CN111004584B - Adhesive film, preparation method of adhesive film and shoe sole comprising adhesive film - Google Patents
Adhesive film, preparation method of adhesive film and shoe sole comprising adhesive film Download PDFInfo
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- CN111004584B CN111004584B CN201911030564.9A CN201911030564A CN111004584B CN 111004584 B CN111004584 B CN 111004584B CN 201911030564 A CN201911030564 A CN 201911030564A CN 111004584 B CN111004584 B CN 111004584B
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- adhesive film
- maleic anhydride
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- sole
- thermoplastic rubber
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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
- C09J7/10—Adhesives in the form of films or foils without carriers
-
- 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
- A43B13/023—Soles with several layers of the same material
-
- 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
- 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
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- 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
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Footwear And Its Accessory, Manufacturing Method And Apparatuses (AREA)
Abstract
The invention discloses an adhesive film, a preparation method of the adhesive film and a sole comprising the adhesive film, wherein the adhesive film comprises the following components in parts by weight, EVA, maleic anhydride grafted SBS rubber, maleic anhydride polybutadiene, liquid polyisobutylene, tackifying resin, zinc stearate, a cross-linking agent and an antioxidant; the adhesive film is a cross-linking adhesive film, and a cross-linking agent is decomposed in the compression molding process to generate active free radicals, so that free radical cross-linking occurs among saturated hydrocarbons in molecular structures of EVA, maleic anhydride grafted SBS rubber, maleic anhydride polybutadiene and liquid polyisobutylene in the adhesive film to form a net structure, and the cohesive force of the adhesive film is improved; meanwhile, the saturated hydrocarbon structure in the adhesive film and the saturated hydrocarbon structure in the EVA insole are subjected to free radical crosslinking, and the saturated hydrocarbon structure in the adhesive film and the saturated hydrocarbon structure in the thermoplastic rubber bottom sheet are subjected to free radical crosslinking, so that the interaction force of the adhesive film, the EVA insole and the thermoplastic rubber bottom sheet is enhanced, and the bonding strength is improved.
Description
Technical Field
The invention relates to the technical field of bonding materials, in particular to an adhesive film, a preparation method of the adhesive film and a sole comprising the adhesive film.
Background
With the progress of living standard, sole with single component such as rubber sole, EVA sole, etc. can not meet the requirement of client, the rubber sole has the obvious characteristics of good wear resistance, good slip resistance, etc., but the specific gravity is large, and the wearing is inconvenient; the EVA sole has good elasticity and small specific gravity, but has poor wear resistance and slip resistance. In the prior art, the sole with superior comprehensive performance comprises an outsole and a midsole, wherein the outsole is generally a rubber sole, a TPR sole and the like, the midsole is generally an EVA sole, a PU sole and the like, and the outsole and the midsole are generally connected through an adhesive film.
The existing glue film comprises the components of epoxidized SBS rubber, chlorinated EVA resin, chloroprene rubber, liquid butyl rubber, aromatic modified aliphatic hydrocarbon resin, stearic acid, zinc stearate and an antioxidant; the adhesive film is used for bonding the vulcanized rubber sole or the TPR sole formed by thermoplastic molding with the secondary EVA insole, changes the traditional bonding mode, has no need of brushing a treating agent, PU glue and other processes, has good adhesion, good heat resistance and good water resistance, simplifies the processing procedures, and is environment-friendly and energy-saving.
However, in the process of implementing the technical solution of the invention in the embodiments of the present application, the inventors of the present application find that the above-mentioned technology has at least the following technical problems:
the initial bonding strength of the sole made of the existing adhesive film is lower than 40N/cm, but after humidification and aging (70 ℃, 95% humidity and 72), the bonding strength is obviously reduced, the average bonding strength is about 28N/cm, and the bonding strength is too poor.
Disclosure of Invention
The adhesive film, the preparation method of the adhesive film and the sole comprising the adhesive film solve the problem that viscosity of the adhesive film in the sole is obviously reduced after humidification and aging in the prior art, achieve that after a damp-heat aging test (70 ℃, 95% humidity, 72h), the adhesive strength can also reach 4.2N/mm, is far higher than the adhesive strength requirement of the existing combined sole, and can effectively avoid the phenomenon of glue failure of the combined sole caused by damp aging and heat aging.
The embodiment of the application provides an adhesive film, which comprises the following components in parts by weight:
further, the composition comprises the following components in parts by weight:
further, the maleic anhydride grafting rate of the maleic anhydride grafted SBS rubber is 5% -7%; the maleic anhydride grafting ratio of the maleic anhydrided polybutadiene is 10-20%, and the vinyl content is 25-35%.
A preparation method of an adhesive film comprises the steps of carrying out banburying, open milling and sheet discharging on EVA, maleic anhydride grafted SBS rubber, maleic anhydride polybutadiene, liquid polyisobutene, tackifying resin, zinc stearate, a cross-linking agent and an antioxidant at 105 ℃, carrying out tape casting by using release paper as a base film through a tape casting machine, and obtaining the adhesive film using the release paper as the base film.
A shoe sole including an adhesive film, comprising:
(a) banburying the thermoplastic rubber according to the formula requirement, then pouring, milling, discharging, covering the adhesive film by a film covering machine, and finally blanking to obtain a film-covered thermoplastic rubber bottom sheet with a specific shape;
(d) placing the film-coated thermoplastic rubber substrate prepared in the step (a) into a secondary oil pressure die, enabling the side, provided with the adhesive film, of the film-coated thermoplastic rubber substrate to face upwards, and tearing off release paper of the adhesive film; and adhering the EVA middle sole subjected to primary mould pressing foaming and leather wheel roughening to a film-coated thermoplastic rubber substrate, closing the mould, carrying out mould pressing at 180 ℃ for 300 seconds, cooling and taking out to obtain the finished product sole adhered by the adhesive film.
One or more technical solutions provided in the embodiments of the present application have at least the following technical effects or advantages:
1. the adhesive film is a cross-linking adhesive film, and a cross-linking agent is decomposed in the compression molding process to generate active free radicals, so that free radical cross-linking occurs among saturated hydrocarbons in molecular structures of EVA, maleic anhydride grafted SBS rubber, maleic anhydride polybutadiene and liquid polyisobutylene in the adhesive film to form a net structure, and the cohesive force of the adhesive film is improved; meanwhile, the saturated hydrocarbon structure in the adhesive film and the saturated hydrocarbon structure in the EVA insole are subjected to free radical crosslinking, and the saturated hydrocarbon structure in the adhesive film and the saturated hydrocarbon structure in the thermoplastic rubber bottom sheet are subjected to free radical crosslinking, so that the interaction force of the adhesive film, the EVA insole and the thermoplastic rubber bottom sheet is enhanced, and the bonding strength is improved.
2. The adhesive film disclosed by the invention does not use any chemical solvent, is energy-saving, environment-friendly and pollution-free, has no toxic or side effect on related workers, protects the health of the workers and reduces the pollution to the environment; and the traditional bonding process is changed, the treatment procedures of shoe sole thickening, water brushing, drying, glue brushing, heating activation and the like are reduced, the production efficiency is improved, and the production cost is reduced. After the prepared combined sole is tested by humid heat aging (70 ℃, 95% humidity and 72h), the bonding strength can also reach 4.2N/mm, which is far higher than the bonding strength requirement of the existing combined sole, and the phenomenon of glue failure of the combined sole caused by humid aging and heat aging can be effectively avoided.
Detailed Description
In order to better understand the technical scheme, the technical scheme is described in detail in the following with reference to specific embodiments of the specification.
The following are a summary of the raw material compositions of the examples and comparative examples, resulting in table 1:
TABLE 1 summary of the raw material compositions of the examples and comparative examples
Example 1:
in the embodiment, the adhesive film comprises the following components in parts by weight: EVA15015 parts, EVA7A60H25 parts, maleic anhydride grafted SBS rubber (grafting ratio is 7%) 21 parts, maleic anhydride polybutadiene 173114 parts, liquid polyisobutylene 12 parts, M80 resin 10 parts, zinc stearate 1 part, cross-linking agent BIBP0.2 part, and antioxidant B10040.1 parts. And banburying the raw materials at 105 ℃, carrying out open milling, discharging, and carrying out tape casting in a tape casting machine to obtain the adhesive film with release paper as a base film, wherein the thickness of the adhesive film is 0.5-3 mm.
And banburying the thermoplastic rubber according to the formula requirement, then pouring, milling and discharging, covering the prepared adhesive film on a thermoplastic rubber sheet by a film covering machine, and finally blanking to obtain the film-covered thermoplastic rubber bottom sheet with a specific shape. Placing the prepared film-coated thermoplastic rubber substrate into a secondary oil pressure die, enabling the surface of the film-coated thermoplastic rubber substrate provided with the adhesive film to face upwards, and tearing off release paper of the adhesive film; and adhering the EVA middle sole subjected to primary mould pressing foaming and leather wheel roughening to a film-coated thermoplastic rubber substrate, closing the mould, carrying out mould pressing at 180 ℃ for 300 seconds, cooling and taking out to obtain the finished product sole adhered by the adhesive film.
The initial bonding strength of the finished product sole prepared by the method is 5.1N/mm; the adhesive strength after heat aging was 4.9N/mm; the adhesive strength after humid aging was 4.4N/mm.
Example 2:
in this example, the preparation method and the application method of the adhesive film are the same as those in example 1, except that:
the raw materials varied in composition (see table 1 for details).
The initial bonding strength of the finished product sole prepared by the method is 4.9N/mm; after heat aging, the adhesive strength was 4.4N/mm; the adhesive strength after humid aging was 4.3N/mm.
Example 3:
in this example, the preparation method and the application method of the adhesive film are the same as those in example 1, except that:
the raw materials varied in composition (see table 1 for details).
The initial bonding strength of the finished product sole prepared by the method is 5.3N/mm; after heat aging, the adhesive strength was 4.8N/mm; the adhesive strength after humid aging was 4.2N/mm.
Example 4:
in this example, the preparation method and the application method of the adhesive film are the same as those in example 1, except that:
the raw materials varied in composition (see table 1 for details).
The initial bonding strength of the finished product sole prepared by the method is 4.7N/mm; after heat aging, the adhesive strength was 4.3N/mm; the adhesive strength after humid aging was 4.3N/mm.
Comparative example a:
in this comparative example, the biodegradable foamed shoe sole was prepared in the same manner as in example 1, except that:
the raw materials varied in composition (see table 1 for details).
The initial bonding strength of the finished product sole prepared by the method is 2.4N/mm; after heat aging, the adhesive strength was 1.9N/mm; the adhesive strength after humid aging was 1.1N/mm.
Comparative example B:
in this comparative example, the biodegradable foamed shoe sole was prepared in the same manner as in example 1, except that:
the raw materials varied in composition (see table 1 for details).
The initial bonding strength of the finished product sole prepared by the method is 3.3N/mm; after heat aging, the adhesive strength was 2.2N/mm; the adhesive strength after humid aging was 1.7N/mm.
Comparative example C:
in this comparative example, the biodegradable foamed shoe sole was prepared in the same manner as in example 1, except that:
the raw materials varied in composition (see table 1 for details).
The initial bonding strength of the finished product sole prepared by the method is 2.8N/mm; after heat aging, the adhesive strength was 2.1N/mm; the adhesive strength after humid aging was 1.5N/mm.
After the data of the above examples 1-4 and comparative examples A/B/C are collated, the following Table 2 is obtained (note: adhesive strength is measured according to GB/T532-2008 for outsole and midsole, and heat aging and humidity aging are measured according to GB/T3903.7-2005):
table 2: performance parameter comparison table of energy-saving and environment-friendly adhesive film prepared in examples 1-4 and comparative example A/B/C
From experimental data, example 1 compared to comparative example a, in which no crosslinking agent BIBP was used, the initial adhesive strength of example 1 was much higher than that of comparative example a, and the adhesive strength after aging was still higher than that of comparative example a despite heat aging and humid aging; comparative example B, which did not have maleic anhydride polybutadiene 1731 added, had much higher initial bond strength than comparative example B, which was still higher after aging than comparative example B despite heat aging, humid aging; in comparison to comparative example C, which had no maleic anhydride-grafted SBS rubber added, the initial adhesive strength of example 1 was much higher than that of comparative example C, and the adhesive strength after aging was still higher than that of comparative example C despite heat aging, humid aging.
In conclusion, when the adhesive film is used for bonding the EVA foaming insole and the thermoplastic rubber outsole of the sole, the traditional bonding mode is changed, the sole does not need to be subjected to treatment such as thickening and primer coating, the processing procedure is simplified, the adhesive film is environment-friendly and energy-saving, and the adhesive film is a cross-linking type adhesive film, has a free radical cross-linking effect with the thermoplastic rubber and the foaming insole in the heating forming process, is strong in adhesive force and good in heat and water resistance, can effectively avoid the phenomenon of rubber stripping of the combined sole caused by wet aging and heat aging, and has good market prospect.
The above description is only an embodiment utilizing the technical content of the present disclosure, and any modification and variation made by those skilled in the art can be covered by the claims of the present disclosure, and not limited to the embodiments disclosed.
Claims (5)
1. The adhesive film is characterized by comprising the following components in parts by weight:
2. the adhesive film according to claim 1, which comprises the following components in parts by weight:
3. the adhesive film of claim 1, wherein: the maleic anhydride grafting rate of the maleic anhydride grafted SBS rubber is 5% -7%; the maleic anhydride grafting ratio of the maleic anhydrided polybutadiene is 10-20%, and the vinyl content is 25-35%.
4. The method for preparing the adhesive film according to any one of claims 1 to 3, wherein: mixing EVA, maleic anhydride grafted SBS rubber, maleic anhydride polybutadiene, liquid polyisobutylene, tackifying resin, zinc stearate, a crosslinking agent BIBP and an antioxidant at 105 ℃, carrying out open milling, and carrying out sheet discharge, then taking release paper as a base membrane, and carrying out tape casting in a tape casting machine to obtain the adhesive membrane taking the release paper as the base membrane.
5. A method for preparing a sole using the adhesive film of any one of claims 1 to 3, comprising:
(a) banburying the thermoplastic rubber according to the formula requirement, then pouring, milling, discharging, covering the adhesive film by a film covering machine, and finally blanking to obtain a film-covered thermoplastic rubber bottom sheet with a specific shape;
(b) placing the film-coated thermoplastic rubber substrate prepared in the step (a) into a secondary oil pressure die, enabling the side, provided with the adhesive film, of the film-coated thermoplastic rubber substrate to face upwards, and tearing off release paper of the adhesive film; and adhering the EVA middle sole subjected to primary mould pressing foaming and leather wheel roughening to a film-coated thermoplastic rubber substrate, closing the mould, carrying out mould pressing at 180 ℃ for 300 seconds, cooling and taking out to obtain the finished product sole adhered by the adhesive film.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201911030564.9A CN111004584B (en) | 2019-10-28 | 2019-10-28 | Adhesive film, preparation method of adhesive film and shoe sole comprising adhesive film |
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| CN201911030564.9A CN111004584B (en) | 2019-10-28 | 2019-10-28 | Adhesive film, preparation method of adhesive film and shoe sole comprising adhesive film |
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| CN114806454A (en) * | 2021-01-29 | 2022-07-29 | 大东树脂化学股份有限公司 | Method for attaching vulcanized shoes |
| TWI805998B (en) * | 2021-01-29 | 2023-06-21 | 大東樹脂化學股份有限公司 | Bonding method in adhesive technology for vulcanization shoes |
| CN115637117A (en) * | 2022-07-26 | 2023-01-24 | 广东汇齐新材料有限公司 | Low-temperature activated hot melt adhesive film for sole mould pressing and attaching |
| CN115305025A (en) * | 2022-08-01 | 2022-11-08 | 广东汇齐新材料有限公司 | Composite hot melt adhesive film for shoe sole and preparation method thereof |
| CN115404026B (en) * | 2022-09-16 | 2024-08-02 | 浙江理工大学 | A hot-melt strong high-performance adhesive |
| CN115537159B (en) * | 2022-12-02 | 2023-03-21 | 广州鹿山新材料股份有限公司 | Weather-resistant waterproof coiled material hot-melt pressure-sensitive adhesive and preparation method and application thereof |
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| JP4070472B2 (en) * | 2001-02-05 | 2008-04-02 | リケンテクノス株式会社 | Thermoplastic resin composition and method for producing the same |
| US20030127169A1 (en) * | 2001-10-30 | 2003-07-10 | Bridgestone/Firestone, Inc. | Elastomers with long chain crosslinks to increase abrasion resistance |
| CN104789169B (en) * | 2015-04-09 | 2017-01-04 | 茂泰(福建)鞋材有限公司 | A kind of rubber bound film and preparation method thereof and for bond sole time using method |
| CN110330924B (en) * | 2019-06-04 | 2021-06-11 | 广州市豪特粘接材料有限公司 | Hot melt adhesive for laminating automobile soundproof cotton and preparation method thereof |
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