CN110982438A - Solvent-free adhesive film and preparation method thereof - Google Patents
Solvent-free adhesive film and preparation method thereof Download PDFInfo
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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
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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- 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
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
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- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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- 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
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- 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
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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
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
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- 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
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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
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
- C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer
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Abstract
The invention discloses a solvent-free adhesive film and a preparation method thereof. The method comprises the following steps: mixing nitrile rubber and epoxy resin, and reacting to obtain a prepolymer; adding a diluent, a curing agent, an accelerator, an inorganic filling material and an auxiliary agent into the prepolymer, and reacting to obtain a solvent-free glue solution; and depositing the solvent-free glue solution on a carrier layer, and curing to obtain the solvent-free glue film. In the preparation process of the adhesive film, an organic solvent harmful to the environment is not used, so that the environmental protection requirement of the application industry can be met; meanwhile, the prepared solvent-free glue solution has excellent adhesive property and can be well adhered to metal substrates, plastic and other carrier layers; furthermore, because no organic solvent is used in the preparation process of the adhesive film, no solvent residue exists in the prepared adhesive film, so that the heat resistance and breakdown voltage resistance of the adhesive film are ensured, and the requirements of subsequent production processes and product use can be met.
Description
Technical Field
The invention relates to the field of printed circuit boards, in particular to a solvent-free adhesive film and a preparation method thereof.
Background
The existing adhesive film for the aluminum substrate industry is prepared by a solvent type adhesive solution through a coating process, and most of solvents are organic solvents such as dimethylformamide, butanone, acetone, propylene glycol monomethyl ether, xylene and ethyl acetate. It is known that solvents are basically toxic, which causes more or less physical harm to the production workers, and also causes environmental pollution. In the production process, the solvent is finally volatilized, recovered and combusted, so that some treatment cost is increased for enterprises. The formulation contains a large amount of solvent, and a certain amount of residue is left in the subsequent curing process of the resin, which affects the breakdown voltage resistance and the heat resistance of the product. To ensure the breakdown voltage resistance of the product, the thickness of the heat-conducting insulating layer needs to be increased, so that the thermal resistance is increased, and the development of the product to the high performance is limited.
Accordingly, the prior art is yet to be improved and developed.
Disclosure of Invention
In view of the above-mentioned shortcomings of the prior art, the present invention aims to provide a solvent-free adhesive film and a method for preparing the same, which aims to solve the problems of low breakdown voltage and poor heat resistance of the existing adhesive film.
The technical scheme of the invention is as follows:
a preparation method of a solvent-free adhesive film comprises the following steps:
mixing nitrile rubber and epoxy resin, and reacting to obtain a prepolymer;
adding a diluent, a curing agent, an accelerator, an inorganic filling material and an auxiliary agent into the prepolymer, and reacting to obtain a solvent-free glue solution;
and depositing the solvent-free glue solution on a carrier layer, and curing to obtain the solvent-free glue film.
Further, the nitrile rubber is selected from one or more of CTBN1300X8, CTBN1300X13, CTBN1300X31, CTBN1300X18, CTBN1300X9 and CTBN2000X 162.
Further, the epoxy resin is selected from one or more of bisphenol a type epoxy resin, bisphenol F type epoxy resin, novolac epoxy resin, glycidyl amine type epoxy resin, cresol formaldehyde type epoxy resin, linear aliphatic epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin, and urethane-modified epoxy resin.
Further, the step of mixing the nitrile rubber and the epoxy resin for reaction to prepare the prepolymer specifically comprises:
mixing nitrile rubber and epoxy resin according to the molar ratio of carboxyl to epoxy being 1:1.2, and reacting for 2-8 hours at the temperature of 130-160 ℃ to obtain the prepolymer.
Further, the viscosity of the prepolymer ranges from 100000-.
Further, the addition amount of the diluent is 5-35% of the total mass of the nitrile rubber and the epoxy resin.
Further, the addition amount of the curing agent is such that the molar ratio of the epoxy groups of the epoxy resin to the reactive groups of the curing agent is 1:0.5-1: 1.2.
Further, the addition amount of the accelerator is 0.15-0.5% of the total mass of the epoxy resin, the diluent and the curing agent.
Further, the curing temperature is 80-170 ℃ and the curing time is 1-10 min.
The solvent-free adhesive film is prepared by the method.
Has the advantages that: the invention provides a solvent-free adhesive film and a preparation method thereof, wherein an organic solvent harmful to the environment is not used in the preparation process of the adhesive film, so that the environmental protection requirement of the application industry can be met; meanwhile, the prepared solvent-free glue solution has excellent adhesive property and can be well adhered to metal substrates, plastic and other carrier layers; furthermore, because no organic solvent is used in the preparation process of the adhesive film, no solvent residue exists in the prepared adhesive film, so that the heat resistance and breakdown voltage resistance of the adhesive film are ensured, and the requirements of subsequent production processes and product use can be met.
Drawings
Fig. 1 is a schematic flow chart of a method for preparing a solvent-free adhesive film according to an embodiment of the present invention.
Detailed Description
The invention provides a solvent-free adhesive film and a preparation method thereof, and the invention is further described in detail below in order to make the purpose, technical scheme and effect of the invention clearer and clearer. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Referring to fig. 1, fig. 1 is a schematic flow chart of a method for preparing a solvent-free adhesive film according to an embodiment of the present invention, as shown in fig. 1, which includes the steps of:
s10, mixing nitrile rubber and epoxy resin, and reacting to obtain a prepolymer;
s20, adding a diluent, a curing agent, an accelerator, an inorganic filling material and an auxiliary agent into the prepolymer, and reacting to obtain a solvent-free glue solution;
and S30, depositing the solvent-free glue solution on a carrier layer, and curing to obtain the solvent-free glue film.
Based on the fact that a large amount of toxic organic solvents are needed in the existing heat-conducting adhesive film preparation process, and the added organic solvents can affect the breakdown voltage resistance and the heat resistance of the prepared heat-conducting adhesive film, the embodiment provides a preparation method of a solvent-free adhesive film.
In this embodiment, two ends of a nitrile rubber molecular chain are active functional group carboxyl groups, an epoxy resin has an extremely active epoxy group in a structure, and a prepolymer with a medium-high molecular weight is obtained by a ring-opening crosslinking reaction between the carboxyl group on the nitrile rubber molecular chain and the epoxy group on the epoxy resin molecular chain. A small amount of epoxy groups are remained in the prepolymer, because the epoxy resin is excessive relative to the nitrile rubber during raw material matching, so that carboxyl groups in the nitrile rubber are reacted completely, and epoxy groups are formed at two ends of the prepolymer; furthermore, a small amount of the remaining epoxy resin does not participate in the ring-opening crosslinking reaction. Meanwhile, the nitrile rubber has a-CN group with extremely strong polarity, so that the nitrile rubber has better miscibility with the epoxy resin and can be well dispersed in the epoxy resin matrix in the prepolymer preparation process and the curing reaction process. And then, carrying out curing reaction on the prepolymer, the retained epoxy groups, the curing agent and the accelerator to form a pre-cured product with a certain crosslinking degree. In the embodiment, the prepolymer and the reserved epoxy group are cured to form a macromolecular skeleton structure, so that the overall strength and toughness of the solvent-free adhesive film can be ensured. In addition, the nitrile rubber contains-CN group, and the adhesive strength of the material is improved by introducing the nitrile rubber into the adhesive film.
Further, a diluent, a curing agent, an accelerator, an inorganic filling material and an auxiliary agent are added in the embodiment, wherein the inorganic filling material plays a role in heat conduction, the diluent can adjust the viscosity of the glue solution and is beneficial to the dispersion of the inorganic filling material, the curing agent can enable the retained epoxy resin to continue to be crosslinked and cured to form a crosslinked network structure, the accelerator added can control the gelling time of the glue solution and adjust the curing process, in addition, the auxiliary agent is also added in the solvent-free glue solution, and the auxiliary agent can be a leveling agent, a wetting dispersant, an antifoaming agent, a coupling agent and the like.
In step S10, the nitrile rubber is a liquid nitrile rubber resin terminated with carboxyl groups, abbreviated as CTBN, and its structural formula is as follows:
in one embodiment, the nitrile rubber may be selected from one or more of CTBN1300X8 (acrylonitrile content 18%, viscosity 135000cps @27 ℃, molecular weight Mn3550), CTBN1300X13 (acrylonitrile content 26%, viscosity 500000cps @27 ℃, molecular weight Mn3150), CTBN1300X31 (acrylonitrile content 10%, viscosity 60000cps @27 ℃, molecular weight Mn3800), CTBN1300X18 (acrylonitrile content 21.5%, viscosity 350000cps @27 ℃, molecular weight Mn3400), CTBN1300X9 (acrylonitrile content 18%, viscosity 160000cps @27 ℃, molecular weight Mn3600), and CTBN2000X162 (viscosity 60000cps @27 ℃, molecular weight Mn4200), and the like. It should be noted that the above percentages are mass percentages.
In this embodiment, a liquid epoxy resin is preferable in view of the processing property of the glue solution. In one embodiment, the epoxy resin may be selected from one or more of bisphenol a type epoxy resin, bisphenol F type epoxy resin, novolac epoxy resin, glycidyl amine type epoxy resin, cresol formaldehyde type epoxy resin, linear aliphatic epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin, urethane modified epoxy resin, and the like. The bisphenol A epoxy resin may be epoxy E42, epoxy E44, epoxy E51, epoxy E54, or the like. The bisphenol F type epoxy resin can be NPEF-170 (epoxy equivalent 160-. The novolac epoxy resin can be NPPN-631 (epoxy equivalent 168-178g/eq, viscosity 1100-1700cps @52 ℃), EPALLOY8220 (epoxy equivalent 164-176g/eq, viscosity 1100-2800cps @25 ℃), EPALLOY8230 (epoxy equivalent 164-176g/eq, viscosity 3500-4700cps @25 ℃), EPALLOY8240 (epoxy equivalent 164-178g/eq, viscosity 18000-28000cps @25 ℃), EPALLOY8330 (epoxy equivalent 171-183g/eq, viscosity 20000-30000cps @52 ℃) and the like. The alicyclic epoxy resin may be Celloxide 2000 (viscosity 1.5cps @25 ℃ C.), Celloxide 2021P (epoxy equivalent 128-145g/eq, viscosity 100-600cps @25 ℃ C.), Celloxide 2081 (epoxy equivalent 200g/eq, viscosity 340cps @25 ℃ C.), etc.
In one embodiment, the step of mixing nitrile rubber and epoxy resin and reacting to obtain the prepolymer specifically comprises:
mixing nitrile rubber and epoxy resin according to the molar ratio of carboxyl to epoxy being 1:1.2, and reacting for 2-8 hours at the temperature of 130-160 ℃ to obtain the prepolymer. Wherein, the viscosity of the prepolymer is in the range of 100000-200000cps at 25 ℃. This viscosity range allows the prepolymer to remain in a liquid state, facilitating the addition and dispersion of subsequent processes.
Two ends of the molecular chain of the nitrile rubber are active functional group carboxyl, and the carboxyl of the nitrile rubber can generate ring-opening crosslinking reaction with the epoxy group in the epoxy resin to form a prepolymer. And the nitrile rubber has a-CN group with extremely strong polarity, has better miscibility with the epoxy resin, and can be well dispersed in the epoxy resin matrix in the prepolymerization reaction and the curing reaction processes. The reaction equation for the synthesis of the prepolymer is as follows:
in one embodiment, the diluent is added in an amount of 5 to 35% of the total mass of the nitrile rubber and the epoxy resin. In this embodiment, the diluent may be a monofunctional reactive diluent or a multifunctional reactive diluent, and may be, for example, propylene oxide butyl ether or tetradecyl glycidyl ether. In this embodiment, a diluent is added to adjust the viscosity of the glue solution, and since a solvent is not utilized in the preparation process, the added inorganic filling material is not easy to disperse, and a proper amount of the diluent needs to be added to improve the dispersion condition of the inorganic filling material, wherein the amount of the diluent is 5-35% of the total mass of the nitrile rubber and the epoxy resin, if the amount of the diluent is too small, the dispersion effect of the inorganic filling material is affected, and if the amount of the diluent is too large, the heat resistance of the prepared solvent-free glue film is affected.
In one embodiment, the curing agent is added in an amount such that the epoxy groups of the epoxy resin are in a molar ratio to the reactive groups of the curing agent of from 1:0.5 to 1: 1.2. In this embodiment, the curing agent may be one or more of an amine curing agent, a phenol curing agent, an acid anhydride curing agent, and the like, wherein the amine curing agent may be one or more of polyetheramine D-230, alicyclic amine H-100S, JH-5826, modified amine JH-930, JH-5903, JH-5953, JH-5402, JH-5408, JH-5601, JH-5465, aromatic amine Ethacure200, Ethacure300, and the like, the phenol curing agent may be one or more of a phenol type phenolic resin, an o-cresol type phenolic resin, a bisphenol a type phenolic resin, a nitrogen-containing phenolic resin, and the like, and the acid anhydride curing agent is preferably methyl tetrahydrophthalic anhydride (MTHPA).
In the embodiment, the amount of the curing agent is determined by the ratio of epoxy groups on the epoxy resin to corresponding reactive groups on the curing agent, and when the molar ratio of the epoxy groups on the epoxy resin to the corresponding reactive groups on the curing agent is 1:0.5-1:1.2, the heat resistance of the prepared solvent-free adhesive film is not affected.
In one embodiment, the accelerator is added in an amount of 0.15 to 0.5% of the total mass of the epoxy resin, diluent and curing agent. In this embodiment, the accelerator may be an imidazole accelerator, for example, may be one or more of 2-methylimidazole (2MZ), 2-ethyl, 4-methylimidazole (2E4MZ), 2-phenylimidazole (2PZ), 2-phenyl, 4-methylimidazole (2P4MZ), and the like, and preferably 2-ethyl, 4-methylimidazole (2E4MZ), which is liquid at room temperature, is compatible with the glue solution system, has good mixing property, and further has stronger curing activity but is not as vigorous as 2-methylimidazole (2MZ), can better adjust the gelling time of the glue solution, and is more advantageous for storing the glue solution. The accelerator is used for adjusting the gelling time of the glue solution, namely adjusting the curing process of the epoxy resin, accelerating the curing reaction process or slowing down the curing reaction, if the usage of the accelerator exceeds 0.5 percent of the total mass of the epoxy resin, the diluent and the curing agent, the added amount is too much, the curing reaction time is short, the solvent-free adhesive film is not easy to store, the adhesive film may lose efficacy before being used by a user, and if the usage of the accelerator is less than 0.15 percent of the total mass of the epoxy resin, the diluent and the curing agent, the usage is too little, and the effect of adjusting the gelling time of the glue solution cannot be achieved.
In some embodiments, the inorganic filler material comprises 60-80% of the total mass of the solvent-free cement. In the present embodiment, the inorganic filler may be one or more of silica, alumina, barium sulfate, magnesium oxide, boron nitride, aluminum nitride, silicon carbide, aluminum borate, barium titanate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, calcium zirconate, and the like. The inorganic filling material accounts for 60-80% of the mass of the solvent-free glue solution, if the mass of the inorganic filling material is greater than 80% of the mass of the solvent-free glue solution, the inorganic filling material is difficult to disperse, the breakdown voltage resistance, the heat resistance and the peel strength of the prepared solvent-free glue solution are reduced, and if the mass of the inorganic filling material is less than 60% of the mass of the solvent-free glue solution, the overall heat conductivity coefficient of the prepared solvent-free glue film is not high, and the heat conductivity effect is influenced.
In some embodiments, the auxiliary agent may be one or more of a leveling agent, a wetting dispersant, a defoaming agent, a coupling agent, and the like. In the embodiment, the flatting agent can be BYK-310, BYK-330, BYK-333, BYK-390 or FC4430, and the using amount of the flatting agent can be 0.1-0.2% of the total mass of the solvent-free glue solution; the wetting dispersant can be BYK-W903, BYK-W9010, KYC-918 and KYC-919, and the dosage of the wetting dispersant can be 0.5-2% of the mass of the inorganic filling material; the defoaming agent can be BYK-530 or DP-60, and the using amount of the defoaming agent can be 0.1-1.5% of the total mass of the solvent-free glue solution; the coupling agent can be KH540, KH550 and KH650, and the dosage of the coupling agent can be 0.1-1.5% of the total mass of the solvent-free glue solution. The added auxiliary agent can further improve the performance of the solvent-free adhesive film.
In step S30, the deposition may be coating, etc., but is not limited thereto, and the coating may be one coating, two coatings, multiple coatings in a molding process. The coating process according to the equipment can be a spraying process, a film coating process, an inclined plate scraper coating process, a gum licking process, a tape casting coating process and the like.
In this embodiment, the carrier layer is not particularly limited, and may be made of a plastic film material or a metal material. The plastic film material may be polyolefin such as polyethylene, polypropylene, polyvinyl chloride, etc., polyester such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polycarbonate, etc., or may be polyimide. As the plastic film, PET is preferable, the thickness is preferably 30-80um, and the PET film can be a carrier film material treated in a release manner. The metal material can be copper foil, aluminum sheet and other alloy materials.
In the embodiment, the curing process is a thermosetting process and mainly comprises 2 factors of temperature and time, the curing temperature is selected to be 80-170 ℃, and the heating time is selected to be 1-10 min. Generally, the curing process is carried out in a tunnel oven, and specific parameters can be exemplified as follows:
the adhesive film surface drying detection method comprises the following steps:
stage I: when the fingers lightly touch the adhesive film, the surface of the adhesive layer has no viscosity or the adhesive layer has no transfer, and the adhesive film has certain strength, namely the adhesive film reaches 'surface dryness'.
And II, stage: the glue film is twisted by fingers, and the glue film has no viscosity and does not crack.
Grade III: and scratching the surface of the adhesive film by using a fingernail, wherein the adhesive film has no scratch, namely the adhesive film is completely cured.
The present invention is further illustrated by the following specific examples.
Example 1
Solvent-free glue solution: 5 parts of CTBN1300X8 (acrylonitrile content is 18%, viscosity is 135000cps @27 ℃, molecular weight is Mn3550), 10 parts of bisphenol A type epoxy resin (south Asia epoxy 128, epoxy equivalent 190), 2 parts of epoxypropane butyl ether (501 reactive diluent), 2.2 parts of Ethacure200 aromatic amine, 2E4MZ 0.034.034 parts, 51 parts of silicon dioxide (particle size is 1-5um), BYK-3330.106 parts, KYC-9185.1 parts, DP-600.071 parts and KH5600.071 parts.
Coating the solvent-free glue solution on the release surface of the release PET film by an inclined plate scraper, wherein the thickness of the PET film is 36um, and the curing process comprises the following steps:
example 2
Solvent-free glue solution: 3 parts of CTBN1300X8 (acrylonitrile content is 18 percent, viscosity is 135000cps @27 ℃ and molecular weight is Mn3550), 10 parts of CTBN1300X13 (acrylonitrile content is 26 percent, viscosity is 500000cps @27 ℃ and molecular weight is Mn3150), 2 parts of bisphenol F epoxy resin NPEF-170 (epoxy equivalent is 160-eq, viscosity is 2000-5000cps @25 ℃), 2 parts of epoxypropane butyl ether (501 reactive diluent), 2 parts of Ethacure200 aromatic amine, 3 parts of methyl tetrahydrophthalic anhydride (MTHPA), 2E4MZ 0.034.034, 51 parts of silicon dioxide (particle size is 1-5um), BYK-3330.106 parts, KYC-9185.1 parts, DP-600.071 and KH5600.071 parts.
Coating the solvent-free glue solution on the release surface of the release PET film by an inclined plate scraper, wherein the thickness of the PET film is 36um, and the curing process comprises the following steps:
example 3
Solvent-free glue solution: 3 parts of CTBN1300X8 (acrylonitrile content is 18%, viscosity is 135000cps @27 ℃ and molecular weight is Mn3550), 3 parts of CTBN1300X13 (acrylonitrile content is 26%, viscosity is 500000cps @27 ℃ and molecular weight is Mn3150), 5 parts of bisphenol A type epoxy resin (south Asia epoxy 128, epoxy equivalent 190), 5 parts of bisphenol F type epoxy resin NPEF-170 (epoxy equivalent 160 g/eq, viscosity is 2000 cps @25 ℃), 2 parts of epoxypropane butyl ether (501 reactive diluent), 2 parts of Ethacure200 aromatic amine, 3 parts of methyl tetrahydrophthalic anhydride (MTHPA), 2E4MZ 0.034 parts, 51 parts of alumina (particle size is 5um), BYK-3330.106 parts, KYC-9185.1 parts, DP-600.071 and KH5600.071 parts.
Coating the solvent-free glue solution on the release surface of the release PET film by an inclined plate scraper, wherein the thickness of the PET film is 36um, and the curing process comprises the following steps:
example 4
Solvent-free glue solution: 3 parts of CTBN1300X8 (acrylonitrile content is 18%, viscosity is 135000cps @27 ℃ and molecular weight is Mn3550), 3 parts of CTBN1300X13 (acrylonitrile content is 26%, viscosity is 500000cps @27 ℃ and molecular weight is Mn3150), 7 parts of bisphenol A type epoxy resin (south Asia epoxy 128, epoxy equivalent 190), 3 parts of alicyclic epoxy resin Celloxide 2021P (epoxy equivalent 128-145g/eq, viscosity is 100 cps @25 ℃), 2 parts of epoxypropane butyl ether (501 reactive diluent), 2 parts of Ethacure200 aromatic amine, 3 parts of methyl tetrahydrophthalic anhydride (MTHPA), 0.034 part of 2E4MZ 0.034, 51 parts of magnesium oxide (particle size is 5um), BYK-3330.106 parts, KYC-9185.1 parts, DP-600.071 and KH5600.071 parts.
Coating the solvent-free glue solution on the release surface of the release PET film by an inclined plate scraper, wherein the thickness of the PET film is 36um, and the curing process comprises the following steps:
the test results for examples 1-4 above are as follows:
as is apparent from the table above, the solvent-free adhesive film prepared by the embodiment has good heat resistance and high breakdown voltage resistance, and can meet the requirements of subsequent production processes and product use.
In summary, the invention provides a solvent-free adhesive film and a preparation method thereof, and the solvent-free adhesive film and the preparation method thereof do not use an organic solvent harmful to the environment in the preparation process of the adhesive film, so that the environmental protection requirement of the application industry can be met; meanwhile, the prepared solvent-free glue solution has excellent adhesive property and can be well adhered to metal substrates, plastic and other carrier layers; furthermore, because no organic solvent is used in the preparation process of the adhesive film, no solvent residue exists in the prepared adhesive film, so that the heat resistance and breakdown voltage resistance of the adhesive film are ensured, and the requirements of subsequent production processes and product use can be met.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.
Claims (10)
1. The preparation method of the solvent-free adhesive film is characterized by comprising the following steps:
mixing nitrile rubber and epoxy resin, and reacting to obtain a prepolymer;
adding a diluent, a curing agent, an accelerator, an inorganic filling material and an auxiliary agent into the prepolymer, and reacting to obtain a solvent-free glue solution;
and depositing the solvent-free glue solution on a carrier layer, and curing to obtain the solvent-free glue film.
2. The method for preparing the solvent-free adhesive film according to claim 1, wherein the nitrile rubber is one or more selected from the group consisting of CTBN1300X8, CTBN1300X13, CTBN1300X31, CTBN1300X18, CTBN1300X9 and CTBN2000X 162.
3. The method for preparing the solventless adhesive film according to claim 1, wherein the epoxy resin is selected from one or more of bisphenol a type epoxy resin, bisphenol F type epoxy resin, novolac epoxy resin, glycidyl amine type epoxy resin, cresol formaldehyde type epoxy resin, linear aliphatic epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin, and urethane-modified epoxy resin.
4. The method for preparing the solvent-free adhesive film according to claim 1, wherein the step of mixing the nitrile rubber and the epoxy resin for reaction to obtain the prepolymer comprises:
mixing nitrile rubber and epoxy resin according to the molar ratio of carboxyl to epoxy being 1:1.2, and reacting for 2-8 hours at the temperature of 130-160 ℃ to obtain the prepolymer.
5. The method for preparing a solventless adhesive film according to claim 1, wherein the viscosity of the prepolymer is 100000-200000cps at 25 ℃.
6. The method for preparing the solvent-free adhesive film according to claim 1, wherein the amount of the diluent added is 5-35% of the total mass of the nitrile rubber and the epoxy resin.
7. The method for preparing the solvent-free adhesive film according to claim 1, wherein the curing agent is added in an amount such that the molar ratio of the epoxy groups of the epoxy resin to the reactive groups of the curing agent is 1:0.5-1: 1.2.
8. The method for preparing the solvent-free adhesive film according to claim 1, wherein the amount of the accelerator added is 0.15-0.5% of the total mass of the epoxy resin, the diluent and the curing agent.
9. The method for preparing the solvent-free adhesive film according to claim 1, wherein the curing temperature is 80-170 ℃ and the curing time is 1-10 min.
10. A solventless adhesive film characterized by being prepared by the method of any one of claims 1 to 9.
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