can be in contact with water, weak acids, alkali, etc., has excellent tensile strength, large surface friction coefficient, and good low temperature performance , with excellent electrical properties and good processability, it is currently the most consumed thermoplastic elastomer.
  • SBS As an adhesive, SBS has the characteristics of high solid content, quick drying, and low temperature resistance. At high temperatures, it can be directly plasticized. Due to its strong cohesion and high bonding strength, it is an important base material for hot melt adhesives.
  • SBS can be grafted with polyethylene and 2-hydroxyethyl acrylate copolymer. , polyethylene-ethyl acrylate copolymer is blended to increase the cohesive strength of the blend, and the rubber component styrene-butadiene block copolymer that can be co-vulcanized can interpenetrate with the rubber sheet to be vulcanized and participate in the rubber process. The chemical cross-linking process of the sole integrates the rubber film and the rubber outsole.
  • Terpene resins are some thermoplastic block copolymers, which are polymerized from terpene mixtures. They are an excellent tackifier with strong adhesion, good anti-aging properties, high cohesion, heat resistance, light resistance, acid resistance, Excellent properties such as alkali resistance, odor resistance, and non-toxicity.
  • This resin is an excellent tackifier for styrene-butadiene block copolymer (SBR), phenylacetic acid-isoprene-styrene (SIS) and styrene (SBS). Its tackifier performance is better than that of rosin resin. , modified rosin resin and petroleum resin, etc.
  • Blending terpene resin with polyethylene grafted 2-hydroxyethyl acrylate copolymer, polyethylene-ethyl acrylate copolymer, and styrene-butadiene block copolymer can increase the initial tack and flow of hot melt adhesive films. properties, easy to granulate and film, and can reduce production costs.
  • BPO Dibenzoyl peroxide
  • BPO is a diacyl organic peroxide that is used as an initiator for polymerization reactions to control the rate of polymerization reactions to a certain extent.
  • BPO produces BPO through a smooth, stable, and controllable decomposition reaction.
  • the cross-linking agent and initiator are properly introduced to increase the molecular weight of the mixture, which can improve the bonding strength, heat resistance, water washing resistance, chemical resistance, aging resistance, and storage stability of the hot melt adhesive film.
  • the EVA film layer of the composite hot-melt adhesive film for soles in Examples 1-3 is bonded to the midsole by hot-melting, and the EVA/rubber elastomer composite layer is bonded to the outsole by hot-melting.
  • the sole has high bonding strength and the outsole and midsole are not easy to separate.
  • the composite hot-melt adhesive film for soles obtained in the above-mentioned Examples 1-3 is compounded with a rubber outsole and an EVA midsole respectively according to the existing technology to obtain a composite sole. Cut the composite sole into a strip 2.5cm wide and 20cm long, and test the peel strength on a tensile testing machine at a speed of 100mm/min. See Table 1 for specific test results.
  • the composite hot-melt adhesive film for shoe soles of the present invention is a three-layer composite adhesive film material.
  • the surface layer is a graft-modified EVA adhesive film layer, which is used to bond the EVA midsole.
  • the middle layer is a high-strength TPU/EVA alloy layer, and the bottom layer is EVA.
  • Rubber elastomer composite layer uses a three-layer thermal bonding method to make a composite film, which is then used for sole bonding. Through the multi-layer composite film method, the poor bonding strength of the sole is solved, and it can adapt to different midsoles and outsole
  • the sole is heat-resistant, hydrolysis-resistant and washable.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Footwear And Its Accessory, Manufacturing Method And Apparatuses (AREA)

Abstract

A composite hot melt adhesive film for soles and a preparation method therefor. The composite hot melt adhesive film comprises: a TPU/EVA alloy base layer; an EVA adhesive film layer located on the upper surface of the TPU/EVA alloy base layer; and an EVA/rubber elastomer composite layer located on the lower surface of the TPU/EVA alloy base layer, wherein the EVA adhesive film layer and the EVA/rubber elastomer composite layer are bonded with the TPU/EVA alloy base layer by means of thermal bonding to form the composite hot melt adhesive film for soles. The composite hot melt adhesive film for soles is a three-layer composite adhesive film material, wherein the surface layer is a graft modified EVA adhesive film layer and used for bonding an EVA insole, the middle layer is a high-strength TPU/EVA alloy layer, and the bottom is the EVA/rubber elastomer composite layer. The composite film is prepared by using a three-layer thermal bonding method, and is then used for bonding an outsole and the insole of the sole. By means of a multilayer composite film, the problems of the sole having a poor bonding strength and the outsole and the insole being prone to separating are solved, and the manufactured sole has good heat resistance, good hydrolysis resistance and good washing resistance.

Description

鞋底用复合热熔胶膜及其制备方法Composite hot melt adhesive film for shoe soles and preparation method thereof
相关申请的交叉引用。Cross-references to related applications.
本申请要求于2022年08月01日提交中国专利局，申请号为CN202210916523.5，发明名称为“鞋底用复合热熔胶膜及其制备方法”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。This application requires the priority of the Chinese patent application submitted to the China Patent Office on August 1, 2022, with the application number CN202210916523.5, and the invention name is "Composite hot melt adhesive film for shoe soles and preparation method thereof", and its entire content has been approved This reference is incorporated into this application.
技术领域Technical field
本发明涉及鞋底材料领域，尤其是涉及一种鞋底用复合热熔胶膜及其制备方法。The invention relates to the field of shoe sole materials, and in particular to a composite hot melt adhesive film for shoe soles and a preparation method thereof.
背景技术Background technique
随着高分子材料的性能改良与混炼技术的提升，鞋底的制作与其材料亦是日益被改良。鞋底一般主要是由中底与大底所组成。大底与地面接触，具有耐磨性能好、止滑性能好等特点，故该大底制作上是以碳橡胶具有耐磨耗特性的材质所制成。中底是通过涂布成型的黏胶层胶合于该大底的顶面上。中底作为鞋子的支撑体，以吸收并缓冲移动时的反作用力，故该中底制作上是以聚氨酯能提供缓冲性能的材质所制成。As the performance of polymer materials improves and mixing technology improves, the production of soles and their materials are also increasingly improved. The sole is generally mainly composed of the midsole and the outsole. The outsole is in contact with the ground and has good wear resistance and anti-slip properties. Therefore, the outsole is made of carbon rubber, which has wear resistance. The midsole is glued to the top surface of the outsole through a coated and formed adhesive layer. The midsole serves as the support body of the shoe to absorb and buffer the reaction force during movement. Therefore, the midsole is made of polyurethane, which can provide cushioning properties.
技术问题technical problem
然而，由于大底和中底是由不同的材质所制成，且该黏胶层与不同材质之间的接触力有差异；因此，经常因为该黏胶层与该大底之间的接触力及该黏胶层与该中底之间的接触力有落差，使得该中底及该大底难以通过该黏胶层稳固地相结合为一体而容易相分离。故现有技术的鞋底具有因胶合强度不足所导致的易解体的问题。However, since the outsole and midsole are made of different materials, and the contact force between the adhesive layer and different materials is different; therefore, the contact force between the adhesive layer and the outsole is often And there is a gap in the contact force between the adhesive layer and the midsole, making it difficult for the midsole and the outsole to be firmly integrated into one through the adhesive layer and easily separated. Therefore, the shoe soles of the prior art have the problem of being easily disintegrated due to insufficient gluing strength.
技术解决方案Technical solutions
根据本申请的各种实施例，本发明的目的是提供一种鞋底用复合热熔胶膜及其制备方法，解决因鞋底复合胶膜粘结力不足，导致大底和中底易解体的问题。According to various embodiments of the present application, the purpose of the present invention is to provide a composite hot melt adhesive film for shoe soles and a preparation method thereof, so as to solve the problem that the outsole and midsole are easily disintegrated due to insufficient adhesive force of the composite adhesive film for shoe soles. .
一种鞋底用复合热熔胶膜，包括：A composite hot melt adhesive film for shoe soles, including:
TPU/EVA合金基层；TPU/EVA alloy base layer;
以及位于TPU/EVA合金基层上表面的EVA胶膜层；And the EVA film layer located on the upper surface of the TPU/EVA alloy base layer;
以及位于TPU/EVA合金基层下表面的EVA/橡胶弹性体复合层；and an EVA/rubber elastomer composite layer located on the lower surface of the TPU/EVA alloy base layer;
所述EVA胶膜层及所述EVA/橡胶弹性体复合层通过热贴合方式黏合TPU/EVA合金基层，形成所述鞋底用复合热熔胶膜。The EVA adhesive film layer and the EVA/rubber elastomer composite layer are bonded to the TPU/EVA alloy base layer through thermal bonding to form the composite hot melt adhesive film for shoe soles.
进一步地，所述TPU/EVA合金基层包括如下重量份的原料：EVA树脂50-70份、TPU 15-30份、硬脂酸锌0.1-1份、偶氮二甲酰胺0.5-1.5份、丙烯酸缩水甘油酯5-15份、抗氧剂0.1-0.5份、硬脂酸0.5-1.5份、抗UV助剂0.5-1.5份、过氧化异丙苯0.1-0.5份、滑石粉1-5份。Further, the TPU/EVA alloy base layer includes the following raw materials by weight: 50-70 parts of EVA resin, 15-30 parts of TPU, 0.1-1 part of zinc stearate, 0.5-1.5 parts of azodicarbonamide, acrylic acid 5-15 parts of glycidyl ester, 0.1-0.5 parts of antioxidant, 0.5-1.5 parts of stearic acid, 0.5-1.5 parts of anti-UV additive, 0.1-0.5 parts of cumene peroxide, and 1-5 parts of talc.
进一步地，所述EVA胶膜层包括如下重量份的原料：EVA接枝马来酸酐60-80份、聚醚多元醇15-30份、微晶蜡1-5份、萜烯树脂2-6份、抗氧剂0.5-1.5份、乙烯基三氯硅烷0.2-0.5份、过氧化异丙苯0.5-1.5份。Further, the EVA film layer includes the following raw materials by weight: 60-80 parts of EVA grafted maleic anhydride, 15-30 parts of polyether polyol, 1-5 parts of microcrystalline wax, and 2-6 parts of terpene resin. parts, antioxidant 0.5-1.5 parts, vinyl trichlorosilane 0.2-0.5 parts, cumene peroxide 0.5-1.5 parts.
进一步地，所述聚醚多元醇的分子量为400～4000。Further, the molecular weight of the polyether polyol is 400-4000.
进一步地，所述EVA接枝马来酸酐中VA含量28％，马来酸酐接枝率为1.2％。Further, the VA content in the EVA-grafted maleic anhydride is 28%, and the grafting rate of maleic anhydride is 1.2%.
进一步地，EVA/橡胶弹性体复合层包括如下重量份的原料：EVA主体树脂50-80份、苯乙烯-丁二烯嵌段共聚物1-5份、氨基酸改性马来酸酐接枝聚乙烯10-15份、萜烯树脂3-10份、过氧化异丙苯0.1-1份、抗氧化剂0.1-1份。Further, the EVA/rubber elastomer composite layer includes the following raw materials in parts by weight: 50-80 parts by weight of EVA main resin, 1-5 parts by styrene-butadiene block copolymer, and amino acid-modified maleic anhydride grafted polyethylene. 10-15 parts, terpene resin 3-10 parts, cumene peroxide 0.1-1 part, antioxidant 0.1-1 part.
上述的鞋底用复合热熔胶膜的制备方法，包括如下步骤：The above-mentioned preparation method of composite hot-melt adhesive film for shoe soles includes the following steps:
将EVA接枝马来酸酐60-80份、聚醚多元醇15-30份、微晶蜡1-5份、萜烯树脂2-6份、抗氧剂0.5-1.5份、乙烯基三氯硅烷0.2-0.5份、过氧化异丙苯0.5-1.5份加入混合机进行预混合，然后投入螺杆挤出机中熔融挤出、造粒、流延成膜，得到EVA胶膜层；Graft EVA with 60-80 parts of maleic anhydride, 15-30 parts of polyether polyol, 1-5 parts of microcrystalline wax, 2-6 parts of terpene resin, 0.5-1.5 parts of antioxidant, and vinyl trichlorosilane 0.2-0.5 parts and 0.5-1.5 parts of cumene peroxide are added to the mixer for premixing, and then put into a screw extruder for melt extrusion, granulation, and casting to form a film to obtain an EVA film layer;
将EVA树脂50-70份、TPU 15-30份、硬脂酸锌0.1-1份、偶氮二甲酰胺0.5-1.5份、丙烯酸缩水甘油酯5-15份、抗氧剂0.1-0.5份、硬脂酸0.5-1.5份、抗UV助剂0.5-1.5份、过氧化异丙苯0.1-0.5份、滑石粉1-5份加入混合机进行预混合，然后投入螺杆挤出机中熔融挤出、造粒、流延成膜，得到TPU/EVA合金基层；Combine 50-70 parts of EVA resin, 15-30 parts of TPU, 0.1-1 part of zinc stearate, 0.5-1.5 parts of azodicarbonamide, 5-15 parts of glycidyl acrylate, 0.1-0.5 parts of antioxidant, Add 0.5-1.5 parts of stearic acid, 0.5-1.5 parts of anti-UV additive, 0.1-0.5 parts of cumene peroxide, and 1-5 parts of talc powder into the mixer for premixing, then put it into the screw extruder for melt extrusion , granulating, and casting to form a film to obtain a TPU/EVA alloy base layer;
将EVA主体树脂50-80份、苯乙烯-丁二烯嵌段共聚物1-5份、氨基酸改性马来酸酐接枝聚乙烯10-15份、萜烯树脂3-10份、过氧化异丙苯0.1-1份、抗 氧化剂0.1-1份加入混合机进行预混合，然后投入螺杆挤出机中熔融挤出、造粒、流延成膜，得到EVA/橡胶弹性体复合层；Mix 50-80 parts of EVA main resin, 1-5 parts of styrene-butadiene block copolymer, 10-15 parts of amino acid-modified maleic anhydride grafted polyethylene, 3-10 parts of terpene resin, and isoperoxide 0.1-1 part of propylbenzene and 0.1-1 part of antioxidant are added to the mixer for premixing, and then put into a screw extruder for melt extrusion, granulation, and casting to form a film to obtain an EVA/rubber elastomer composite layer;
将EVA胶膜层和EVA/橡胶弹性体复合层通过热贴合方式分别黏合在TPU/EVA合金基层的上表面和下表面，形成所述鞋底用复合热熔胶膜。The EVA adhesive film layer and the EVA/rubber elastomer composite layer are respectively bonded to the upper surface and lower surface of the TPU/EVA alloy base layer through thermal bonding to form the composite hot melt adhesive film for shoe soles.
进一步地，所述预混合温度是120-150℃，搅拌速度为250-500r/min，搅拌时间为4-10分钟。Further, the premixing temperature is 120-150°C, the stirring speed is 250-500r/min, and the stirring time is 4-10 minutes.
进一步地，所述螺杆挤出机的挤出温度是160-200℃，搅拌速度为300-600r/min。Further, the extrusion temperature of the screw extruder is 160-200°C, and the stirring speed is 300-600r/min.
进一步地，所述流延成膜中流延温度为160-200℃。Further, the casting temperature in the film forming process is 160-200°C.
有益效果beneficial effects
本发明鞋底用复合热熔胶膜为三层复合胶膜材料，表层为接枝改性EVA胶膜层，用于粘结EVA中底，中间层为高强度TPU/EVA合金层，底部为EVA/橡胶弹性体复合层，采用三层热贴合方式，做成复合膜，然后用于鞋底粘结，通过多层复合膜的方式，解决鞋底粘结强度差，可以适应不同的中底和大底，制成鞋底耐热，耐水解，耐水洗性能好。The composite hot-melt adhesive film for shoe soles of the present invention is a three-layer composite adhesive film material. The surface layer is a graft-modified EVA adhesive film layer, which is used to bond the EVA midsole. The middle layer is a high-strength TPU/EVA alloy layer, and the bottom layer is EVA. / Rubber elastomer composite layer uses a three-layer thermal bonding method to make a composite film, which is then used for sole bonding. Through the multi-layer composite film method, the poor bonding strength of the sole is solved, and it can adapt to different midsoles and outsole The sole is heat-resistant, hydrolysis-resistant and washable.
本发明的实施方式Embodiments of the invention
下面将结合本发明的具体实施方式，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to specific implementation modes of the present invention. Obviously, the described embodiments are only some, not all, of the embodiments of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts fall within the scope of protection of the present invention.
本发明所用试剂或仪器未注明生产厂商者，均为可以通过市售购买获得的常规产品。If the manufacturer of the reagents or instruments used in the present invention is not indicated, they are all conventional products that can be purchased on the market.
实施例1Example 1
将EVA接枝马来酸酐70份、聚醚多元醇25份、微晶蜡3份、萜烯树脂4份、抗氧剂1份、乙烯基三氯硅烷0.3份、过氧化异丙苯1份加入混合机，在温度是120℃、搅拌速度为400r/min下进行预混合，搅拌时间为8分钟，然后投入螺杆挤出机中，螺杆挤出机的挤出温度是160℃，搅拌速度为600r/min，经螺 杆挤出机熔融挤出、造粒、160℃流延成膜，得到EVA胶膜层；Graft EVA with 70 parts of maleic anhydride, 25 parts of polyether polyol, 3 parts of microcrystalline wax, 4 parts of terpene resin, 1 part of antioxidant, 0.3 parts of vinyltrichlorosilane, and 1 part of cumene peroxide. Add to the mixer, premix at a temperature of 120°C and a stirring speed of 400r/min. The stirring time is 8 minutes, and then put into the screw extruder. The extrusion temperature of the screw extruder is 160°C and the stirring speed is 600r/min, melt extrusion, granulation, and casting at 160°C to form a film through a screw extruder to obtain an EVA film layer;
将EVA树脂60份、TPU 25份、硬脂酸锌0.5份、偶氮二甲酰胺1份、丙烯酸缩水甘油酯10份、抗氧剂0.3份、硬脂酸1份、抗UV助剂1份、过氧化异丙苯0.3份、滑石粉3份加入混合机，在温度是150℃、搅拌速度为500r/min下进行预混合，搅拌时间为4分钟，然后投入螺杆挤出机中，螺杆挤出机的挤出温度是200℃，搅拌速度为300r/min，经螺杆挤出机挤出、造粒、200℃流延成膜，得到TPU/EVA合金基层；Combine 60 parts of EVA resin, 25 parts of TPU, 0.5 parts of zinc stearate, 1 part of azodicarbonamide, 10 parts of glycidyl acrylate, 0.3 parts of antioxidant, 1 part of stearic acid, and 1 part of anti-UV additive , 0.3 parts of cumene peroxide and 3 parts of talcum powder were added to the mixer, pre-mixed at a temperature of 150°C and a stirring speed of 500r/min. The stirring time was 4 minutes, and then put into the screw extruder. The screw extruded The extrusion temperature of the extruder is 200°C, the stirring speed is 300r/min, and the TPU/EVA alloy base layer is obtained through screw extruder extrusion, granulation, and film casting at 200°C;
将EVA主体树脂60份、苯乙烯-丁二烯嵌段共聚物3份、氨基酸改性马来酸酐接枝聚乙烯12份、萜烯树脂8份、过氧化异丙苯0.5份、抗氧化剂0.5份加入混合机在温度是130℃、搅拌速度为350r/min下进行预混合，搅拌时间为10分钟，然后投入螺杆挤出机中，螺杆挤出机的挤出温度是180℃，搅拌速度为450r/min，经螺杆挤出机挤出、造粒、180℃流延成膜，得到EVA/橡胶弹性体复合层；Mix 60 parts of EVA main resin, 3 parts of styrene-butadiene block copolymer, 12 parts of amino acid-modified maleic anhydride grafted polyethylene, 8 parts of terpene resin, 0.5 parts of cumene peroxide, and 0.5 parts of antioxidant. Add parts into the mixer for premixing at a temperature of 130°C and a stirring speed of 350r/min. The stirring time is 10 minutes, and then put into the screw extruder. The extrusion temperature of the screw extruder is 180°C and the stirring speed is 450r/min, extruded by a screw extruder, granulated, and cast into a film at 180°C to obtain an EVA/rubber elastomer composite layer;
将EVA胶膜层和EVA/橡胶弹性体复合层通过热贴合方式分别黏合在TPU/EVA合金基层的上表面和下表面，形成所述鞋底用复合热熔胶膜。The EVA adhesive film layer and the EVA/rubber elastomer composite layer are respectively bonded to the upper surface and lower surface of the TPU/EVA alloy base layer through thermal bonding to form the composite hot melt adhesive film for shoe soles.
实施例2Example 2
将EVA接枝马来酸酐60份、聚醚多元醇15份、微晶蜡1份、萜烯树脂2份、抗氧剂0.5份、乙烯基三氯硅烷0.2份、过氧化异丙苯0.5份加入混合机，在温度是120℃、搅拌速度为400r/min下进行预混合，搅拌时间为8分钟，然后投入螺杆挤出机中，螺杆挤出机的挤出温度是160℃，搅拌速度为600r/min，经螺杆挤出机熔融挤出、造粒、160℃流延成膜，得到EVA胶膜层；Graft EVA with 60 parts of maleic anhydride, 15 parts of polyether polyol, 1 part of microcrystalline wax, 2 parts of terpene resin, 0.5 part of antioxidant, 0.2 part of vinyltrichlorosilane, and 0.5 part of cumene peroxide. Add to the mixer, premix at a temperature of 120°C and a stirring speed of 400r/min. The stirring time is 8 minutes, and then put into the screw extruder. The extrusion temperature of the screw extruder is 160°C and the stirring speed is 600r/min, melt extrusion, granulation, and casting at 160°C to form a film through a screw extruder to obtain an EVA film layer;
将EVA树脂70份、TPU 30份、硬脂酸锌1份、偶氮二甲酰胺1.5份、丙烯酸缩水甘油酯15份、抗氧剂0.5份、硬脂酸1.5份、抗UV助剂1.5份、过氧化异丙苯0.5份、滑石粉5份加入混合机，在温度是150℃、搅拌速度为500r/min下进行预混合，搅拌时间为4分钟，然后投入螺杆挤出机中，螺杆挤出机的挤出温度是200℃，搅拌速度为300r/min，经螺杆挤出机挤出、造粒、200℃流延成膜，得到TPU/EVA合金基层；Combine 70 parts of EVA resin, 30 parts of TPU, 1 part of zinc stearate, 1.5 parts of azodicarbonamide, 15 parts of glycidyl acrylate, 0.5 parts of antioxidant, 1.5 parts of stearic acid, and 1.5 parts of anti-UV additives , 0.5 parts of cumene peroxide and 5 parts of talcum powder were added to the mixer, pre-mixed at a temperature of 150°C and a stirring speed of 500r/min. The stirring time was 4 minutes, and then put into the screw extruder. The screw extruded The extrusion temperature of the extruder is 200°C, the stirring speed is 300r/min, and the TPU/EVA alloy base layer is obtained through screw extruder extrusion, granulation, and film casting at 200°C;
将EVA主体树脂80份、苯乙烯-丁二烯嵌段共聚物5份、氨基酸改性马来酸酐接枝聚乙烯10份、萜烯树脂10份、过氧化异丙苯1份、抗氧化剂1份加入混 合机在温度是130℃、搅拌速度为250r/min下进行预混合，搅拌时间为10分钟，然后投入螺杆挤出机中，螺杆挤出机的挤出温度是180℃，搅拌速度为450r/min，经螺杆挤出机挤出、造粒、180℃流延成膜，得到EVA/橡胶弹性体复合层；Combine 80 parts of EVA main resin, 5 parts of styrene-butadiene block copolymer, 10 parts of amino acid-modified maleic anhydride grafted polyethylene, 10 parts of terpene resin, 1 part of cumene peroxide, and 1 part of antioxidant Add parts into the mixer for premixing at a temperature of 130°C and a stirring speed of 250r/min. The stirring time is 10 minutes, and then put into the screw extruder. The extrusion temperature of the screw extruder is 180°C and the stirring speed is 450r/min, extruded by a screw extruder, granulated, and cast into a film at 180°C to obtain an EVA/rubber elastomer composite layer;
将EVA胶膜层和EVA/橡胶弹性体复合层通过热贴合方式分别黏合在TPU/EVA合金基层的上表面和下表面，形成所述鞋底用复合热熔胶膜。The EVA adhesive film layer and the EVA/rubber elastomer composite layer are respectively bonded to the upper surface and lower surface of the TPU/EVA alloy base layer through thermal bonding to form the composite hot melt adhesive film for shoe soles.
实施例3Example 3
将EVA接枝马来酸酐60份、聚醚多元醇30份、微晶蜡5份、萜烯树脂6份、抗氧剂1.5份、乙烯基三氯硅烷0.5份、过氧化异丙苯1.5份加入混合机，在温度是120℃、搅拌速度为400r/min下进行预混合，搅拌时间为8分钟，然后投入螺杆挤出机中，螺杆挤出机的挤出温度是160℃，搅拌速度为600r/min，经螺杆挤出机熔融挤出、造粒、160℃流延成膜，得到EVA胶膜层；Graft EVA with 60 parts of maleic anhydride, 30 parts of polyether polyol, 5 parts of microcrystalline wax, 6 parts of terpene resin, 1.5 parts of antioxidant, 0.5 parts of vinyltrichlorosilane, and 1.5 parts of cumene peroxide. Add to the mixer, premix at a temperature of 120°C and a stirring speed of 400r/min. The stirring time is 8 minutes, and then put into the screw extruder. The extrusion temperature of the screw extruder is 160°C and the stirring speed is 600r/min, melt extrusion, granulation, and casting at 160°C to form a film through a screw extruder to obtain an EVA film layer;
将EVA树脂50份、TPU 15份、硬脂酸锌0.1份、偶氮二甲酰胺0.5份、丙烯酸缩水甘油酯5份、抗氧剂0.1份、硬脂酸0.5份、抗UV助剂0.5份、过氧化异丙苯0.1份、滑石粉1份加入混合机，在温度是150℃、搅拌速度为500r/min下进行预混合，搅拌时间为4分钟，然后投入螺杆挤出机中，螺杆挤出机的挤出温度是200℃，搅拌速度为300r/min，经螺杆挤出机挤出、造粒、200℃流延成膜，得到TPU/EVA合金基层；Combine 50 parts of EVA resin, 15 parts of TPU, 0.1 part of zinc stearate, 0.5 part of azodicarbonamide, 5 parts of glycidyl acrylate, 0.1 part of antioxidant, 0.5 part of stearic acid, and 0.5 part of anti-UV additive , 0.1 part of cumene peroxide and 1 part of talcum powder were added to the mixer, pre-mixed at a temperature of 150°C and a stirring speed of 500r/min. The stirring time was 4 minutes, and then put into the screw extruder. The screw extruded The extrusion temperature of the extruder is 200°C, the stirring speed is 300r/min, and the TPU/EVA alloy base layer is obtained through screw extruder extrusion, granulation, and film casting at 200°C;
将EVA主体树脂50份、苯乙烯-丁二烯嵌段共聚物1份、氨基酸改性马来酸酐接枝聚乙烯15份、萜烯树脂3份、过氧化异丙苯0.1份、抗氧化剂0.1份加入混合机在温度是130℃、搅拌速度为350r/min下进行预混合，搅拌时间为10分钟，然后投入螺杆挤出机中，螺杆挤出机的挤出温度是180℃，搅拌速度为450r/min，经螺杆挤出机挤出、造粒、180℃流延成膜，得到EVA/橡胶弹性体复合层；Mix 50 parts of EVA main resin, 1 part of styrene-butadiene block copolymer, 15 parts of amino acid-modified maleic anhydride-grafted polyethylene, 3 parts of terpene resin, 0.1 part of cumene peroxide, and 0.1 part of antioxidant. Add parts into the mixer for premixing at a temperature of 130°C and a stirring speed of 350r/min. The stirring time is 10 minutes, and then put into the screw extruder. The extrusion temperature of the screw extruder is 180°C and the stirring speed is 450r/min, extruded by a screw extruder, granulated, and cast into a film at 180°C to obtain an EVA/rubber elastomer composite layer;
将EVA胶膜层和EVA/橡胶弹性体复合层通过热贴合方式分别黏合在TPU/EVA合金基层的上表面和下表面，形成所述鞋底用复合热熔胶膜。The EVA adhesive film layer and the EVA/rubber elastomer composite layer are respectively bonded to the upper surface and lower surface of the TPU/EVA alloy base layer through thermal bonding to form the composite hot melt adhesive film for shoe soles.
聚乙烯-丙烯酸乙酯共聚物(EVA)是聚烯烃中韧性及柔度最大的一族，是乙烯和丙烯酸乙酯的无规共聚物，与乙烯-醋酸乙烯酯相比，聚乙烯-丙烯酸乙酯共聚物有更高的热稳定性和对非极性基质有优良的粘合力，并属于非腐蚀性降解产品。马来酸酐接枝EVA经反应挤出接枝马来酸酐制得，在EVA分子主链上引入了 强极性的侧基，接枝EVA成为增进极性材料与非极性材料粘接性和相容性的桥梁，粘接强度有显著提高。Polyethylene-ethyl acrylate copolymer (EVA) is the toughest and most flexible group of polyolefins. It is a random copolymer of ethylene and ethyl acrylate. Compared with ethylene-vinyl acetate, polyethylene-ethyl acrylate The copolymer has higher thermal stability and excellent adhesion to non-polar substrates, and is a non-corrosive degradation product. Maleic anhydride-grafted EVA is produced by reaction extrusion and grafting of maleic anhydride. Strongly polar side groups are introduced into the main chain of the EVA molecule. The grafted EVA becomes a material that improves the adhesion and adhesion between polar materials and non-polar materials. Compatible bridges, the bonding strength is significantly improved.
由于乙烯-醋酸乙烯共聚物发泡率高时，材料变形大，力学性能显著下降，热塑性聚氨酯(TPU)因其优越的性能和环保概念日益受到人们的欢迎，其具有的良好的机械性能、耐磨性、低温柔顺性以及黏合性等优点恰好可与乙烯-醋酸乙烯共聚物形成性能互补优势，尤其适用于鞋底材料。Because when the foaming rate of ethylene-vinyl acetate copolymer is high, the material deforms greatly and the mechanical properties decrease significantly. Thermoplastic polyurethane (TPU) is increasingly popular because of its superior performance and environmental protection concept. It has good mechanical properties, durability and durability. The advantages of abrasion, low-temperature compliance and adhesion can form complementary advantages with ethylene-vinyl acetate copolymer, especially for shoe sole materials.
苯乙烯-丁二烯嵌段共聚物简称SBS，SBS热塑性弹性体是以苯乙烯、丁二烯为单体的三嵌段共聚物，既有聚苯乙烯(PS)的溶解性和热塑性，又有顺丁橡胶(PB)的柔韧性和回弹性，兼具热塑性塑料和硫化橡胶的双重特点，SBS可以和水、弱酸、碱等接触，具有优良的拉伸强度，表面摩擦系数大，低温性能好，电性能优良，加工性能好等特性，是目前消费量最大的热塑性弹性体。SBS作为粘合剂具有高固体物质含量、快干、耐低温的特点。而在高温下则可直接塑化成型,由于其内聚力强，粘接强度高，所以它是热熔胶的一种重要基料，SBS可以和聚乙烯接枝丙烯酸-2-羟乙酯共聚物、聚乙烯-丙烯酸乙酯共聚物共混，增加共混物的内聚强度，采用能共硫化的橡胶组分苯乙烯-丁二烯嵌段共聚物能与待硫化橡胶片相互渗透，参与橡胶大底的化学交联过程，使胶膜和橡胶大底融为一体。Styrene-butadiene block copolymer is referred to as SBS. SBS thermoplastic elastomer is a tri-block copolymer with styrene and butadiene as monomers. It has the solubility and thermoplasticity of polystyrene (PS) and the It has the flexibility and resilience of butadiene rubber (PB), and has the dual characteristics of thermoplastics and vulcanized rubber. SBS can be in contact with water, weak acids, alkali, etc., has excellent tensile strength, large surface friction coefficient, and good low temperature performance , with excellent electrical properties and good processability, it is currently the most consumed thermoplastic elastomer. As an adhesive, SBS has the characteristics of high solid content, quick drying, and low temperature resistance. At high temperatures, it can be directly plasticized. Due to its strong cohesion and high bonding strength, it is an important base material for hot melt adhesives. SBS can be grafted with polyethylene and 2-hydroxyethyl acrylate copolymer. , polyethylene-ethyl acrylate copolymer is blended to increase the cohesive strength of the blend, and the rubber component styrene-butadiene block copolymer that can be co-vulcanized can interpenetrate with the rubber sheet to be vulcanized and participate in the rubber process. The chemical cross-linking process of the sole integrates the rubber film and the rubber outsole.
萜烯树脂是一些热塑性嵌段共聚物，是由萜烯混合物聚合而成，是一种优良的增粘剂，具有粘接力强、抗老化性能好、内聚力高、耐热、耐光、耐酸、耐碱、耐臭、无毒等优良性能。该树脂是苯乙烯-丁二烯嵌段共聚物(SBR)、苯乙酸-异戊二烯-苯乙烯(SIS)和苯乙烯(SBS)的优良增粘剂，其增粘性能优于松香树脂、松香树脂改性物及石油树脂等。萜烯树脂与聚乙烯接枝丙烯酸-2-羟乙酯共聚物、聚乙烯-丙烯酸乙酯共聚物、苯乙烯-丁二烯嵌段共聚物共混可以增加热熔胶膜的初粘性和流动性，易于造粒和制膜，同时可以降低生产成本。Terpene resins are some thermoplastic block copolymers, which are polymerized from terpene mixtures. They are an excellent tackifier with strong adhesion, good anti-aging properties, high cohesion, heat resistance, light resistance, acid resistance, Excellent properties such as alkali resistance, odor resistance, and non-toxicity. This resin is an excellent tackifier for styrene-butadiene block copolymer (SBR), phenylacetic acid-isoprene-styrene (SIS) and styrene (SBS). Its tackifier performance is better than that of rosin resin. , modified rosin resin and petroleum resin, etc. Blending terpene resin with polyethylene grafted 2-hydroxyethyl acrylate copolymer, polyethylene-ethyl acrylate copolymer, and styrene-butadiene block copolymer can increase the initial tack and flow of hot melt adhesive films. properties, easy to granulate and film, and can reduce production costs.
过氧化二苯甲酰(BPO)是一种二酰基有机过氧化物，用作聚合反应的引发剂，一定程度的控制了聚合反应的速率，BPO通过平滑、稳定、可控制的分解反应，产生高线性和分子量的聚合物。交联剂和引发剂适当的引入交联，以提高混合物的分子量，可以提高热熔胶膜的粘接强度、耐热性、耐水洗性、耐化学药品性、耐老化性、储存稳定性。Dibenzoyl peroxide (BPO) is a diacyl organic peroxide that is used as an initiator for polymerization reactions to control the rate of polymerization reactions to a certain extent. BPO produces BPO through a smooth, stable, and controllable decomposition reaction. High linearity and molecular weight polymers. The cross-linking agent and initiator are properly introduced to increase the molecular weight of the mixture, which can improve the bonding strength, heat resistance, water washing resistance, chemical resistance, aging resistance, and storage stability of the hot melt adhesive film.
将实施例1-3中的鞋底用复合热熔胶膜的EVA胶膜层通过热熔方式与中底 粘合，EVA/橡胶弹性体复合层通过热熔方式与大底粘合，所制得鞋底的鞋底粘结强度高，大底和中底不易分离。The EVA film layer of the composite hot-melt adhesive film for soles in Examples 1-3 is bonded to the midsole by hot-melting, and the EVA/rubber elastomer composite layer is bonded to the outsole by hot-melting. The sole has high bonding strength and the outsole and midsole are not easy to separate.
将上述实施例1-3所获得的鞋底用复合热熔胶膜按照现有工艺分别和橡胶大底和EVA中底复合，得到复合鞋底。将复合鞋底裁剪宽2.5cm，长20cm的样条，在拉力试验机以100mm/min的速度测试剥离强度。具体测试结果见表1。The composite hot-melt adhesive film for soles obtained in the above-mentioned Examples 1-3 is compounded with a rubber outsole and an EVA midsole respectively according to the existing technology to obtain a composite sole. Cut the composite sole into a strip 2.5cm wide and 20cm long, and test the peel strength on a tensile testing machine at a speed of 100mm/min. See Table 1 for specific test results.
表1Table 1
 ​ 剥离强度(N/cm)Peel strength(N/cm)
实施例1Example 1 38.238.2
实施例2Example 2 39.139.1
实施例3Example 3 38.638.6
本发明鞋底用复合热熔胶膜为三层复合胶膜材料，表层为接枝改性EVA胶膜层，用于粘结EVA中底，中间层为高强度TPU/EVA合金层，底部为EVA/橡胶弹性体复合层，采用三层热贴合方式，做成复合膜，然后用于鞋底粘结，通过多层复合膜的方式，解决鞋底粘结强度差，可以适应不同的中底和大底，制成鞋底耐热，耐水解，耐水洗性能好。The composite hot-melt adhesive film for shoe soles of the present invention is a three-layer composite adhesive film material. The surface layer is a graft-modified EVA adhesive film layer, which is used to bond the EVA midsole. The middle layer is a high-strength TPU/EVA alloy layer, and the bottom layer is EVA. / Rubber elastomer composite layer uses a three-layer thermal bonding method to make a composite film, which is then used for sole bonding. Through the multi-layer composite film method, the poor bonding strength of the sole is solved, and it can adapt to different midsoles and outsole The sole is heat-resistant, hydrolysis-resistant and washable.
根据上述说明书的揭示，本发明所属领域的技术人员还可以对上述实施方式进行适当的变更和修改。因此，本发明并不局限于上面揭示和描述的具体实施方式，对本发明的一些修改和变更也应当落入本发明的权利要求的保护范围内。此外，尽管本说明书中使用了一些特定的术语，但这些术语只是为了方便说明，并不对本发明构成任何限制。Based on the disclosure of the above description, those skilled in the art to which the present invention belongs can also make appropriate changes and modifications to the above embodiments. Therefore, the present invention is not limited to the specific embodiments disclosed and described above, and some modifications and changes to the present invention should also fall within the protection scope of the claims of the present invention. In addition, although some specific terms are used in this specification, these terms are only for convenience of explanation and do not constitute any limitation on the present invention.

Claims (10)

  1. 一种鞋底用复合热熔胶膜，其特征在于：包括：A composite hot-melt adhesive film for shoe soles, which is characterized by: including:
    TPU/EVA合金基层；TPU/EVA alloy base layer;
    以及位于TPU/EVA合金基层上表面的EVA胶膜层；And the EVA film layer located on the upper surface of the TPU/EVA alloy base layer;
    以及位于TPU/EVA合金基层下表面的EVA/橡胶弹性体复合层；and an EVA/rubber elastomer composite layer located on the lower surface of the TPU/EVA alloy base layer;
    所述EVA胶膜层及所述EVA/橡胶弹性体复合层通过热贴合方式黏合TPU/EVA合金基层，形成所述鞋底用复合热熔胶膜。The EVA adhesive film layer and the EVA/rubber elastomer composite layer are bonded to the TPU/EVA alloy base layer through thermal bonding to form the composite hot melt adhesive film for shoe soles.
  2. 根据权利要求1所述的鞋底用复合热熔胶膜，其特征在于：所述TPU/EVA合金基层包括如下重量份的原料：EVA树脂50-70份、TPU 15-30份、硬脂酸锌0.1-1份、偶氮二甲酰胺0.5-1.5份、丙烯酸缩水甘油酯5-15份、抗氧剂0.1-0.5份、硬脂酸0.5-1.5份、抗UV助剂0.5-1.5份、过氧化异丙苯0.1-0.5份、滑石粉1-5份。The composite hot melt adhesive film for shoe soles according to claim 1, characterized in that: the TPU/EVA alloy base layer includes the following raw materials by weight: 50-70 parts of EVA resin, 15-30 parts of TPU, zinc stearate 0.1-1 part, azodicarbonamide 0.5-1.5 part, glycidyl acrylate 5-15 part, antioxidant 0.1-0.5 part, stearic acid 0.5-1.5 part, anti-UV additive 0.5-1.5 part, Cumene oxide 0.1-0.5 parts, talc 1-5 parts.
  3. 根据权利要求1所述的鞋底用复合热熔胶膜，其特征在于：所述EVA胶膜层包括如下重量份的原料：EVA接枝马来酸酐60-80份、聚醚多元醇15-30份、微晶蜡1-5份、萜烯树脂2-6份、抗氧剂0.5-1.5份、乙烯基三氯硅烷0.2-0.5份、过氧化异丙苯0.5-1.5份。The composite hot melt adhesive film for shoe soles according to claim 1, characterized in that: the EVA adhesive film layer includes the following parts by weight of raw materials: 60-80 parts of EVA grafted maleic anhydride, 15-30 parts of polyether polyol parts, microcrystalline wax 1-5 parts, terpene resin 2-6 parts, antioxidant 0.5-1.5 parts, vinyl trichlorosilane 0.2-0.5 parts, cumene peroxide 0.5-1.5 parts.
  4. 根据权利要求3所述的鞋底用复合热熔胶膜，其特征在于：所述聚醚多元醇的分子量为400～4000。The composite hot melt adhesive film for shoe soles according to claim 3, wherein the polyether polyol has a molecular weight of 400 to 4000.
  5. 根据权利要求4所述的鞋底用复合热熔胶膜，其特征在于：所述EVA接枝马来酸酐中VA含量28％，马来酸酐接枝率为1.2％。The composite hot-melt adhesive film for shoe soles according to claim 4, characterized in that: the VA content in the EVA-grafted maleic anhydride is 28%, and the maleic anhydride grafting rate is 1.2%.
  6. 根据权利要求1所述的鞋底用复合热熔胶膜，其特征在于：EVA/橡胶弹性体复合层包括如下重量份的原料：EVA主体树脂50-80份、苯乙烯-丁二烯嵌段共聚物1-5份、氨基酸改性马来酸酐接枝聚乙烯10-15份、萜烯树脂3-10份、过氧化异丙苯0.1-1份、抗氧化剂0.1-1份。The composite hot-melt adhesive film for shoe soles according to claim 1, characterized in that: the EVA/rubber elastomer composite layer includes the following parts by weight of raw materials: 50-80 parts by weight of EVA main resin, styrene-butadiene block copolymer 1-5 parts of amino acid-modified maleic anhydride-grafted polyethylene, 3-10 parts of terpene resin, 0.1-1 part of cumene peroxide, and 0.1-1 part of antioxidant.
  7. 一种根据权利要求1至6任一项所述的鞋底用复合热熔胶膜的制备方法，其特征在于：包括如下步骤：A method for preparing a composite hot melt adhesive film for shoe soles according to any one of claims 1 to 6, characterized in that it includes the following steps:
    将EVA接枝马来酸酐60-80份、聚醚多元醇15-30份、微晶蜡1-5份、萜烯树脂2-6份、抗氧剂0.5-1.5份、乙烯基三氯硅烷0.2-0.5份、过氧化异丙苯0.5-1.5份加入混合机进行预混合，然后投入螺杆挤出机中熔融挤出、造粒、流 延成膜，得到EVA胶膜层；Graft EVA with 60-80 parts of maleic anhydride, 15-30 parts of polyether polyol, 1-5 parts of microcrystalline wax, 2-6 parts of terpene resin, 0.5-1.5 parts of antioxidant, and vinyl trichlorosilane 0.2-0.5 parts and 0.5-1.5 parts of cumene peroxide are added to the mixer for premixing, and then put into a screw extruder for melt extrusion, granulation, and casting to form a film to obtain an EVA film layer;
    将EVA树脂50-70份、TPU 15-30份、硬脂酸锌0.1-1份、偶氮二甲酰胺0.5-1.5份、丙烯酸缩水甘油酯5-15份、抗氧剂0.1-0.5份、硬脂酸0.5-1.5份、抗UV助剂0.5-1.5份、过氧化异丙苯0.1-0.5份、滑石粉1-5份加入混合机进行预混合，然后投入螺杆挤出机中熔融挤出、造粒、流延成膜，得到TPU/EVA合金基层；Combine 50-70 parts of EVA resin, 15-30 parts of TPU, 0.1-1 part of zinc stearate, 0.5-1.5 parts of azodicarbonamide, 5-15 parts of glycidyl acrylate, 0.1-0.5 parts of antioxidant, Add 0.5-1.5 parts of stearic acid, 0.5-1.5 parts of anti-UV additive, 0.1-0.5 parts of cumene peroxide, and 1-5 parts of talc powder into the mixer for premixing, then put it into the screw extruder for melt extrusion , granulating, and casting to form a film to obtain a TPU/EVA alloy base layer;
    将EVA主体树脂50-80份、苯乙烯-丁二烯嵌段共聚物1-5份、氨基酸改性马来酸酐接枝聚乙烯10-15份、萜烯树脂3-10份、过氧化异丙苯0.1-1份、抗氧化剂0.1-1份加入混合机进行预混合，然后投入螺杆挤出机中熔融挤出、造粒、流延成膜，得到EVA/橡胶弹性体复合层；Mix 50-80 parts of EVA main resin, 1-5 parts of styrene-butadiene block copolymer, 10-15 parts of amino acid-modified maleic anhydride grafted polyethylene, 3-10 parts of terpene resin, and isoperoxide 0.1-1 part of propylbenzene and 0.1-1 part of antioxidant are added to the mixer for premixing, and then put into a screw extruder for melt extrusion, granulation, and casting to form a film to obtain an EVA/rubber elastomer composite layer;
    将EVA胶膜层和EVA/橡胶弹性体复合层通过热贴合方式分别黏合在TPU/EVA合金基层的上表面和下表面，形成所述鞋底用复合热熔胶膜。The EVA adhesive film layer and the EVA/rubber elastomer composite layer are respectively bonded to the upper surface and lower surface of the TPU/EVA alloy base layer through thermal bonding to form the composite hot melt adhesive film for shoe soles.
  8. 根据权利要求7所述的鞋底用复合热熔胶膜的制备方法，其特征在于：所述预混合温度是120-150℃，搅拌速度为250-500r/min，搅拌时间为4-10分钟。The preparation method of composite hot melt adhesive film for shoe soles according to claim 7, characterized in that: the premixing temperature is 120-150°C, the stirring speed is 250-500r/min, and the stirring time is 4-10 minutes.
  9. 根据权利要求7所述的鞋底用复合热熔胶膜的制备方法，其特征在于：所述螺杆挤出机的挤出温度是160-200℃，搅拌速度为300-600r/min。The method for preparing a composite hot-melt adhesive film for shoe soles according to claim 7, characterized in that: the extrusion temperature of the screw extruder is 160-200°C, and the stirring speed is 300-600r/min.
  10. 根据权利要求7所述的鞋底用复合热熔胶膜的制备方法，其特征在于：所述流延成膜中流延温度为160-200℃。The method for preparing a composite hot-melt adhesive film for shoe soles according to claim 7, characterized in that: the casting temperature during the casting film formation is 160-200°C.
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011110105A (en) * 2009-11-24 2011-06-09 Daicel-Evonik Ltd Sheet for shoe sole, and shoe sole using the same
CN104559843A (en) * 2014-12-31 2015-04-29 广州鹿山新材料股份有限公司 Hot melt adhesive film for adhering rubber/foamed EVA (ethylene-vinyl acetate copolymer) composite sole and preparation method thereof
CN107698860A (en) * 2017-10-30 2018-02-16 美瑞新材料股份有限公司 A kind of sole high resilience composition expanded material and preparation method thereof
CN110551337A (en) * 2019-10-14 2019-12-10 上海联景高分子材料有限公司 EVA and TPU melt blending to prepare elastomer alloy and composition foaming material thereof
CN112226180A (en) * 2020-10-10 2021-01-15 厦门联合信诺新材料有限公司 Hot melt adhesive film for composite shoe sole and preparation method thereof
CN217012955U (en) * 2022-04-24 2022-07-22 泉州安力鞋服有限公司 High-viscosity composite hot-melt adhesive sheet for soles

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN211211650U (en) * 2019-08-28 2020-08-11 杭州佳思米新材料有限公司 Hot melt film with tie coat
CN111004584B (en) * 2019-10-28 2021-06-15 茂泰(福建)鞋材有限公司 Adhesive film, preparation method of adhesive film and shoe sole comprising adhesive film
CN112143391A (en) * 2020-09-14 2020-12-29 东莞市汇齐新材料有限公司 Glue film suitable for mold pressing insole glue brushing-free

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011110105A (en) * 2009-11-24 2011-06-09 Daicel-Evonik Ltd Sheet for shoe sole, and shoe sole using the same
CN104559843A (en) * 2014-12-31 2015-04-29 广州鹿山新材料股份有限公司 Hot melt adhesive film for adhering rubber/foamed EVA (ethylene-vinyl acetate copolymer) composite sole and preparation method thereof
CN107698860A (en) * 2017-10-30 2018-02-16 美瑞新材料股份有限公司 A kind of sole high resilience composition expanded material and preparation method thereof
CN110551337A (en) * 2019-10-14 2019-12-10 上海联景高分子材料有限公司 EVA and TPU melt blending to prepare elastomer alloy and composition foaming material thereof
CN112226180A (en) * 2020-10-10 2021-01-15 厦门联合信诺新材料有限公司 Hot melt adhesive film for composite shoe sole and preparation method thereof
CN217012955U (en) * 2022-04-24 2022-07-22 泉州安力鞋服有限公司 High-viscosity composite hot-melt adhesive sheet for soles

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