CN115093818B - Electronic grade adhesive and preparation method thereof - Google Patents
Electronic grade adhesive and preparation method thereof Download PDFInfo
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- CN115093818B CN115093818B CN202210732671.1A CN202210732671A CN115093818B CN 115093818 B CN115093818 B CN 115093818B CN 202210732671 A CN202210732671 A CN 202210732671A CN 115093818 B CN115093818 B CN 115093818B
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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
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
- C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
- C08G59/063—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols with epihalohydrins
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- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
- C08G59/4014—Nitrogen containing compounds
- C08G59/4021—Ureas; Thioureas; Guanidines; Dicyandiamides
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- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/56—Amines together with other curing agents
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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
- 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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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2170/00—Compositions for adhesives
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- C08G2190/00—Compositions for sealing or packing joints
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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
- C08K3/28—Nitrogen-containing compounds
- C08K2003/282—Binary compounds of nitrogen with aluminium
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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
- C08K3/38—Boron-containing compounds
- C08K2003/382—Boron-containing compounds and nitrogen
- C08K2003/385—Binary compounds of nitrogen with boron
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- C08K2201/00—Specific properties of additives
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- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts
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Abstract
The application relates to the field of electronic device packaging, and particularly discloses an electronic adhesive and a preparation method thereof. The electronic adhesive comprises an adhesive component and a curing agent component, wherein the adhesive component comprises the following raw materials: epoxy resin, filler, silane coupling agent, maleated polybutadiene, wherein the filler comprises spherical alumina; the preparation method comprises the following steps: mixing p-methylphenyl diglycidyl ether and bisphenol A diglycidyl ether type epoxy resin; adding spherical alumina, high-heat-conductivity aluminum nitride, surface modified boron nitride, a silane coupling agent and maleic anhydride polybutadiene to prepare an adhesive component; uniformly mixing 2-methylimidazole and dicyandiamide to prepare a curing agent component; and uniformly stirring the adhesive component and the curing agent component in proportion to prepare the electronic adhesive. The application has the advantage of improving the heat conductivity of the electronic grade adhesive.
Description
Technical Field
The application relates to the field of electronic device packaging, in particular to an electronic grade adhesive and a preparation method thereof.
Background
The electronic-grade adhesive is specially used for bonding, sealing, encapsulating, coating, structural bonding, co-running coating, SMT (surface mounted technology) patch and the like of electronic and electric components and has wider application. The common electronic-grade adhesive also has the characteristics of excellent adhesive property, waterproof property and the like, less toxic volatile substances, corrosion resistance, oxidation resistance, high temperature resistance and the like, and can be divided into an insulating adhesive and a conductive adhesive according to requirements.
The electronic adhesive is generally adhered between joints of the electronic components to fixedly connect the electronic components, and after the adhesive is adhered, the electronic components may be in a sealed state. The adhesive has poor heat conductivity, and the electronic equipment can continuously generate heat during operation, so that the heat dissipation performance of the electronic equipment can be reduced after the adhesive is adhered. If the heat in the electronic equipment cannot be timely dissipated, the normal operation of the electronic equipment can be affected, and even the service life of the electronic equipment is reduced.
Disclosure of Invention
In order to improve the heat conductivity of the electronic grade adhesive, the application provides the electronic grade adhesive and a preparation method thereof.
In a first aspect, the present application provides an electronic grade adhesive, which adopts the following technical scheme:
the electronic grade adhesive comprises an adhesive component and a curing agent component, wherein the adhesive component comprises the following raw materials in parts by weight: 60-80 parts of epoxy resin, 40-60 parts of filler, 1-2 parts of silane coupling agent and 13-14 parts of maleinized polybutadiene, wherein the filler comprises 16-42 parts of spherical aluminum oxide with a particle size distribution of 12-14 mu m, 6-7 mu m and 1.5-1.7 mu m in one or more combinations, and the spherical aluminum oxide with a particle size distribution of 12-14 mu m, 6-7 mu m and 1.5-1.7 mu m is in a mass ratio of 4-8:1-5:1.
by adopting the technical scheme, the thermal resistance and the concentration of the heat conduction chains are important parameters affecting the heat conduction performance, spherical alumina with different particle diameters is adopted for compounding, so that the filler can form the spatial distribution of large particles, medium particles and small particles, the filler is stacked more tightly, the interface phonon scattering and the interface thermal resistance are reduced, a heat conduction path is easier to form, the maximum stacking degree is formed, the number of the heat conduction chains is increased, the concentration of the heat conduction chains is improved, the heat conductivity of the adhesive is improved, the surface of the alumina contains hydroxyl groups, the surface treatment is carried out by using a silane coupling agent, the epoxy resin and the alumina can be bonded by covalent bonds, the filler and the epoxy resin are combined, the adhesive strength between the filler and the epoxy resin is enhanced, and the interface thermal resistance is reduced, so that the heat conductivity of the adhesive is further improved; the maleinized polybutadiene can improve the dispersibility of the filler and the heat conduction property brought by the filler.
Preferably, the filler also comprises 4-18 parts of high-heat-conductivity aluminum nitride, wherein the high-heat-conductivity aluminum nitride is prepared by adopting a silane coupling agent to carry out surface treatment, the particle size distribution of the high-heat-conductivity aluminum nitride is 1.1-1.5 mu m, and the mass ratio of the spherical aluminum oxide to the high-heat-conductivity aluminum nitride is 4-6:1-3.
By adopting the technical scheme, after the filler for improving the heat conduction performance is added into the epoxy resin, the performance of the adhesive is reduced, a small amount of aluminum nitride is added, the attractive force between aluminum nitride particles is reduced after the aluminum nitride is modified by the silane coupling agent, the dispersibility in the epoxy resin is improved, the silane coupling agent can connect the aluminum nitride with the epoxy resin to form a chemical bond, and the bonding strength between the aluminum nitride and the epoxy resin and the tensile strength of the adhesive are enhanced; a small amount of aluminum nitride can effectively transfer stress in the process of curing the epoxy resin, reduce the shrinkage rate of the epoxy resin and prevent crack propagation, so that the bending strength of the adhesive is improved; the small amount of aluminum nitride can reduce the thermal effect of the epoxy resin curing process, so that the defect of the bonding surface of the adhesive is reduced, the bonding quality is improved, and the bonding strength is improved; the aluminum nitride can also improve the heat resistance of the adhesive; the modified aluminum nitride also effectively improves the heat conduction performance of the adhesive; the difference of the grain diameter sizes of aluminum nitride has an influence on the heat conducting property.
Preferably, the preparation of the high heat conduction aluminum nitride comprises the following steps:
step 1: weighing and accurately metering a silane coupling agent, and dissolving the silane coupling agent in absolute ethyl alcohol with the volume being 2-4 times of that of the silane coupling agent to prepare a coupling agent absolute ethyl alcohol solution;
and 2, weighing and metering the aluminum nitride accurately, adding the aluminum nitride into an absolute ethanol solution of a coupling agent, stirring, performing ultrasonic dispersion, then heating to 80-85 ℃, refluxing for 30-40min under a nitrogen atmosphere, cooling, centrifuging, and finally drying for 2-3h at 120-130 ℃ to obtain the high-heat-conductivity aluminum nitride.
Preferably, the filler further comprises 9-24 parts of surface modified boron nitride; the surface modified boron nitride is prepared by adopting a silane coupling agent to carry out surface treatment; the particle size distribution of the surface modified boron nitride is 2.3-2.9 mu m; the silane coupling agent is one or more of KH-570, KH-550 and KH-560.
By adopting the technical scheme, the surface modified boron nitride is particles with good heat conduction performance, the particle size of the spherical aluminum oxide is larger than that of the aluminum nitride and that of the surface modified boron nitride, and the aluminum nitride particles and the surface modified boron nitride particles can be embedded in gaps of the spherical aluminum oxide particles to form a net-shaped or chain-shaped space distribution configuration, form a plurality of effective heat conduction channels and improve the heat conduction coefficient.
Preferably, the mass ratio of the spherical aluminum oxide, the high-heat-conductivity aluminum nitride and the surface modified boron nitride is 4-6:1-3:2-4.
By adopting the technical scheme, when the mass ratio of spherical alumina, high heat conduction aluminum nitride and surface modified boron nitride is 4-6:1-3:2-4, the stacking degree among spherical alumina, high-heat-conductivity aluminum nitride and surface modified boron nitride is better, more heat conduction channels can be formed, and the improved heat conduction coefficient is also more.
Preferably, the epoxy resin comprises one or more combinations of p-methylphenyl diglycidyl ether, bisphenol a diglycidyl ether type epoxy resin.
By adopting the technical scheme, the bisphenol A diglycidyl ether type epoxy resin is called brominated epoxy resin for short, the brominated epoxy resin has high-temperature resistance, the flame retardant property is better, the molecular weight of the brominated epoxy resin is lower, the problem that the brominated epoxy resin is difficult to dissolve can be solved by mixing the p-methylphenyl diglycidyl ether with the brominated epoxy resin, the p-methylphenyl diglycidyl ether contains a biphenyl structure, the heat resistance of the adhesive can be improved, the larger the addition amount of the filler is, the better the heat conductivity is, and the p-methylphenyl diglycidyl ether has good fluidity because of the biphenyl structure and can be mixed with more fillers, and has better effect when being mixed with aluminum nitride, surface modified boron nitride and aluminum oxide.
Preferably, the mass ratio of the p-methylphenyl diglycidyl ether to the bisphenol A diglycidyl ether type epoxy resin is 6-8:2-4.
By adopting the technical scheme, the mass ratio of the p-methylphenyl diglycidyl ether to the bisphenol A diglycidyl ether type epoxy resin is limited, so that the overall performance is better.
Preferably, the preparation method of the p-methylphenyl diglycidyl ether comprises the following steps:
s1: mixing p-methylaniline and sodium nitrite in the molar ratio of 1-1.2:1-1.1 into distilled water, wherein the volume of the distilled water is 2-3 times that of the mixed p-methylaniline and sodium nitrite, dropwise adding 37% -40% hydrochloric acid and continuously stirring, and the molar ratio of the hydrochloric acid to the sodium nitrite is 1-1.2:1-1.3, adding p-benzoquinone and sodium bicarbonate after the hydrochloric acid dropwise addition is completed, wherein the molar ratio of the p-methylaniline to the p-benzoquinone to the sodium bicarbonate is 1-1.2:1-1.3:1-1.3, continuously stirring for 3-4 hours, performing vacuum filtration, and drying at 70-80 ℃ for 1-2 hours to obtain the p-methylphenyl p-benzoquinone;
s2: p-methylphenyl p-benzoquinone, zinc powder and deionized water are mixed according to the molar ratio of 1:2:10-15, uniformly mixing and stirring, heating to 90-95 ℃ to generate reflux reaction, dropwise adding 37% hydrochloric acid and continuously stirring, wherein the molar ratio of the hydrochloric acid to the zinc powder is 0.9-1.1:1-1.2, continuously carrying out reflux reaction for 3-4 hours after the dripping is finished, continuously stirring, and finally filtering to obtain p-methylphenyl hydroquinone;
s3: adding epoxy chloropropane and tetrabutyl ammonium bromide into the p-methylphenyl hydroquinone, mixing and stirring, wherein the molar ratio of the p-methylphenyl hydroquinone to the epoxy chloropropane to the tetrabutyl ammonium bromide is 1:2-2.5:0.1-0.2, heating to 80-90 ℃, continuously heating for 4-5h, and removing unreacted epichlorohydrin by adopting a reduced pressure distillation method to prepare a pre-product;
s4: toluene and 30% -35% sodium hydroxide solution are added into the pre-product, and the molar ratio of the pre-product, the 30% sodium hydroxide solution and the toluene is as follows: 1:2-2.5:3-4, heating to 80-90 ℃, continuing for 2-3 hours, cooling, washing with deionized water to be neutral, removing toluene and deionized water by a reduced pressure distillation method, and drying at 60-70 ℃ for 4-5 hours to obtain the p-methylphenyl diglycidyl ether.
By adopting the technical scheme, zinc powder and methylphenyl-p-benzoquinone are mixed, deionized water is added, hydrochloric acid is dripped, hydrochloric acid can react with the zinc powder to generate free hydrogen ions, the free hydrogen ions can react with the methylphenyl-p-benzoquinone to break double bonds and perform addition reaction to prepare the p-methylphenyl-hydroquinone, and the byproduct zinc chloride is solid salt with the maximum solubility and is easy to filter along with the deionized water; the epoxy chloropropane and the p-methylphenyl hydroquinone undergo ring-opening polymerization reaction, then sodium hydroxide is added to dechlorinate the epoxy chloropropane and ring-closure again to form epoxy groups, so that the p-methylphenyl diglycidyl ether is generated, tetrabutylammonium bromide is a catalyst of the reaction, and toluene is a solvent of the reaction.
Preferably, the curing agent component comprises the following raw materials: 2-methylimidazole and dicyandiamide, wherein the mass ratio of the 2-methylimidazole to the dicyandiamide is 10-11:1-1.5, and the weight ratio of the adhesive component to the curing agent component is 50:3-5.
By adopting the technical scheme, dicyandiamide is a latent curing agent, has a longer applicable period with epoxy resin without deterioration, can be rapidly cured under corresponding external conditions, can effectively reduce the temperature required by dicyandiamide curing, can participate in addition reaction of epoxy groups by active hydrogen on secondary amine groups of 2-methylimidazole, plays a role of the curing agent, can catalyze the curing of epoxy resin through nitrogen atoms on tertiary amine, and can be used as a curing accelerator of dicyandiamide, and 2-methylimidazole can improve the heat resistance and mechanical properties of the adhesive and prolong the service life of the adhesive; the curing time and the curing temperature of the adhesive component can change along with the change of the quality of the curing agent component, and the addition of the filler can also prevent the polymerization of the epoxy resin, so that the optimal ratio of the adhesive component to the curing agent component is provided, the processing performance of the adhesive is improved, and the overall performance of the adhesive is improved.
In a second aspect, the application provides a preparation method of an electronic grade adhesive, which adopts the following technical scheme:
the preparation method of the electronic grade adhesive comprises the following steps:
step 1: preparing an adhesive component; meanwhile, preparing a curing agent component, namely uniformly mixing 2-methylimidazole and dicyandiamide which are accurately measured, and stirring for 20-30min to prepare the curing agent component;
step 1.1: mixing and stirring accurately measured p-methylphenyl diglycidyl ether and bisphenol A diglycidyl ether type epoxy resin uniformly, continuously stirring for 20-25min at 80-90 ℃, and vacuumizing to obtain epoxy resin;
step 1.2: firstly adding spherical alumina and a silane coupling agent which are accurately measured, stirring for 5-10min, then adding high-heat-conductivity aluminum nitride, surface modified boron nitride and maleic anhydride polybutadiene which are accurately measured, stirring for 30-45min in a vacuum environment, keeping the temperature at 70-80 ℃, and cooling to obtain an adhesive component;
step 2: and mixing and stirring the adhesive component and the curing agent component uniformly according to the weight ratio for 15-20min to obtain the electronic adhesive.
Through adopting above-mentioned technical scheme, when preparing epoxy, take out the bubble that vacuum was taken to epoxy, with the bubble in the resin to make the filler more even mix in epoxy, in order to improve the heat conductivility of gluing agent, and gluing agent component and curing agent component can be simultaneously in different containers preparation, when needs use, mix the stirring with both can obtain the curing agent that directly uses.
In summary, the application has the following beneficial effects:
1. because spherical alumina with different particle sizes is adopted as the filler, the spherical alumina with different particle sizes is compounded, so that the filler is piled up more tightly, interface phonon scattering and interface thermal resistance are reduced, a heat conduction path is easier to form, the maximum piling degree is formed, the quantity of heat conduction chains is increased, the concentration of the heat conduction chains is improved, the heat conductivity of the adhesive is improved, the silane coupling agent is adopted to modify the spherical alumina, the bonding strength between the spherical alumina and epoxy resin is enhanced, the interface thermal resistance is reduced, and the heat conductivity of the adhesive is further improved.
2. According to the application, modified aluminum oxide and surface modified boron nitride are preferably adopted as fillers, and because the particle sizes of the modified aluminum oxide and the surface modified boron nitride are smaller than those of spherical aluminum oxide, aluminum nitride particles and surface modified boron nitride particles can be embedded in gaps of spherical aluminum oxide particles to form a net-shaped or chain-shaped spatial distribution configuration, so that a plurality of effective heat conduction channels are formed, the heat conduction coefficient is improved, and three groups of fillers are mixed into p-methylphenyl diglycidyl ether and bisphenol A diglycidyl ether type epoxy resin, so that the heat resistance of the adhesive can be effectively improved, and the heat conduction performance of the adhesive can be better exerted.
3. According to the method, the thermal conductivity of the adhesive is improved by controlling the weight ratio of spherical aluminum oxide, high-thermal-conductivity aluminum nitride and surface-modified boron nitride, the adhesive with better thermal conductivity is obtained by adjusting the weight ratio of epoxy resin to filler, and the mass ratio of the adhesive component to the curing agent component is controlled, so that the adhesive has good performance.
Detailed Description
Raw materials
Para-methylaniline, CAS:106-49-0;
bisphenol a diglycidyl ether, CAS:1675-54-3;
epichlorohydrin, CAS:106-89-8;
tetrabutylammonium bromide, CAS:10549-76-5;
p-benzoquinone, CAS:106-51-4.
Preparation example
Preparation example 1
Preparation of p-methylphenyl diglycidyl ether:
s1: adding 6kg of p-methylaniline, 4kg of sodium nitrite and 22kg of distilled water into a stainless steel jacketed reaction kettle, uniformly mixing and stirring, dropwise adding 2.2kg of 37% hydrochloric acid, continuously stirring, dropwise adding 500mL/min of hydrochloric acid, adding 6kg of p-benzoquinone and 4.7kg of sodium bicarbonate after the dropwise adding of the hydrochloric acid is finished, continuously stirring for 4 hours, performing vacuum filtration through a vacuum filter, and drying at 80 ℃ for 2 hours to obtain p-methylphenyl p-benzoquinone;
s2: adding p-methylphenyl-p-benzoquinone in the step S1 and 4kg of zinc powder into a stainless steel jacket reaction kettle, uniformly mixing and stirring, adding 5kg of deionized water at a rotating speed of 700r/min, heating to 95 ℃ to generate reflux reaction, dropwise adding 2.2kg of 37% hydrochloric acid and continuously stirring, dropwise adding 500mL/min at a dropwise adding speed, continuously carrying out reflux reaction for 4 hours and continuously stirring after the dropwise adding is finished, and finally filtering by a vacuum filter to obtain p-methylphenyl hydroquinone;
s3: adding 5.6kg of epoxy chloropropane and 1kg of tetrabutyl ammonium bromide into the p-methylphenyl hydroquinone in the step S2, mixing and stirring, heating to 90 ℃, and distilling at the rotating speed of 800r/min under reduced pressure for 5 hours by a distiller to remove unreacted epoxy chloropropane to obtain a pre-product;
s4: 2kg of toluene and 2.45kg of 30% sodium hydroxide solution are added into the pre-product in the step S3, the mixture is heated to 90 ℃ at the rotating speed of 600r/min for 3 hours, cooled and washed to be neutral by deionized water, reduced pressure distillation is carried out by a distiller, toluene and deionized water are removed, and then the mixture is dried for 5 hours at 70 ℃ to obtain the p-methylphenyl diglycidyl ether.
Preparation example 2
Preparation of epoxy resin:
mixing 4.2kg of p-methylphenyl diglycidyl ether in preparation example 1 and 2.8kg of bisphenol A diglycidyl ether type epoxy resin, stirring uniformly at a rotating speed of 1000r/min, maintaining the temperature at 80 ℃, stirring for 25min, and vacuumizing by a vacuumizing machine to obtain the epoxy resin.
Preparation example 3
Preparation 3 differs from preparation 2 in that: 5.6kg of p-methylphenyl diglycidyl ether in preparation example 1 and 1.4kg of bisphenol A diglycidyl ether type epoxy resin are mixed and stirred uniformly, the rotating speed is 1000r/min, the temperature is 80 ℃, the heat preservation is carried out, the stirring is continued for 25min, and then the vacuum pumping is carried out by a vacuum pumping machine, so that the epoxy resin is prepared.
Preparation example 4
Preparation example 4 differs from preparation example 2 in that: mixing 4.9kg of p-methylphenyl diglycidyl ether in preparation example 1 and 2.1kg of bisphenol A diglycidyl ether type epoxy resin, stirring uniformly at a rotating speed of 1000r/min, maintaining the temperature at 80 ℃, stirring for 25min, and vacuumizing by a vacuumizing machine to obtain the epoxy resin.
Preparation example 5
Preparation 5 differs from preparation 2 in that: 3.5kg of p-methylphenyl diglycidyl ether in preparation example 1 and 3.5kg of bisphenol A diglycidyl ether type epoxy resin are mixed and stirred uniformly, the rotating speed is 1000r/min, the temperature is 80 ℃, the heat preservation is carried out, the stirring is continued for 25min, and then the vacuum pumping is carried out by a vacuum pumping machine, so that the epoxy resin is prepared.
Preparation example 6
Preparation example 6 differs from preparation example 2 in that: mixing and stirring 6.3kg of p-methylphenyl diglycidyl ether in preparation example 1 and 0.7kg of bisphenol A diglycidyl ether type epoxy resin uniformly, rotating at 1000r/min, maintaining the temperature at 80 ℃, continuously stirring for 25min, and vacuumizing by a vacuumizing machine to obtain the epoxy resin.
Preparation example 7
Preparation of high-heat-conductivity aluminum nitride:
step 1: adding 0.2kg of coupling agent KH-560 and 0.5kg of absolute ethyl alcohol into a stirrer, and uniformly mixing and stirring to prepare coupling agent absolute ethyl alcohol solution;
screening aluminum nitride by using a 8000-mesh screen, taking screened aluminum nitride, screening aluminum nitride by using a 10000-mesh screen, taking unscreened aluminum nitride, weighing 1.8kg of screened aluminum nitride into an absolute ethanol solution of a coupling agent, stirring for 30min at the rotating speed of 600r/min, then performing ultrasonic dispersion for 30min by using an ultrasonic dispersing instrument, heating to 85 ℃, refluxing for 35min under nitrogen atmosphere, performing centrifugal dispersion by using a centrifugal machine after cooling, removing the absolute ethanol solution, and finally drying in a dryer at 130 ℃ for 3h to obtain the high-heat-conductivity aluminum nitride.
Preparation example 8
Preparation of surface modified boron nitride:
adding 2g of boron nitride powder, 0.1g of coupling agent KH-570 and 200g of deionized water into a stirrer, mixing and stirring uniformly for 30 minutes at a rotating speed of 300-400r/min, carrying out suction filtration by a suction filter, and drying at 90 ℃ for 3 hours to obtain the surface modified boron nitride.
Examples
Example 1
The preparation method of the electronic grade adhesive comprises the following steps:
step 1: preparing an adhesive component; adding 4.2kg of spherical alumina and 0.2kg of coupling agent KH-570 into 7kg of epoxy resin in preparation example 2, wherein the spherical alumina is formed by compounding spherical alumina with particle size distribution of 12 μm, 7 μm and 1.5 μm respectively, sieving the spherical alumina with a 1000-mesh sieve, sieving the sieved part with a 1340-mesh sieve, sieving the non-sieved part with a spherical alumina with particle size distribution of 12 μm, sieving the spherical alumina with a 1340-mesh sieve, sieving the sieved part with a 2000-mesh sieve, sieving the non-sieved part with a spherical alumina with particle size distribution of 7 μm, sieving the spherical alumina with a 8000-mesh sieve, sieving the sieved part with a 10000-mesh sieve, sieving the non-sieved part with a spherical alumina with particle size distribution of 1.5 μm respectively, and the spherical alumina with particle size distribution of 12 μm, 7 μm and 1.5 μm respectively in a mass ratio of 4:5:1, stirring for 10min at the rotating speed of 600r/min at the total filling amount of 60% of epoxy resin, adding 1.2kg of maleinized polybutadiene, stirring for 40min in a vacuum environment, keeping the temperature at 80 ℃, and cooling to obtain an adhesive component;
simultaneously, preparing a curing agent component, namely uniformly mixing 2kg of 2-methylimidazole and 0.2kg of dicyandiamide, and stirring for 30min at the rotating speed of 600r/min to prepare the curing agent component;
step 2: the adhesive component and the curing agent component are mixed according to the weight ratio of 50:3, uniformly mixing and stirring for 20min to obtain the electronic adhesive.
Example 2
Example 2 differs from example 1 in that: the mass ratio of the spherical alumina with the particle size distribution of 12 mu m, 7 mu m and 1.5 mu m is changed into 5:4:1.
example 3
Example 3 differs from example 1 in that: the mass ratio of the spherical alumina with the particle size distribution of 12 mu m, 7 mu m and 1.5 mu m is changed to 6:3:1.
example 4
Example 4 differs from example 1 in that: the mass ratio of the spherical alumina with the particle size distribution of 12 mu m, 7 mu m and 1.5 mu m is changed into 7:2:1.
example 5
Example 5 differs from example 1 in that: the mass ratio of the spherical alumina with the particle size distribution of 12 mu m, 7 mu m and 1.5 mu m is changed to 8:1:1.
example 6
Example 6 differs from example 5 in that: in the step 1, 3.6kg of spherical alumina and 0.2kg of coupling agent KH-570 are added into 7kg of epoxy resin in preparation example 2, stirring is carried out for 10min at the rotating speed of 600r/min, and then 0.6kg of high heat conduction aluminum nitride and 1.2kg of maleinized polybutadiene in preparation example 7 are added, so that the weight ratio of the spherical alumina to the high heat conduction aluminum nitride is 6:1, stirring for 40min in a vacuum environment with the total filling amount of the filler being 60% of that of the epoxy resin, keeping the temperature at 80 ℃, and cooling to obtain the adhesive component.
Example 7
Example 7 differs from example 6 in that: 2.8kg of spherical alumina and 1.4kg of high-heat-conductivity aluminum nitride in preparation example 7 are added in the step 1 instead, so that the weight ratio of the spherical alumina to the high-heat-conductivity aluminum nitride is 6:3, the total filling amount of the filler is 60% of the epoxy resin.
Example 8
Example 8 differs from example 6 in that: 3.15kg of spherical alumina and 1.05kg of high-heat-conductivity aluminum nitride in preparation example 7 are added in the step 1 instead, so that the weight ratio of the spherical alumina to the high-heat-conductivity aluminum nitride is 6:2, the total filling amount of the filler is 60% of the epoxy resin.
Example 9
Example 9 differs from example 6 in that: 3.36kg of spherical alumina and 8.4kg of high-heat-conductivity aluminum nitride in preparation example 7 are added in the step 1 instead, so that the weight ratio of the spherical alumina to the high-heat-conductivity aluminum nitride is 4:1, the total filling amount of the filler is 60% of the epoxy resin.
Example 10
Example 10 differs from example 6 in that: 2.4kg of spherical alumina and 1.8kg of high-heat-conductivity aluminum nitride in preparation example 7 are added in the step 1 instead, so that the weight ratio of the spherical alumina to the high-heat-conductivity aluminum nitride is 4:3, the total filling amount of the filler is 60% of the epoxy resin.
Example 11
Example 11 differs from example 6 in that: 3.5kg of spherical alumina and 0.7kg of high heat conduction aluminum nitride in preparation example 7 are added in the step 1 instead, so that the weight ratio of the spherical alumina to the high heat conduction aluminum nitride is 5:1, the total filling amount of the filler is 60% of the epoxy resin.
Example 12
Example 12 differs from example 6 in that: 2.63kg of spherical alumina and 1.58kg of high-heat-conductivity aluminum nitride in preparation example 7 are added in the step 1 instead, so that the weight ratio of the spherical alumina to the high-heat-conductivity aluminum nitride is 5:3, the total filling amount of the filler is 60% of the epoxy resin.
Example 13
Example 13 differs from example 6 in that: 3kg of spherical alumina and 1.2kg of high-heat-conductivity aluminum nitride in preparation example 7 are added in the step 1 instead, so that the weight ratio of the spherical alumina to the high-heat-conductivity aluminum nitride is 5:2, the total filling amount of the filler is 60% of the epoxy resin.
Example 14
Example 14 differs from example 13 in that: in the step 1, 1.91kg of spherical alumina and 0.2kg of coupling agent KH-570 are added into 7kg of epoxy resin in preparation example 2, stirring is carried out for 10min at the rotating speed of 600r/min, then 0.76kg of high heat conduction aluminum nitride in preparation example 7, 1.53kg of surface modified boron nitride in preparation example 8 and 1.2kg of maleic anhydride polybutadiene are added, the particle size distribution of the surface modified boron nitride is 2.6 mu m, the surface modified boron nitride with the particle size distribution of 2.6 mu m is sieved by using a 5000-mesh sieve, the sieved part is taken out, and then the sieving is carried out by using a 6000-mesh sieve, the non-sieved part is the surface modified boron nitride with the particle size distribution of 2.6 mu m, so that the weight ratio of the spherical alumina to the high heat conduction aluminum nitride is 5:2: and 4, stirring for 40min in a vacuum environment with the total filling amount of the filler being 60% of that of the epoxy resin, keeping the temperature at 80 ℃, and cooling to obtain the adhesive component.
Example 15
Example 15 differs from example 14 in that: 2.34kg of spherical alumina, 0.93kg of high-heat-conductivity aluminum nitride in preparation example 7 and 0.93kg of surface modified boron nitride in preparation example 8 are added in the step 1 instead, so that the weight ratio of the spherical alumina to the high-heat-conductivity aluminum nitride is 5:2:2, the particle size distribution of the surface modified boron nitride is 2.6 mu m, and the total filling amount of the filler is 60% of that of the epoxy resin.
Example 16
Example 16 differs from example 14 in that: 2.1kg of spherical alumina, 0.84kg of high-heat-conductivity aluminum nitride in preparation example 7 and 1.26kg of surface modified boron nitride in preparation example 8 are added in the step 1 instead, so that the weight ratio of the spherical alumina to the high-heat-conductivity aluminum nitride is 5:2:3, the particle size distribution of the surface modified boron nitride is 2.6 mu m, and the total filling amount of the filler is 60% of that of the epoxy resin.
Example 17
Example 17 differs from example 16 in that: 2.45kg of spherical alumina, 0.98kg of high-heat-conductivity aluminum nitride in preparation example 7 and 1.47kg of surface modified boron nitride in preparation example 8 are added in the step 1 instead, so that the weight ratio of the spherical alumina to the high-heat-conductivity aluminum nitride is 5:2:3, the total filling amount of the filler is 70% of the epoxy resin.
Example 18
Example 18 differs from example 16 in that: 2.8kg of spherical alumina, 1.12kg of high-heat-conductivity aluminum nitride in preparation example 7 and 1.68kg of surface modified boron nitride in preparation example 8 are added in the step 1 instead, so that the weight ratio of the spherical alumina to the high-heat-conductivity aluminum nitride is 5:2:3, the total filling amount of the filler is 80% of that of the epoxy resin.
Example 19
Example 19 differs from example 18 in that: the epoxy resin of preparation 2 added in step 1 was changed to the epoxy resin of preparation 3.
Example 20
Example 20 differs from example 18 in that: the epoxy resin of preparation 2 added in step 1 was changed to the epoxy resin of preparation 4.
Example 21
Example 21 differs from example 20 in that: changing the weight ratio of the adhesive component to the curing agent component in the step 3 into 50:5.
example 22
Example 22 differs from example 20 in that: changing the weight ratio of the adhesive component to the curing agent component in the step 3 into 50:4.
comparative example
Comparative example 1
Comparative example 1 differs from example 1 in that: the spherical alumina in the step 1 is spherical alumina with the particle size distribution of 12 mu m.
Comparative example 2
Comparative example 2 is different from example 1 in that: the spherical alumina in the step 1 is spherical alumina with a particle size distribution of 7 μm.
Comparative example 3
Comparative example 3 is different from example 1 in that: the spherical alumina in the step 1 is spherical alumina with a particle size distribution of 1.5 μm.
Comparative example 4
Comparative example 4 differs from example 13 in that: the high thermal conductivity aluminum nitride of preparation 7 added in step 1 was changed to unmodified aluminum nitride having a particle size distribution of 1.4 μm.
Comparative example 5
Comparative example 5 differs from example 16 in that: the addition amount of the spherical alumina, the high heat conduction aluminum nitride and the surface modified boron nitride in the step 1 is changed to 3.15kg of spherical alumina, 1.26kg of the high heat conduction aluminum nitride and 1.89kg of the surface modified boron nitride in the preparation example 7, so that the weight ratio of the spherical alumina, the high heat conduction aluminum nitride and the surface modified boron nitride is 5:2: and 3, the total filling amount of the filler is 90% of that of the epoxy resin.
Comparative example 6
Comparative example 6 differs from example 16 in that: the addition amount of the spherical alumina, the high heat conduction aluminum nitride and the surface modified boron nitride in the step 1 is changed to 1.75kg of spherical alumina, 0.7kg of the high heat conduction aluminum nitride and 1.05kg of the surface modified boron nitride in the preparation example 7, so that the weight ratio of the spherical alumina, the high heat conduction aluminum nitride and the surface modified boron nitride is 5:2:3, the total filling amount of the filler is 50% of that of the epoxy resin.
Comparative example 7
Comparative example 7 differs from example 20 in that: the epoxy resin of preparation 2 added in step 1 was changed to the epoxy resin of preparation 5.
Comparative example 8
Comparative example 8 differs from example 20 in that: the epoxy resin of preparation 2 added in step 1 was changed to the epoxy resin of preparation 6.
Comparative example 9
Comparative example 9 is different from example 1 in that: no coupling agent KH-570 was added in step 1.
Comparative example 10
Comparative example 10 differs from example 1 in that: no maleinized polybutadiene was added in step 1.
Detection method
1. Thermal conductivity coefficient: GB/T22588-2008 "flash measurement of thermal diffusivity or Heat conductivity", the thermal conductivity of examples 1-22 and comparative examples 1-10 was measured by flash thermal conductivity meter, manufacturer: model of Shimadzu corporation, japan: LFA467HyperFlash.
2. Heat resistance: GB/T40396-2021 method for Dynamic Mechanical Analysis (DMA) of Polymer-based composite glass transition temperature test method glass transition temperatures were measured for examples 1-22 and comparative examples 1-10 using a dynamic mechanical Analyzer, manufacturer: U.S. TA, model: q800.
3. Adhesive properties: GB/T7124-2008 "determination of tensile shear Strength of adhesive", adhesive strength of examples 13-22 and comparative examples 5-8 was determined by an electronic Universal tester, manufacturer: shandong Lugong mechanical Equipment Co., ltd., model: WDW-100.
TABLE 1 Performance test of examples 1-5 and comparative examples 1-3, 9-10
Table 2 performance tests of examples 5-13 and comparative example 4
TABLE 3 Performance test of examples 13-18 and comparative examples 5-6
TABLE 4 Performance test of examples 18-22 and comparative examples 7-8
It can be seen from the combination of examples 1 to 5 and comparative examples 1 to 3 and 9 to 10 and the combination of table 1 that the heat conductive properties of the spherical alumina compounded with different sizes are significantly better than those of the spherical alumina not compounded with different sizes, so that when the spherical alumina compounded with different sizes, the heat conductive properties of the adhesive can be effectively improved, and the ratio of the three kinds of the spherical aluminas having an effect on the heat conductive properties, as well as the reference examples 1 and 9 and 10, when the spherical alumina is modified without adding KH-570, the heat conductive properties and the heat resistant properties of the adhesive are both reduced, and when the maleated polybutadiene is not added, the compatibility between the spherical alumina and the epoxy resin is deteriorated, and the heat conductive properties and the heat resistant properties of the adhesive are both reduced, so that when the ratio in example 5 is adopted, the heat conductive properties and the heat resistant properties are better, in combination.
As can be seen by combining examples 5-13 and comparative example 4 and combining Table 2, the thermal conductivity when the spherical alumina and the high thermal conductivity aluminum nitride are compounded is obviously better than that when the spherical alumina and the high thermal conductivity aluminum nitride are compounded without the two fillers, the spherical alumina and the high thermal conductivity aluminum nitride can both improve the thermal conductivity and the heat resistance of the adhesive, the spherical alumina and the high thermal conductivity aluminum nitride have different particle size and can be compounded to generate the heat conducting channel, and when the spherical alumina, the high thermal conductivity aluminum nitride and the surface modified boron nitride are compounded in different proportions, the spherical alumina, the high thermal conductivity aluminum nitride and the surface modified boron nitride have different thermal conductivity, and when the weight ratio of the spherical alumina, the high thermal conductivity aluminum nitride and the surface modified boron nitride is 5:2, the modified aluminum nitride can be obviously seen through example 13 and comparative example 4, and the modified aluminum nitride has better thermal conductivity and heat resistance, so the performance of example 13 is better.
As can be seen from the combination of examples 13 to 18 and comparative examples 5 to 6 and from table 3, in comparative examples 13 to 16, the heat conductive properties when three kinds of fillers of spherical alumina, highly heat conductive aluminum nitride and surface modified boron nitride are compounded are obviously better than those when two kinds of fillers are compounded, and the heat conductive properties and heat resistance of the adhesive can be improved by the spherical alumina, highly heat conductive aluminum nitride and surface modified boron nitride, and the particle size of the spherical alumina, highly heat conductive aluminum nitride and surface modified boron nitride are different, and the heat conductive channels can be produced by compounding, and when the proportions of the spherical alumina, highly heat conductive aluminum nitride and surface modified boron nitride are compounded in different proportions, the heat conductive properties and heat resistance are all optimal when the weight proportion of the spherical alumina, highly heat conductive aluminum nitride and surface modified boron nitride is 5:2:3, and in comparative examples 16 to 18, the heat conductive properties and heat resistance of the adhesive are all better when the filler is more filled, but relatively, the adhesive bonding properties and heat resistance are also reduced when the filler is too much filled, and the adhesive bonding properties are better when the filler is too low, and the heat conductive properties and heat resistance are not optimal.
As can be seen from the combination of examples 18 to 22 and comparative examples 7 to 8 and from table 4, in the epoxy resin, when the proportions of the p-methylphenyl diglycidyl ether and the bisphenol a diglycidyl ether type epoxy resin are different, the performances of the adhesive are also different, when the p-methylphenyl diglycidyl ether is too small, the filler cannot be sufficiently dispersed in the epoxy resin, so that the thermal conductivity and the thermal conductivity of the adhesive are reduced, and the adhesive performance is also insufficient, when the p-methylphenyl diglycidyl ether is too much, the volumes of the filler and the epoxy resin are too different, the thermal conductivity and the thermal resistance of the filler cannot be fully exerted, and when the bisphenol a diglycidyl ether type epoxy resin is different in weight proportion from the adhesive, the thermal conductivity, the thermal resistance and the adhesive performance of the adhesive are all different, and when the curing agent is too much, the thermal conductivity and the thermal resistance of the adhesive are not sufficiently improved, but the thermal conductivity of the adhesive is not improved, so that the thermal conductivity and the thermal resistance of the adhesive are both reduced, and the best thermal conductivity of the adhesive are considered, and the adhesive performance is combined.
The present embodiment is only for explanation of the present application and is not to be construed as limiting the present application, and modifications to the present embodiment, which may not creatively contribute to the present application as required by those skilled in the art after reading the present specification, are all protected by patent laws within the scope of claims of the present application.
Claims (5)
1. The electronic grade adhesive is characterized by comprising an adhesive component and a curing agent component, wherein the adhesive component comprises the following raw materials in parts by weight: 60-80 parts of epoxy resin, 40-60 parts of filler, 1-2 parts of silane coupling agent and 13-14 parts of maleinized polybutadiene, wherein the filler comprises 16-42 parts of spherical aluminum oxide, the particle size distribution of the spherical aluminum oxide is 12-14 mu m, 6-7 mu m and the mass ratio of 1.5-1.7 mu m is 4-8:1-5:1, a step of;
the filler also comprises 4-18 parts of high-heat-conductivity aluminum nitride, wherein the high-heat-conductivity aluminum nitride is prepared by adopting a silane coupling agent to carry out surface treatment, the particle size distribution of the high-heat-conductivity aluminum nitride is 1.1-1.5 mu m, and the mass ratio of the spherical aluminum oxide to the high-heat-conductivity aluminum nitride is 4-6:1-3;
the filler also comprises 9-24 parts of surface modified boron nitride; the surface modified boron nitride is prepared by adopting a silane coupling agent to carry out surface treatment; the particle size distribution of the surface modified boron nitride is 2.3-2.9 mu m; the silane coupling agent is one or more of KH-570, KH-550 and KH-560;
the mass ratio of the spherical aluminum oxide to the high-heat-conductivity aluminum nitride to the surface modified boron nitride is 4-6:1-3:2-4;
the epoxy resin comprises p-methylphenyl diglycidyl ether and bisphenol A diglycidyl ether type epoxy resin, wherein the mass ratio of the p-methylphenyl diglycidyl ether to the bisphenol A diglycidyl ether type epoxy resin is (6-8): 2-4.
2. The electronic grade adhesive of claim 1, wherein: the preparation of the high-heat-conductivity aluminum nitride comprises the following steps:
step 1: weighing and accurately metering a silane coupling agent, and dissolving the silane coupling agent in absolute ethyl alcohol with the volume being 2-4 times of that of the silane coupling agent to prepare a coupling agent absolute ethyl alcohol solution;
and 2, weighing and adding aluminum nitride with accurate measurement into an absolute ethanol solution of a coupling agent, uniformly stirring, performing ultrasonic dispersion, then heating to 80-85 ℃, refluxing for 30-40min under a nitrogen atmosphere, cooling, centrifuging, and finally drying at 120-130 ℃ for 2-3h to obtain the high-heat-conductivity aluminum nitride.
3. The electronic grade adhesive of claim 1, wherein: the preparation method of the p-methylphenyl diglycidyl ether comprises the following steps:
s1: mixing p-methylaniline and sodium nitrite in the molar ratio of 1-1.2:1-1.1 into distilled water, wherein the volume of the distilled water is 2-3 times that of the mixed p-methylaniline and sodium nitrite, dropwise adding 37% -40% hydrochloric acid and continuously stirring, and the molar ratio of the hydrochloric acid to the sodium nitrite is 1-1.2:1-1.3, adding p-benzoquinone and sodium bicarbonate after the hydrochloric acid dropwise addition is completed, wherein the molar ratio of the p-methylaniline to the p-benzoquinone to the sodium bicarbonate is 1-1.2:1-1.3:1-1.3, continuously stirring for 3-4 hours, performing vacuum filtration, and drying at 70-80 ℃ for 1-2 hours to obtain the p-methylphenyl p-benzoquinone;
s2: p-methylphenyl p-benzoquinone, zinc powder and deionized water are mixed according to the molar ratio of 1:2:10-15, uniformly mixing and stirring, heating to 90-95 ℃ to generate reflux reaction, dropwise adding 37% hydrochloric acid and continuously stirring, wherein the molar ratio of the hydrochloric acid to the zinc powder is 0.9-1.1:1-1.2, continuously carrying out reflux reaction for 3-4 hours after the dripping is finished, continuously stirring, and finally filtering to obtain p-methylphenyl hydroquinone;
s3: adding epoxy chloropropane and tetrabutyl ammonium bromide into the p-methylphenyl hydroquinone, mixing and stirring, wherein the molar ratio of the p-methylphenyl hydroquinone to the epoxy chloropropane to the tetrabutyl ammonium bromide is 1:2-2.5:0.1-0.2, heating to 80-90 ℃, continuously heating for 4-5h, and removing unreacted epichlorohydrin by adopting a reduced pressure distillation method to prepare a pre-product;
s4: toluene and 30% -35% sodium hydroxide solution are added into the pre-product, and the molar ratio of the pre-product, the 30% sodium hydroxide solution and the toluene is as follows: 1:2-2.5:3-4, heating to 80-90 ℃, continuing for 2-3 hours, cooling, washing with deionized water to be neutral, removing toluene and deionized water by a reduced pressure distillation method, and drying at 60-70 ℃ for 4-5 hours to obtain the p-methylphenyl diglycidyl ether.
4. The electronic grade adhesive of claim 1, wherein: the curing agent comprises the following raw materials: 2-methylimidazole and dicyandiamide, wherein the mass ratio of the 2-methylimidazole to the dicyandiamide is 10-11:1-1.5, and the weight ratio of the adhesive component to the curing agent component is 50:3-5.
5. The method for preparing the electronic grade adhesive according to any one of claims 1 to 4, wherein: the method comprises the following steps:
step 1: preparing an adhesive component; meanwhile, preparing a curing agent component, namely uniformly mixing 2-methylimidazole and dicyandiamide which are accurately measured, and stirring for 20-30min to prepare the curing agent component;
step 1.1: mixing and stirring accurately measured p-methylphenyl diglycidyl ether and bisphenol A diglycidyl ether type epoxy resin uniformly, continuously stirring for 20-25min at 80-90 ℃, and vacuumizing to obtain epoxy resin;
step 1.2: firstly adding spherical alumina and a silane coupling agent which are accurately measured, stirring for 5-10min, then adding high-heat-conductivity aluminum nitride, surface modified boron nitride and maleic anhydride polybutadiene which are accurately measured, stirring for 30-45min in a vacuum environment, keeping the temperature at 70-80 ℃, and cooling to obtain an adhesive component;
step 2: and mixing and stirring the adhesive component and the curing agent component uniformly according to the weight ratio for 15-20min to obtain the electronic adhesive.
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