CN116589939A - Epoxy resin adhesive film and preparation method thereof - Google Patents

Epoxy resin adhesive film and preparation method thereof Download PDF

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Publication number
CN116589939A
CN116589939A CN202310719365.9A CN202310719365A CN116589939A CN 116589939 A CN116589939 A CN 116589939A CN 202310719365 A CN202310719365 A CN 202310719365A CN 116589939 A CN116589939 A CN 116589939A
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epoxy resin
parts
adhesive film
film
dispersing
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余丽娇
张华川
贾沛阳
李晓阳
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Lu Chen New Materials Technology Co ltd
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Lu Chen New Materials Technology Co ltd
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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
    • C09J7/30—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
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/58—Epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
    • C08G18/8006—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32
    • C08G18/8038—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3225
    • 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
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • 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
    • C09J2400/00—Presence of inorganic and organic materials
    • C09J2400/20—Presence of organic materials
    • C09J2400/26—Presence of textile or fabric
    • C09J2400/263—Presence of textile or fabric 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
    • C09J2400/00—Presence of inorganic and organic materials
    • C09J2400/20—Presence of organic materials
    • C09J2400/28—Presence of paper
    • 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
    • C09J2467/00—Presence of polyester
    • C09J2467/006—Presence of polyester in the substrate
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The application discloses an epoxy resin adhesive film and a preparation method thereof, wherein the epoxy resin adhesive film comprises a resin matrix and a carrier, and the resin matrix comprises the following components in parts by weight: 40-60 parts of liquid epoxy resin containing hydroxyl, 15-40 parts of toughening agent, 10-20 parts of aromatic isocyanate compound, 5-12 parts of curing agent, 1-5 parts of thixotropic agent and 1-5 parts of silane coupling agent, wherein the aromatic isocyanate has at least 2 NCO-reactive groups; the carrier is polyester felt or glass fiber thin cloth. The epoxy resin adhesive film has the advantages of simple molding operation, convenient operation and the like, and the molded adhesive film has good quality, so that the problems of poor adhesive film quality, high energy consumption, complex operation and the like in the preparation process in the prior art can be effectively solved.

Description

Epoxy resin adhesive film and preparation method thereof
Technical Field
The application relates to the technical field of epoxy resin adhesive films, in particular to an epoxy resin adhesive film and a preparation method thereof.
Background
With the rapid development of technology in the aspects of aerospace, automobiles, electronics and the like, the demand for high-performance hot melt adhesive films is increasing. The epoxy adhesive film is used as a thermosetting hot melt adhesive film of a latent curing agent, and is widely applied to the adhesion of various metal materials, nonmetallic materials and composite materials due to the good technological performance, high adhesion strength and good environmental aging resistance.
The preparation process of the epoxy adhesive film used in the current market mainly comprises two processes, namely hot-melt molding and dry molding, namely heating and melting a resin system at 60-110 ℃, adjusting the high-viscosity resin system to a proper viscosity, coating resin on release paper according to the surface density requirement of the adhesive film, and coating a carrier on the resin film to form the adhesive film. In addition, the adhesive film resin system for hot melt molding is generally high in viscosity, and the resin system is required to be mixed at the temperature of 60-200 ℃. In the process of mixing a resin system and preparing a glue film, complex steps such as temperature rising and temperature reducing are needed, and the energy consumption in the process is huge.
The other is a solvent method, commonly called a wet method, which mainly comprises the steps of dissolving resin in a chemical solvent to form a resin solution, then spreading a carrier, continuously passing through a glue tank filled with the resin solution, and drying and volatilizing the redundant solvent in the resin solution at a high temperature to form a glue film. The chemical solvent is used in the impregnation process, so that the whole environment is polluted to a certain extent, and the physical health of on-site operators is also endangered. In addition, in terms of the quality of the adhesive film, a certain amount of solvent often remains in the adhesive film, and voids are easily generated during bonding molding, which affects the bonding performance.
Therefore, the traditional adhesive film preparation method has the problems of high energy consumption, easy pollution generation, poor product quality and the like, and the adhesive film produced by the traditional method limits the large-scale popularization and application in the industrial field to a certain extent on the basis of the low-cost and high-performance requirements of the adhesive film at the present stage.
Disclosure of Invention
Aiming at the defects in the prior art, the application provides the epoxy resin adhesive film and the preparation method thereof, and the epoxy resin adhesive film has the advantages of simple molding operation, convenient operation and the like, and the molded adhesive film has good quality, so that the problems of poor adhesive film quality, high energy consumption, complex operation and the like in the preparation process in the prior art can be effectively solved.
In order to achieve the above purpose, the technical scheme adopted by the application for solving the technical problems is as follows:
the epoxy resin adhesive film comprises a resin matrix and a carrier, wherein the resin matrix comprises the following components in parts by weight: 40-60 parts of liquid epoxy resin containing hydroxyl, 15-40 parts of toughening agent, 10-20 parts of aromatic isocyanate compound, 5-12 parts of curing agent, 1-5 parts of thixotropic agent and 1-5 parts of silane coupling agent; the aromatic isocyanate has at least 2 NCO-reactive groups; the carrier is polyester felt or glass fiber thin cloth.
Further, the hydroxyl group-containing liquid epoxy resin includes at least one of bisphenol a type epoxy resin, bisphenol F type epoxy resin, phenolic type epoxy resin, polyfunctional epoxy resin, and aliphatic alcohol polyglycidyl ether.
Further, the labels of bisphenol A type epoxy resins include DER 661, EPON828 and NPEL-128; the brands of bisphenol F type epoxy resins include DER 354, EPON862, NEPF-170 and NPEF-185; the phenolic type epoxy resin comprises DEN 431, DEN 438, NPPN-638S and NPPN-631; the marks of the multifunctional epoxy resin comprise AG-80 and AFG-90; the trade names of the aliphatic alcohol polyglycidyl ethers include EX-313, EX-314, EX-612, EX-614 and EX-622.
Further, the toughening agent comprises at least one of hydroxyl-terminated nitrile rubber, amine-terminated nitrile rubber, epoxy-terminated nitrile rubber, prepolymer of epoxy resin and nitrile rubber, and dispersed core-shell rubber.
Further, the brand of the hydroxyl-terminated nitrile rubber includes CTBN1300X 8 or CTBN1300X 13; the marks of the amine-terminated nitrile rubber comprise ATBN 1300X 21, ATBN 1300X 16 and ATBN 1300X 35; the brand of the epoxy-terminated nitrile rubber comprises ETBN1300X 40, ETBN1300X 68 or ETBN1300X63; the pre-polymers of epoxy resin and nitrile rubber are numbered HyPox RA1340, hyPox RF1320 and HyPox RM20; the trade names of the dispersed core-shell rubber include MX-153, MX-154 or 21044.
Further, the aromatic isocyanate compound includes at least one of polymeric diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate, and urethane-modified diphenylmethane diisocyanate. In the application, the aromatic isocyanate compound is used as a chain extender, the structure of the aromatic isocyanate compound contains at least 2 NCO-reactive groups, and the NCO-and the hydroxyl in the epoxy resin start to react at a certain temperature (more than 20 ℃) to form a prepolymer with a certain crosslinking degree, so that the viscosity of a resin matrix is increased, and the thickening effect is achieved. In addition, the aromatic isocyanate compound is selected, and the cured product of the obtained epoxy resin composition has higher heat resistance.
Further, the curing agent is a mixture of dicyandiamide and organic urea derivatives, and the organic urea derivatives are one or more of organic urea accelerators such as dichlorophenyl dimethylurea, phenyl dimethylurea, toluene-bis-dimethylurea and the like; the thixotropic agent comprises at least one of fumed silica, nano calcium carbonate and silicon powder.
Further, the silane coupling agent is of the type KH550, KH560, KH570, KH580, KH171 or KH729.
The preparation method of the epoxy resin adhesive film comprises the following steps:
(1) Taking part of liquid epoxy resin, adding a curing agent into the liquid epoxy resin, and stirring and dispersing the liquid epoxy resin at a high speed to obtain a curing agent compound;
(2) Adding a toughening agent, a thixotropic agent and a silane coupling agent into the residual liquid epoxy resin, and stirring and dispersing at a high speed to prepare a mixture;
(3) Adding the cured compound in the step (1) into the mixture in the step (2), stirring and dispersing at a high speed, and then adding an aromatic isocyanate compound into the mixture to continuously stir and disperse to prepare a resin matrix for an epoxy resin adhesive film;
(4) Setting the temperature of a glue spreader to be 25-35 ℃, pouring the epoxy resin matrix in the step (3) into a glue groove of a presoaking machine, coating the epoxy resin matrix on release paper according to a certain unit area mass to form a resin film, sequentially coating a polyester felt or glass fiber thin cloth and a PE film on the upper part of the resin film, winding, and then placing the resin film in a constant temperature chamber at 23-30 ℃ for standing for 45-50 hours to obtain the epoxy resin adhesive film.
Further, the mass ratio of the liquid epoxy resin to the curing agent in the step (1) is 2-3.
Further, the rotation speed of high-speed stirring and dispersing in the step (2) and the step (3) is 200-800r/min, and the dispersing time is 20-40min.
Further, the weight per unit area of the resin film in the step (4) is 210 to 250g/m 2 The method comprises the steps of carrying out a first treatment on the surface of the The weight of the unit area of the polyester felt or the glass fiber thin cloth is 18-22g/m 2 。
Further, the viscosity of the epoxy resin film prepared in the step (4) is 50000-250000cps at 70 ℃.
The beneficial effects of the application are as follows:
the application selects liquid epoxy resin containing hydroxyl as resin component, uses aromatic isocyanate compound containing at least more than 2 NCO-reactive groups as chain extender, reacts with the liquid epoxy resin at the temperature of more than 20 ℃ to thicken the resin matrix, has certain technological operability after thickening, can directly coat the mixed resin matrix and can prepare the required epoxy resin adhesive film after constant temperature standing.
In the operation process, the preparation method provided by the application can be used for mixing the resin matrix and performing thickening reaction at normal temperature without heating, and can be used for reducing the harm to human bodies and the pollution to the environment without using extra solvents; the aromatic isocyanate compound is selected as the chain extender, so that the toughness of the epoxy resin film can be increased, and the heat resistance of the epoxy resin film can be increased.
Detailed Description
The present application will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present application more apparent. It should be understood that the particular embodiments described herein are illustrative only and are not intended to limit the application, i.e., the embodiments described are merely some, but not all, of the embodiments of the application.
Thus, the following detailed description of the embodiments of the application, as provided, is not intended to limit the scope of the application, as claimed, but is merely representative of selected embodiments of the application. All other embodiments, which can be made by a person skilled in the art without making any inventive effort, are intended to be within the scope of the present application.
It is noted that relational terms such as "first" and "second", and the like, are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising one … …" does not exclude the presence of other like elements in a process, method, article, or apparatus that comprises an element.
The features and capabilities of the present application are described in further detail below in connection with examples.
Example 1
An epoxy resin film comprises the following components in parts by weight: bisphenol A type epoxy resin NPEL-128 parts, aliphatic alcohol polyglycidyl ether EX-612 parts, hydroxyl-terminated nitrile rubber CTBN1300X13 parts, polymeric diphenylmethane diisocyanate 20 parts, mixture 9 parts of dicyandiamide and urea, fumed silica 3 parts and silane coupling agent KH5602 parts;
the preparation method comprises the following steps:
(1) Taking aliphatic alcohol polyglycidyl ether EX-612, adding a mixture of dicyandiamide and urea into the mixture, stirring the mixture at a high speed for 40min under the condition of 200r/min, dispersing the mixture, pouring the mixture into a three-roller grinder, and grinding the mixture at a gap of 0.05mm to obtain a cured compound;
(2) Adding hydroxyl-terminated nitrile rubber CTBN1300X13, fumed silica and a silane coupling agent KH560 into bisphenol A epoxy resin NPEL-128, stirring and dispersing at high speed for 40min under the condition of 200r/min to prepare a mixture;
(3) Adding the cured compound in the step (1) into the mixture in the step (2), stirring and dispersing for 40min at a high speed under the condition of 200r/min, and then adding polymeric diphenylmethane diisocyanate into the mixture, and continuing stirring and dispersing for 40min at a high speed under the condition of 200r/min to prepare an epoxy resin composition;
(4) Pouring the epoxy resin composition in the step (3) into a glue tank of a presoaking machine at 25 ℃ to coat the epoxy resin composition on release paper to form a resin film, wherein the weight per unit area of the resin film is 210g/m 2 Sequentially coating a polyester felt or glass fiber thin cloth and a PE film on the upper part, wherein the weight of the polyester felt or glass fiber thin cloth per unit area is 22g/m 2 And (3) standing the wound film in a room temperature environment at 30 ℃ for 45 hours to obtain an epoxy resin film, wherein the viscosity of the epoxy resin film at 70 ℃ is 50000-250000cps.
Example 2
An epoxy resin film comprises the following components in parts by weight: bisphenol A type epoxy resin NPEL-128 40 parts, aliphatic alcohol polyglycidyl ether EX-612 parts, epoxy resin and nitrile rubber prepolymer HyPox RA1340 30 parts, polymeric diphenylmethane diisocyanate 10 parts, carbodiimide modified diphenylmethane diisocyanate 8 parts, dicyandiamide and urea mixture 9 parts, fumed silica 3 parts and silane coupling agent KH5602 parts;
the preparation method comprises the following steps:
(1) Taking aliphatic alcohol polyglycidyl ether EX-612, adding a mixture of dicyandiamide and urea into the mixture, stirring the mixture at a high speed for 20min under the condition of 600r/min, dispersing the mixture, pouring the mixture into a three-roller grinder, and grinding the mixture at a gap of 0.12mm to obtain a cured compound;
(2) Adding a prepolymer HyPox RA1340 of epoxy resin and nitrile rubber, fumed silica and a silane coupling agent KH560 into bisphenol A epoxy resin NPEL-128, and stirring and dispersing at high speed for 20min under the condition of 600r/min to obtain a mixture;
(3) Adding the cured compound in the step (1) into the mixture in the step (2), stirring and dispersing at a high speed for 20min under the condition of 600r/min, and then adding polymeric diphenylmethane diisocyanate and carbodiimide modified diphenylmethane diisocyanate into the mixture, and continuing stirring and dispersing at a high speed for 20min under the condition of 600r/min to prepare an epoxy resin composition;
(4) Pouring the epoxy resin composition in the step (3) into a glue tank of a presoaking machine at 35 ℃ to coat the epoxy resin composition on release paper to form a resin film, wherein the weight of the resin film per unit area is 250g/m 2 Sequentially coating a polyester felt or glass fiber thin cloth and a PE film on the upper part, wherein the weight of the polyester felt or glass fiber thin cloth per unit area is 18g/m 2 And (3) standing the wound film in a room temperature environment at 30 ℃ for 50 hours to obtain an epoxy resin film, wherein the viscosity of the epoxy resin film at 70 ℃ is 50000-250000cps.
Example 3
An epoxy resin film comprises the following components in parts by weight: 40 parts of bisphenol A epoxy resin NEPF-170 parts, 20 parts of aliphatic alcohol polyglycidyl ether EX-622 parts, 1340 20 parts of epoxy resin and nitrile rubber prepolymer HyPox RA, 20 parts of dispersed core-shell rubber MX-154 parts, 10 parts of polymerized diphenylmethane diisocyanate, 10 parts of carbodiimide modified diphenylmethane diisocyanate, 8 parts of a mixture of dicyandiamide and urea, 3 parts of fumed silica and 560 parts of a silane coupling agent KH;
the preparation method comprises the following steps:
(1) Taking aliphatic alcohol polyglycidyl ether EX-622, adding a mixture of dicyandiamide and urea into the mixture, stirring the mixture at a high speed for 30min under the condition of 400r/min, dispersing the mixture, pouring the mixture into a three-roller grinder, and grinding the mixture at a gap of 0.09mm to obtain a cured compound;
(2) Adding a prepolymer HyPox RA1340 of epoxy resin and nitrile rubber, dispersed core-shell rubber MX-154, fumed silica and a silane coupling agent KH560 into bisphenol A epoxy resin NEPF-170, and stirring and dispersing at high speed for 30min under the condition of 400r/min to obtain a mixture;
(3) Adding the cured compound in the step (1) into the mixture in the step (2), stirring and dispersing for 30min at a high speed under the condition of 400r/min, and then adding polymeric diphenylmethane diisocyanate and carbodiimide modified diphenylmethane diisocyanate into the mixture, and continuing stirring and dispersing for 30min at a high speed under the condition of 400r/min to prepare an epoxy resin composition;
(4) Pouring the epoxy resin composition in the step (3) into a glue tank of a presoaking machine at 30 ℃ to coat the epoxy resin composition on release paper to form a resin film, wherein the weight of the resin film per unit area is 230g/m 2 Sequentially coating a polyester felt or glass fiber thin cloth and a PE film on the upper part, wherein the weight of the polyester felt or glass fiber thin cloth per unit area is 20g/m 2 And (3) standing the wound film for 48 hours in a room temperature environment at 30 ℃ to prepare an epoxy resin film, wherein the viscosity of the epoxy resin film is 50000-250000cps at 70 ℃.
Test examples
1. LY12-CZ aluminum material (thickness 2 mm) is adopted, 5052 aluminum honeycomb is subjected to metal single lap shear strength and roller stripping sample preparation, aluminum material surface treatment is carried out according to HBZ197 structural adhesive aluminum alloy phosphoric acid anodized process Specification, and the curing temperature condition is 130 ℃ and the temperature is kept for 2 hours, and the pressure is 0.2-0.3MPa.
2. The metal single lap shear strength and the drum peel strength were measured according to ASTM D1002 and ASTM D1781, respectively, and the specific test results are shown in table 1 below.
The conventional adhesive films in the table are prepared by a conventional hot-melting method, and by comparing the performance of the adhesive films with the performance of the adhesive films prepared in examples 1-3, it can be seen that the aluminum-aluminum single lap shear strength and the aluminum honeycomb roller peel strength of the adhesive film prepared by the method are higher than those of the conventional adhesive film, and by comparing the preparation methods, the preparation method is simpler, does not need heating operation, and has the advantages of low energy consumption and convenient operation.

Claims (10)

1. The epoxy resin adhesive film is characterized by comprising a resin matrix and a carrier, wherein the resin matrix comprises the following components in parts by weight: 40-60 parts of liquid epoxy resin containing hydroxyl, 15-40 parts of toughening agent, 10-20 parts of aromatic isocyanate compound, 5-12 parts of curing agent, 1-5 parts of thixotropic agent and 1-5 parts of silane coupling agent; the aromatic isocyanate has at least 2 NCO-reactive groups; the carrier is polyester felt or glass fiber thin cloth.
2. The epoxy adhesive film of claim 1, wherein the hydroxyl-containing liquid epoxy resin comprises at least one of bisphenol a type epoxy resin, bisphenol F type epoxy resin, phenolic type epoxy resin, multifunctional epoxy resin, and aliphatic alcohol polyglycidyl ether.
3. The epoxy adhesive film of claim 1, wherein the toughening agent comprises at least one of a hydroxyl terminated nitrile rubber, an amine terminated nitrile rubber, an epoxy terminated nitrile rubber, a prepolymer of epoxy and nitrile rubber, and a dispersed core shell rubber.
4. The epoxy adhesive film of claim 1, wherein the aromatic isocyanate compound comprises at least one of a polymeric diphenylmethane diisocyanate, a carbodiimide-modified diphenylmethane diisocyanate, and a urethane-modified diphenylmethane diisocyanate.
5. The epoxy adhesive film of claim 1, wherein the curing agent is a mixture of dicyandiamide and an organic urea derivative; the thixotropic agent comprises at least one of fumed silica, nano calcium carbonate and silicon powder.
6. The method for preparing the epoxy resin adhesive film as claimed in claims 1 to 5, comprising the steps of:
(1) Taking part of liquid epoxy resin, adding a curing agent into the liquid epoxy resin, and stirring and dispersing the liquid epoxy resin at a high speed to obtain a curing agent compound;
(2) Adding a toughening agent, a thixotropic agent and a silane coupling agent into the residual liquid epoxy resin, and stirring and dispersing at a high speed to prepare a mixture;
(3) Adding the cured compound in the step (1) into the mixture in the step (2), stirring and dispersing at a high speed, and then adding an aromatic isocyanate compound into the mixture to continuously stir and disperse to prepare a resin matrix for an epoxy resin adhesive film;
(4) Setting the temperature of a glue spreader to be 25-35 ℃, pouring the epoxy resin matrix in the step (3) into a glue groove of a presoaking machine, coating the epoxy resin matrix on release paper according to a certain unit area mass to form a resin film, sequentially coating a polyester felt or glass fiber thin cloth and a PE film on the upper part of the resin film, winding, and then placing the resin film in a constant temperature chamber at 23-30 ℃ for standing for 45-50 hours to obtain the epoxy resin adhesive film.
7. The method for preparing an epoxy resin adhesive film according to claim 6, wherein the mass ratio of the amount of the liquid epoxy resin to the amount of the curing agent in the step (1) is 2-3, the high-speed stirring and dispersing speed is 200-600r/min, and the dispersing time is 20-40min.
8. The method of producing an epoxy resin film as defined in claim 6, wherein the high-speed stirring and dispersing in the step (2) and the step (3) are carried out at a rotational speed of 200 to 800r/min for a dispersing time of 20 to 40min.
9. The method for producing an epoxy resin film as claimed in claim 6, wherein the weight per unit area of the resin film in the step (4) is 210 to 250g/m 2 The method comprises the steps of carrying out a first treatment on the surface of the The weight of the unit area of the polyester felt or the glass fiber thin cloth is 18-22g/m 2 。
10. The method of producing an epoxy resin film as claimed in claim 6, wherein the epoxy resin film produced in the step (4) has a viscosity of 50000 to 250000cps at 70 ℃.
CN202310719365.9A 2023-06-16 2023-06-16 Epoxy resin adhesive film and preparation method thereof Pending CN116589939A (en)

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