CN107513359A - A kind of preparation method of high thermal conductivity conductive adhesive for high-power LED encapsulation - Google Patents

A kind of preparation method of high thermal conductivity conductive adhesive for high-power LED encapsulation Download PDF

Info

Publication number
CN107513359A
CN107513359A CN201710917074.5A CN201710917074A CN107513359A CN 107513359 A CN107513359 A CN 107513359A CN 201710917074 A CN201710917074 A CN 201710917074A CN 107513359 A CN107513359 A CN 107513359A
Authority
CN
China
Prior art keywords
added
parts
thermal conductivity
functionalization graphene
stirred
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201710917074.5A
Other languages
Chinese (zh)
Inventor
李娜
李峰
贺国新
张利文
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Yantai Seayu New Materials Corp Ltd
Original Assignee
Yantai Seayu New Materials Corp Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Yantai Seayu New Materials Corp Ltd filed Critical Yantai Seayu New Materials Corp Ltd
Priority to CN201710917074.5A priority Critical patent/CN107513359A/en
Publication of CN107513359A publication Critical patent/CN107513359A/en
Pending legal-status Critical Current

Links

Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C09J9/02—Electrically-conducting adhesives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0806—Silver
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The present invention relates to a kind of preparation method of the high thermal conductivity conductive adhesive for high-power LED encapsulation, epoxy resin and toughener part are added sequentially in double-planet power mixing kettle, revolution stirring is opened and high speed is scattered, at a certain temperature, 1h is stirred, adds self-control functionalization graphene material, and conductive silver powder stirring 1h, add latent curing agent, 1h is stirred, adds aerosil, stirs 1h, 1h is kept under a certain pressure, produces one-component high thermal conductivity conductive adhesive adhesive.Synthesis technique of the present invention is simple, and cost is low；And, high temperature resistant high with intensity, the characteristics of lower shrinkage and excellent thermal conductivity.

Description

A kind of preparation method of high thermal conductivity conductive adhesive for high-power LED encapsulation
Technical field
The present invention relates to a kind of preparation method of the high thermal conductivity conductive adhesive for high-power LED encapsulation.
Background technology
In recent years, with the rise of LED industry, LED semiconductor subassemblies also increasingly receive the attention of people, to LED's Energy-saving and environmental protection and life requirements more and more higher therewith.The LED component life-span on the market was only capable of up to 2~30,000 hours at present, but After good heat transfer and heat loss through convection, the LED component life-span was up to 100,000 hours in theory, therefore the low of glue is led Heating rate and poorly conductive have seriously fettered industry development.In order to improve the thermal conductivity of adhesive system, often select Expensive raw material, cause the increase of production cost.
In great power LED industry, the higher heat conductivility of glue requirement and conduction of bonding effect are played in assembling Property, high-termal conductivity and electric conductivity are considered as an important index of the sector by industry, can greatly prolong great power LED use Life-span, and at this stage for the thermal conductivity colloidality energy of great power LED and bad, formed and restrict LED and sent out to high-power and high-luminance The bottleneck of exhibition.
It is used for LED conducting resinls on the market at this stage more using conducting sphere as filler, the used cladding gold of conducting sphere Owner will have gold（Au）, nickel（Ni）, silver（Ag）, gold, silver, the alloy such as tin are plated on nickel.Simple metal filler is led under normal circumstances It is hot typically to be reduced with the rise of temperature, so simple metal filler is infrequently used in the big great power LED glue of quantity of heat production Above glutinous agent.And craft of gilding then has certain drawback at present, environment is polluted, complex process, cost is higher, it is difficult to extensively should With.Due to electronics macromolecule it is different from the spread speed in metal packing and 2 between Presence of an interface and boundary defect (as empty Gap), therefore electronics can produce various scatterings in transmittance process（Such as electron scattering and defect scattering）, so as to produce interface heat Resistance.Obtain the material of high heat conductance, it is necessary to reduce various scatterings as far as possible.And glue of the conducting sphere as conductive fill is used at present The heat conductivility of glutinous agent is simultaneously bad, and by the basal plane defects effect between the surface treatment reduction matrix and filler to filler not It is good, and by improving the content of inorganic filling material to increase the thermal conductivity of finished product be conditional.
In recent years, for carbon material because it has higher thermal conductivity, the common carbon material of concern for causing researcher has graphite (2000W/(m K)), diamond (2300W/ (mK)), carbon black, CNT (CNT) (3000~3500W / (mK)), Nano graphite lamella etc., CNT has excellent heat conductivility, is often applied in LCD and OLED industries The conductive filler of adhesive.But CNT faces many problems in use.Although there are some researches show CNT exists During packing volume f≤7%, thermal conductivity improves 50%~250%.But CNT can not be good with matrix Coupling, its thermal boundary resistance reach 10mK/W, cause thermal conductivity not increase with addition and significantly improve.And carbon nanometer Cost of the pipe in commercial Application is still very high, is extremely difficult to aligning for CNT, so as to effectively improve the heat of material Conductance.
The content of the invention
The technical problem to be solved by the invention is to provide a kind of high thermal conductivity conducting resinl for high-power LED encapsulation The preparation method of glutinous agent, the present invention solve the problem of adhesive low thermal conductivity, electric conductivity difference, and adhesive strength is high, resistance to 100 DEG C of height Temperature, the service life of high power LED device can be greatly prolonged.
In order to solve the above-mentioned technical problem, the present invention uses following technical scheme：
2~10 parts of 30~50 parts of epoxy resin and toughener are added sequentially in double-planet power mixing kettle, revolution is opened and stirs Mix and stir and disperse at a high speed, under the conditions of temperature is 15~30 DEG C, stir 1h, add 5~10 parts of self-control functionalization graphene material, stir 1h is mixed, adds 30~70 parts of conductive silver powder, stirs 30min, adds 5~20 parts of latent curing agent, stirs 1h, adds gas phase 0~2 part of silica, 1h is stirred, open vavuum pump and vacuumize 1h, vacuum pressure is 0.01~0.098MPa, is produced for big The high thermal conductivity conductive adhesive of power LED package；
The revolution speed of agitator is 15~25r/min, and scattered rotating speed is 800~1500r/min at a high speed；
The epoxy resin is 3,4- epoxycyclohexyls formic acid esters, 4,5~7-oxa-bicyclo[4.1.0~1,2~dioctyl phthalate 2-glycidyl One kind or arbitrary proportion in ester, bisphenol A epoxide resin, bisphenol F epoxy resin and phenolic resin it is two or more；
The toughener is nitrile rubber, core-shell tougheners Kane Ace@MX-125, the and of Initialcreate@ICAM~8627 One kind or arbitrary proportion in ring figured woven silk material chemical industry S~2001 it is two or more；
The latent curing agent is the dicyandiamide of Changzhou common calla Resins Corporation, Ai Di sections EH-4360S, EH~4357S, Aginomoto PN~H, aginomoto PN~23 and one kind in Fuji's chemistry 1020 or arbitrary proportion it is two or more；
The aerosil from TS~720 of Cabot Co., Ltd, EH~5, Ying Chuan companies R202 and Ying Chuan companies One kind or arbitrary proportion in A200 it is two or more；
The self-control functionalization graphene material follows the steps below：
1）Prepare crystalline flake graphite alkene solution：The 105.8g concentrated sulfuric acids are added into dry 500ml round-bottomed flasks, are put into 2~8 DEG C of ice In water-bath, 1.25gNaNO is added3With 2.5g crystalline flake graphite alkene, 1h is stirred, obtains solution；
2）1.25g potassium permanganate is added to step 1）In the solution of gained, 2h is stirred in 2~8 DEG C of ice-water baths, is warming up to 30 ~40 DEG C of reaction 4h, are added dropwise deionized water 115ml, are warming up to 98 DEG C and keep, react 30min；
3）0.35L50 DEG C of water and 6.25ml 30% hydrogenperoxide steam generator are sequentially added, to dispersion liquid color by brown stain to be bright Yellow；
4）Filter while hot, precipitation is washed with 0.5~0.75L hydrochloric acid solutions；
5）Dialysis：By step 4）Precipitation after washing loads bag filter, is put into deionized water and dialyses, to the aobvious neutrality of dialyzate；
6）Ultrasonic wave：By step 5）Precipitation 0.26g is added in 100ml deionized waters, and ultrasonic 3h, is produced under 200W power Graphene oxide dispersion；
7）The preparation of functionalization graphene solution：Weigh 2.35g benzidine to be dissolved in 30ml absolute ethyl alcohol, obtain mixed liquor, will Mixed liquor and step 6）Graphene oxide dispersion be added to together in conical flask, temperature be 90 DEG C under conditions of flow back 10h, add 0.5ml hydrazine hydrates and continue the 10h that flows back；
8）Functionalization graphene extracts：Filtered with the polypropylene filter film that aperture is 0.22 μm, filter residue 3 is washed with absolute ethyl alcohol It is secondary, after filter residue and drying, obtain benzidine functionalization graphene.
Preferably, step 2）Middle potassium permanganate feed postition adds for gradation component.
Preferably, step 4）Described in hydrochloric acid solution be hydrochloric acid and distilled water volume ratio 1:10 solution.
Preferably, silver powder particle diameter is 30 microns and the arbitrary proportion of 5 micron grain sizes combines.
Preferably, by 5 parts of 3,4- epoxycyclohexyls formic acid esters, 30 parts of bisphenol A epoxide resin, core-shell tougheners Kane Ace@MX-125:4 parts are added sequentially in double-planet power mixing kettle, open revolution stirring and high speed is scattered, are 25 in temperature Under the conditions of DEG C, 1h is stirred, 8 parts of self-control functionalization graphene material is added, stirs 1h, adds 42.5 parts of conductive silver powder, stirring 30min adds 10 parts of Ai Dike latent curing agents EH-4360S, stirs 1h, adds 0.5 part of aerosil, stirs 1h, Open vavuum pump and vacuumize 1h, vacuum pressure 0.0988MPa, produce the high thermal conductivity conducting resinl for high-power LED encapsulation Glutinous agent；The revolution speed of agitator is 20r/min, and scattered rotating speed is 800r/min at a high speed；
The self-control functionalization graphene material follows the steps below：
1）Prepare crystalline flake graphite alkene solution：The 105.8g concentrated sulfuric acids are added into dry 500ml round-bottomed flasks, are put into 2~8 DEG C of ice In water-bath, 1.25gNaNO is added3With 2.5g crystalline flake graphite alkene, 1h is stirred, obtains solution；
2）1.25g potassium permanganate is divided 5 times and is added to step 1）In the solution of gained, 2h is stirred in 2~8 DEG C of ice-water baths, is risen Temperature is added dropwise deionized water 115ml, is warming up to 98 DEG C and keeps, react 30min to 35 DEG C of reaction 4h；
3）0.35L50 DEG C of water and 6.25ml 30% hydrogenperoxide steam generator are sequentially added, to dispersion liquid color by brown stain to be bright Yellow；
4）Filter while hot, precipitation is washed with 0.6L hydrochloric acid solutions；
5）Dialysis：By step 4）Precipitation after washing loads bag filter, is put into deionized water and dialyses, to the aobvious neutrality of dialyzate；
6）Ultrasonic wave：By step 5）Precipitation 0.26g is added in 100ml deionized waters, and ultrasonic 3h, is produced under 200W power Graphene oxide dispersion；
7）The preparation of functionalization graphene solution：Weigh 2.35g benzidine to be dissolved in 30ml absolute ethyl alcohol, obtain mixed liquor, will Mixed liquor and step 6）Graphene oxide dispersion be added to together in conical flask, temperature be 90 DEG C under conditions of flow back 10h, add 0.5ml hydrazine hydrates and continue the 10h that flows back；
8）Functionalization graphene extracts：Filtered with the polypropylene filter film that aperture is 0.22 μm, filter residue 3 is washed with absolute ethyl alcohol It is secondary, after filter residue and drying, obtain benzidine functionalization graphene.
Invention has following advantageous effects：
1. the present invention is coordinated using benzidine functionalization graphene and micro-silver powder is used as filler, make adhesive system that there is height Thermal conductivity, pass through heat conducting and radiating.And excellent in electric conductivity, benzidine functionalization graphene provides more for system Electron channel and active position.The encapsulation of high power LED device is applicable to, substantially prolongs the service life and light of device Brightness.
2. the characteristics of preparation method of the present invention is to be aoxidized the excellent graphene filler of electrical and thermal conductivity performance, Ran Houyong The grafting of benzidine, make the active group of graphenic surface, it is good with matrix compatibility, therefore can when addition is higher It is dispersed in matrix resin, and double benzene ring structures of structure add the rigid structure of system and resistance to after benzidine grafting Warm nature energy.Make the adhesive that there is good cementability and temperature tolerance.Synthesis process simply easily operates, and cost is low, can Large-scale production.
Embodiment
Embodiment 1
By 5 parts of 3,4- epoxycyclohexyls formic acid esters, 30 parts of bisphenol A epoxide resin, core-shell tougheners Kane Ace@MX-125:4 parts It is added sequentially in double-planet power mixing kettle, opens revolution stirring and high speed is scattered, under the conditions of temperature is 25 DEG C, stirring 1h, 5 parts of self-control functionalization graphene material is added, stirs 1h, add 45.5 parts of conductive silver powder, stirring 30min adds Ai Dike 10 parts of latent curing agent EH-4360S, 1h is stirred, add 0.5 part of aerosil, stir 1h, it is true to open vacuum pumping Empty 1h, vacuum pressure 0.0988MPa, produce the high thermal conductivity conductive adhesive for high-power LED encapsulation, and the revolution is stirred Mix rotating speed is 20r/min, and scattered rotating speed is 800r/min at a high speed.
The self-control functionalization graphene material follows the steps below：
1）Prepare crystalline flake graphite alkene solution：The 105.8g concentrated sulfuric acids are added into dry 500ml round-bottomed flasks, are put into 2~8 DEG C of ice In water-bath, 1.25gNaNO is added3With 2.5g crystalline flake graphite alkene, 1h is stirred, obtains solution；
3）1.25g potassium permanganate is divided 5 times and is added to step 1）In the solution of gained, 2h is stirred in 2~8 DEG C of ice-water baths, is risen Temperature is added dropwise deionized water 115ml, is warming up to 98 DEG C and keeps, react 30min to 35 DEG C of reaction 4h；
3）0.35L50 DEG C of water and 6.25ml 30% hydrogenperoxide steam generator are sequentially added, to dispersion liquid color by brown stain to be bright Yellow；
4）Filter while hot, precipitation is washed with 0.6L hydrochloric acid solutions；
5）Dialysis：By step 4）Precipitation after washing loads bag filter, is put into deionized water and dialyses, to the aobvious neutrality of dialyzate；
6）Ultrasonic wave：By step 5）Precipitation 0.26g is added in 100ml deionized waters, and ultrasonic 3h, is produced under 200W power Graphene oxide dispersion；
7）The preparation of functionalization graphene solution：Weigh 2.35g benzidine to be dissolved in 30ml absolute ethyl alcohol, obtain mixed liquor, will Mixed liquor and step 6）Graphene oxide dispersion be added to together in conical flask, temperature be 90 DEG C under conditions of flow back 10h, add 0.5ml hydrazine hydrates and continue the 10h that flows back；
8）Functionalization graphene extracts：Filtered with the polypropylene filter film that aperture is 0.22 μm, filter residue 3 is washed with absolute ethyl alcohol It is secondary, after filter residue and drying, obtain benzidine functionalization graphene.
Embodiment 2
By 5 parts of 3,4- epoxycyclohexyls formic acid esters, 30 parts of bisphenol A epoxide resin, core-shell tougheners Kane Ace@MX-125:4 parts It is added sequentially in double-planet power mixing kettle, opens revolution stirring and high speed is scattered, under the conditions of temperature is 25 DEG C, stirring 1h, 6 parts of self-control functionalization graphene material is added, stirs 1h, add 44.5 parts of conductive silver powder, stirring 30min adds Ai Dike 10 parts of latent curing agent EH-4360S, 1h is stirred, add 0.5 part of aerosil, stir 1h, it is true to open vacuum pumping Empty 1h, vacuum pressure 0.0988MPa, produce the high thermal conductivity conductive adhesive for high-power LED encapsulation；The revolution is stirred Mix rotating speed is 20r/min, and scattered rotating speed is 800r/min at a high speed.
The self-control functionalization graphene material follows the steps below：
1）Prepare crystalline flake graphite alkene solution：The 105.8g concentrated sulfuric acids are added into dry 500ml round-bottomed flasks, are put into 2~8 DEG C of ice In water-bath, 1.25gNaNO is added3With 2.5g crystalline flake graphite alkene, 1h is stirred, obtains solution；
2）1.25g potassium permanganate is divided 5 times and is added to step 1）In the solution of gained, 2h is stirred in 2~8 DEG C of ice-water baths, is risen Temperature is added dropwise deionized water 115ml, is warming up to 98 DEG C and keeps, react 30min to 35 DEG C of reaction 4h；
3）0.35L50 DEG C of water and 6.25ml 30% hydrogenperoxide steam generator are sequentially added, to dispersion liquid color by brown stain to be bright Yellow；
4）Filter while hot, precipitation is washed with 0.6L hydrochloric acid solutions；
5）Dialysis：By step 4）Precipitation after washing loads bag filter, is put into deionized water and dialyses, to the aobvious neutrality of dialyzate；
6）Ultrasonic wave：By step 5）Precipitation 0.26g is added in 100ml deionized waters, and ultrasonic 3h, is produced under 200W power Graphene oxide dispersion；
7）The preparation of functionalization graphene solution：Weigh 2.35g benzidine to be dissolved in 30ml absolute ethyl alcohol, obtain mixed liquor, will Mixed liquor and step 6）Graphene oxide dispersion be added to together in conical flask, temperature be 90 DEG C under conditions of flow back 10h, add 0.5ml hydrazine hydrates and continue the 10h that flows back；
8）Functionalization graphene extracts：Filtered with the polypropylene filter film that aperture is 0.22 μm, filter residue 3 is washed with absolute ethyl alcohol It is secondary, after filter residue and drying, obtain benzidine functionalization graphene.
Embodiment 3
By 5 parts of 3,4- epoxycyclohexyls formic acid esters, 30 parts of bisphenol A epoxide resin, core-shell tougheners Kane Ace@MX-125:4 Part, it is added sequentially in double-planet power mixing kettle, opens revolution stirring and high speed is scattered, under the conditions of temperature is 25 DEG C, stir 1h is mixed, 7 parts of self-control functionalization graphene material is added, stirs 1h, adds 43.5 parts of conductive silver powder, stirring 30min adds Ai Di 10 parts of section latent curing agent EH-4360S, 1h is stirred, add 0.5 part of aerosil, stir 1h, open vacuum pumping Vacuum 1h, vacuum pressure 0.0988MPa, produce the high thermal conductivity conductive adhesive for high-power LED encapsulation；The revolution Speed of agitator is 20r/min, and scattered rotating speed is 800r/min at a high speed.
The self-control functionalization graphene material follows the steps below：
1）Prepare crystalline flake graphite alkene solution：The 105.8g concentrated sulfuric acids are added into dry 500ml round-bottomed flasks, are put into 2~8 DEG C of ice In water-bath, 1.25gNaNO is added3With 2.5g crystalline flake graphite alkene, 1h is stirred, obtains solution；
2）1.25g potassium permanganate is divided 5 times and is added to step 1）In the solution of gained, 2h is stirred in 2~8 DEG C of ice-water baths, is risen Temperature is added dropwise deionized water 115ml, is warming up to 98 DEG C and keeps, react 30min to 35 DEG C of reaction 4h；
3）0.35L50 DEG C of water and 6.25ml 30% hydrogenperoxide steam generator are sequentially added, to dispersion liquid color by brown stain to be bright Yellow；
4）Filter while hot, precipitation is washed with 0.6L hydrochloric acid solutions；
5）Dialysis：By step 4）Precipitation after washing loads bag filter, is put into deionized water and dialyses, to the aobvious neutrality of dialyzate；
6）Ultrasonic wave：By step 5）Precipitation 0.26g is added in 100ml deionized waters, and ultrasonic 3h, is produced under 200W power Graphene oxide dispersion；
7）The preparation of functionalization graphene solution：Weigh 2.35g benzidine to be dissolved in 30ml absolute ethyl alcohol, obtain mixed liquor, will Mixed liquor and step 6）Graphene oxide dispersion be added to together in conical flask, temperature be 90 DEG C under conditions of flow back 10h, add 0.5ml hydrazine hydrates and continue the 10h that flows back；
8）Functionalization graphene extracts：Filtered with the polypropylene filter film that aperture is 0.22 μm, filter residue 3 is washed with absolute ethyl alcohol It is secondary, after filter residue and drying, obtain benzidine functionalization graphene.
Embodiment 4
By 5 parts of 3,4- epoxycyclohexyls formic acid esters, 30 parts of bisphenol A epoxide resin, core-shell tougheners Kane Ace@MX-125:4 parts It is added sequentially in double-planet power mixing kettle, opens revolution stirring and high speed is scattered, under the conditions of temperature is 25 DEG C, stirring 1h, 8 parts of self-control functionalization graphene material is added, stirs 1h, add 42.5 parts of conductive silver powder, stirring 30min adds Ai Dike 10 parts of latent curing agent EH-4360S, 1h is stirred, add 0.5 part of aerosil, stir 1h, it is true to open vacuum pumping Empty 1h, vacuum pressure 0.0988MPa, produce the high thermal conductivity conductive adhesive for high-power LED encapsulation；The revolution is stirred Mix rotating speed is 20r/min, and scattered rotating speed is 800r/min at a high speed.
The self-control functionalization graphene material follows the steps below：
1）Prepare crystalline flake graphite alkene solution：The 105.8g concentrated sulfuric acids are added into dry 500ml round-bottomed flasks, are put into 2~8 DEG C of ice In water-bath, 1.25gNaNO is added3With 2.5g crystalline flake graphite alkene, 1h is stirred, obtains solution；
2）1.25g potassium permanganate is divided 5 times and is added to step 1）In the solution of gained, 2h is stirred in 2~8 DEG C of ice-water baths, is risen Temperature is added dropwise deionized water 115ml, is warming up to 98 DEG C and keeps, react 30min to 35 DEG C of reaction 4h；
3）0.35L50 DEG C of water and 6.25ml 30% hydrogenperoxide steam generator are sequentially added, to dispersion liquid color by brown stain to be bright Yellow；
4）Filter while hot, precipitation is washed with 0.6L hydrochloric acid solutions；
5）Dialysis：By step 4）Precipitation after washing loads bag filter, is put into deionized water and dialyses, to the aobvious neutrality of dialyzate；
6）Ultrasonic wave：By step 5）Precipitation 0.26g is added in 100ml deionized waters, and ultrasonic 3h, is produced under 200W power Graphene oxide dispersion；
7）The preparation of functionalization graphene solution：Weigh 2.35g benzidine to be dissolved in 30ml absolute ethyl alcohol, obtain mixed liquor, will Mixed liquor and step 6）Graphene oxide dispersion be added to together in conical flask, temperature be 90 DEG C under conditions of flow back 10h, add 0.5ml hydrazine hydrates and continue the 10h that flows back；
8）Functionalization graphene extracts：Filtered with the polypropylene filter film that aperture is 0.22 μm, filter residue 3 is washed with absolute ethyl alcohol It is secondary, after filter residue and drying, obtain benzidine functionalization graphene.
Embodiment 5
By 5 parts of 3,4- epoxycyclohexyls formic acid esters, 30 parts of bisphenol A epoxide resin, core-shell tougheners Kane Ace@MX-125:4 parts It is added sequentially in double-planet power mixing kettle, opens revolution stirring and high speed is scattered, under the conditions of temperature is 25 DEG C, stirring 1h, 41.5 parts of self-control functionalization graphene material is added, stirs 1h, add 50 parts of conductive silver powder, stirring 30min adds Ai Dike 10 parts of latent curing agent EH-4360S, 1h is stirred, add 0.5 part of aerosil, stir 1h, it is true to open vacuum pumping Empty 1h, vacuum pressure 0.0988MPa, produce the high thermal conductivity conductive adhesive for high-power LED encapsulation；The revolution is stirred Mix rotating speed is 20r/min, and scattered rotating speed is 800r/min at a high speed.
The self-control functionalization graphene material follows the steps below：
1）Prepare crystalline flake graphite alkene solution：The 105.8g concentrated sulfuric acids are added into dry 500ml round-bottomed flasks, are put into 2~8 DEG C of ice In water-bath, 1.25gNaNO is added3With 2.5g crystalline flake graphite alkene, 1h is stirred, obtains solution；
2）1.25g potassium permanganate is divided 5 times and is added to step 1）In the solution of gained, 2h is stirred in 2~8 DEG C of ice-water baths, is risen Temperature is added dropwise deionized water 115ml, is warming up to 98 DEG C and keeps, react 30min to 35 DEG C of reaction 4h；
3）0.35L50 DEG C of water and 6.25ml 30% hydrogenperoxide steam generator are sequentially added, to dispersion liquid color by brown stain to be bright Yellow；
4）Filter while hot, precipitation is washed with 0.6L hydrochloric acid solutions；
5）Dialysis：By step 4）Precipitation after washing loads bag filter, is put into deionized water and dialyses, to the aobvious neutrality of dialyzate；
6）Ultrasonic wave：By step 5）Precipitation 0.26g is added in 100ml deionized waters, and ultrasonic 3h, is produced under 200W power Graphene oxide dispersion；
7）The preparation of functionalization graphene solution：Weigh 2.35g benzidine to be dissolved in 30ml absolute ethyl alcohol, obtain mixed liquor, will Mixed liquor and step 6）Graphene oxide dispersion be added to together in conical flask, temperature be 90 DEG C under conditions of flow back 10h, add 0.5ml hydrazine hydrates and continue the 10h that flows back；
8）Functionalization graphene extracts：Filtered with the polypropylene filter film that aperture is 0.22 μm, filter residue 3 is washed with absolute ethyl alcohol It is secondary, after filter residue and drying, obtain benzidine functionalization graphene.
Embodiment 6
By 5 parts of 3,4- epoxycyclohexyls formic acid esters, 30 parts of bisphenol A epoxide resin, core-shell tougheners Kane Ace@MX-125:4 Part, it is added sequentially in double-planet power mixing kettle, opens revolution stirring and high speed is scattered, under the conditions of temperature is 25 DEG C, stir 1h is mixed, 10 parts of self-control functionalization graphene material is added, stirs 1h, adds 40.5 parts of conductive silver powder, stirring 30min adds Ai Di 10 parts of section latent curing agent EH-4360S, 1h is stirred, add 0.5 part of aerosil, stir 1h, open vacuum pumping Vacuum 1h, vacuum pressure are -0.098MPa, produce the high thermal conductivity conductive adhesive for high-power LED encapsulation；The revolution Speed of agitator is 20r/min, and scattered rotating speed is 800r/min at a high speed.
The self-control functionalization graphene material follows the steps below：
1）Prepare crystalline flake graphite alkene solution：The 105.8g concentrated sulfuric acids are added into dry 500ml round-bottomed flasks, are put into 2~8 DEG C of ice In water-bath, 1.25gNaNO is added3With 2.5g crystalline flake graphite alkene, 1h is stirred, obtains solution；
2）1.25g potassium permanganate is divided 5 times and is added to step 1）In the solution of gained, 2h is stirred in 2~8 DEG C of ice-water baths, is risen Temperature is added dropwise deionized water 115ml, is warming up to 98 DEG C and keeps, react 30min to 35 DEG C of reaction 4h；
3）0.35L50 DEG C of water and 6.25ml 30% hydrogenperoxide steam generator are sequentially added, to dispersion liquid color by brown stain to be bright Yellow；
4）Filter while hot, precipitation is washed with 0.6L hydrochloric acid solutions；
5）Dialysis：By step 4）Precipitation after washing loads bag filter, is put into deionized water and dialyses, to the aobvious neutrality of dialyzate；
6）Ultrasonic wave：By step 5）Precipitation 0.26g is added in 100ml deionized waters, and ultrasonic 3h, is produced under 200W power Graphene oxide dispersion；
7）The preparation of functionalization graphene solution：Weigh 2.35g benzidine to be dissolved in 30ml absolute ethyl alcohol, obtain mixed liquor, will Mixed liquor and step 6）Graphene oxide dispersion be added to together in conical flask, temperature be 90 DEG C under conditions of flow back 10h, add 0.5ml hydrazine hydrates and continue the 10h that flows back；
8）Functionalization graphene extracts：Filtered with the polypropylene filter film that aperture is 0.22 μm, filter residue 3 is washed with absolute ethyl alcohol It is secondary, after filter residue and drying, obtain benzidine functionalization graphene.
Embodiment 7
By 40 parts of 3,4- epoxycyclohexyls formic acid esters, core-shell tougheners Kane Ace@MX-125:3 parts, ring figured woven silk material chemical industry S~2001： 1 part is added sequentially in double-planet power mixing kettle, opens revolution stirring and high speed is scattered, under the conditions of temperature is 25 DEG C, stir 1h is mixed, 10 parts of self-control functionalization graphene material is added, stirs 1h, adds 36 parts of conductive silver powder, stirring 30min adds Ai Dike 9.5 parts of latent curing agent EH-4360S, 1h is stirred, add 0.5 part of aerosil, stir 1h, it is true to open vacuum pumping Empty 1h, vacuum pressure are -0.098MPa, produce the high thermal conductivity conductive adhesive for high-power LED encapsulation；The revolution is stirred Mix rotating speed is 20r/min, and scattered rotating speed is 800r/min at a high speed.
The self-control functionalization graphene material follows the steps below：
1）Prepare crystalline flake graphite alkene solution：The 105.8g concentrated sulfuric acids are added into dry 500ml round-bottomed flasks, are put into 2~8 DEG C of ice In water-bath, 1.25gNaNO is added3With 2.5g crystalline flake graphite alkene, 1h is stirred, obtains solution；
2）1.25g potassium permanganate is divided 2 times and is added to step 1）In the solution of gained, 2h is stirred in 2~8 DEG C of ice-water baths, is risen Temperature is added dropwise deionized water 115ml, is warming up to 98 DEG C and keeps, react 30min to 35 DEG C of reaction 4h；
3）0.35L50 DEG C of water and 6.25ml 30% hydrogenperoxide steam generator are sequentially added, to dispersion liquid color by brown stain to be bright Yellow；
4）Filter while hot, precipitation is washed with 0.7L hydrochloric acid solutions；
5）Dialysis：By step 4）Precipitation after washing loads bag filter, is put into deionized water and dialyses, to the aobvious neutrality of dialyzate；
6）Ultrasonic wave：By step 5）Precipitation 0.26g is added in 100ml deionized waters, and ultrasonic 3h, is produced under 200W power Graphene oxide dispersion；
7）The preparation of functionalization graphene solution：Weigh 2.35g benzidine to be dissolved in 30ml absolute ethyl alcohol, obtain mixed liquor, will Mixed liquor and step 6）Graphene oxide dispersion be added to together in conical flask, temperature be 90 DEG C under conditions of flow back 10h, add 0.5ml hydrazine hydrates and continue the 10h that flows back；
8）Functionalization graphene extracts：Filtered with the polypropylene filter film that aperture is 0.22 μm, filter residue 3 is washed with absolute ethyl alcohol It is secondary, after filter residue and drying, obtain benzidine functionalization graphene.
The present invention is further illustrated with reference to instantiation：
Beneficial effects of the present invention are further illustrated with reference to experimental data：
1 materials and methods：
1.1 test site：Yantai Xin You new materials limited company laboratory.
1.2 experiment detections：
1.2.1 tensile-sbear strength：Three groups are taken, the good AL pieces of frosted, gluing area is 12.5cm*20mm, is solidified after overlap joint at 120 DEG C After 30min, shear strength, record data are tested on tensile testing machine.
1.2.2 heatproof is tested：Take three groups, the good AL pieces of frosted, gluing area is 12.5cm*20mm, at 120 DEG C after overlap joint After solidifying 30min, three groups of AL/AL overlap joint exemplars are taken out after 180 DEG C of baking ovens place 30min, heat surveys shear strength at 180 DEG C. Record data.
1.2.3 the test of thermal conductivity：The making of exemplar：120 DEG C solidification 30 exemplars, it is desirable to sample must not have crackle, deformation, Fusion hole, fall the defects of side and gas cell distribution are uneven.Specimen size is that thickness is above and below 10~25mm 0.5 above and below diameter 180mm 0.5 circular specimen.Experiment takes a data every time, when sample puts dry 3h, side thickness under 110~120 degrees Celsius before experiment, A data are surveyed in sample edge every 120 °, take the mean.
Tester：NETZSCH thermal conductivity meters.
1.2.4 resistivity measurement：
1st, sample preparation：Thickness at least 1-3cm sample block will be solidified at 70 DEG C of sample.Make sample surfaces flat as far as possible.
2nd, resistivity tester is opened, probe pen is placed in sample surfaces flat place, holds and keeps stable about 1 second, survey Test result is displayed on screen.If ensuring that probe pen and samples remained stable single absolute value are more than 4mv, testing Before to compensate.
Tester：Resistivity tester
1.3 material to be tested：For embodiment 1, embodiment 2, embodiment 3, embodiment 4, embodiment 5, embodiment 6 and contrast 1 （In addition to self-control functionalization graphene filler is replaced using aluminum oxide, other preparation methods are consistent with embodiment 4）Effect is done to compare.
In addition to experiment process is different, other operations are consistent for this experiment.
2 results and analysis：
Conclusion：From above example test result it is seen that the best results of embodiment 4.

Claims (5)

  1. A kind of 1. preparation method of high thermal conductivity conductive adhesive for high-power LED encapsulation, it is characterised in that：
    2~10 parts of 30~50 parts of epoxy resin and toughener are added sequentially in double-planet power mixing kettle, revolution is opened and stirs Mix and stir and disperse at a high speed, under the conditions of temperature is 15~30 DEG C, stir 1h, add 5~10 parts of self-control functionalization graphene material, stir 1h is mixed, adds 30~70 parts of conductive silver powder, stirs 30min, adds 5~20 parts of latent curing agent, stirs 1h, adds gas phase 0~2 part of silica, 1h is stirred, open vavuum pump and vacuumize 1h, vacuum pressure is 0.01~0.098MPa, is produced for big The high thermal conductivity conductive adhesive of power LED package；
    The revolution speed of agitator is 15~25r/min, and scattered rotating speed is 800~1500r/min at a high speed；
    The epoxy resin is 3,4- epoxycyclohexyls formic acid esters, 4,5~7-oxa-bicyclo[4.1.0~1,2~dioctyl phthalate 2-glycidyl One kind or arbitrary proportion in ester, bisphenol A epoxide resin, bisphenol F epoxy resin and phenolic resin it is two or more；
    The toughener is nitrile rubber, core-shell tougheners Kane Ace@MX-125, the and of Initialcreate@ICAM~8627 One kind or arbitrary proportion in ring figured woven silk material chemical industry S~2001 it is two or more；
    The latent curing agent is the dicyandiamide of Changzhou common calla Resins Corporation, Ai Di sections EH-4360S, EH~4357S, Aginomoto PN~H, aginomoto PN~23 and one kind in Fuji's chemistry 1020 or arbitrary proportion it is two or more；
    The aerosil from TS~720 of Cabot Co., Ltd, EH~5, Ying Chuan companies R202 and Ying Chuan companies One kind or arbitrary proportion in A200 it is two or more；
    The self-control functionalization graphene material follows the steps below：
    1）Prepare crystalline flake graphite alkene solution：The 105.8g concentrated sulfuric acids are added into dry 500ml round-bottomed flasks, are put into 2~8 DEG C of ice In water-bath, 1.25gNaNO is added3With 2.5g crystalline flake graphite alkene, 1h is stirred, obtains solution；
    1.25g potassium permanganate is added to step 1）In the solution of gained, 2h is stirred in 2~8 DEG C of ice-water baths, it is warming up to 30~ 40 DEG C of reaction 4h, are added dropwise deionized water 115ml, are warming up to 98 DEG C and keep, react 30min；
    3）0.35L50 DEG C of water and 6.25ml 30% hydrogenperoxide steam generator are sequentially added, to dispersion liquid color by brown stain to be bright Yellow；
    4）Filter while hot, precipitation is washed with 0.5~0.75L hydrochloric acid solutions；
    5）Dialysis：By step 4）Precipitation after washing loads bag filter, is put into deionized water and dialyses, to the aobvious neutrality of dialyzate；
    6）Ultrasonic wave：By step 5）Precipitation 0.26g is added in 100ml deionized waters, and ultrasonic 3h, is produced under 200W power Graphene oxide dispersion；
    7）The preparation of functionalization graphene solution：Weigh 2.35g benzidine to be dissolved in 30ml absolute ethyl alcohol, obtain mixed liquor, will Mixed liquor and step 6）Graphene oxide dispersion be added to together in conical flask, temperature be 90 DEG C under conditions of flow back 10h, add 0.5ml hydrazine hydrates and continue the 10h that flows back；
    8）Functionalization graphene extracts：Filtered with the polypropylene filter film that aperture is 0.22 μm, filter residue 3 is washed with absolute ethyl alcohol It is secondary, after filter residue and drying, obtain benzidine functionalization graphene.
  2. 2. it is used for the preparation method of the high thermal conductivity conductive adhesive of high-power LED encapsulation, its feature as claimed in claim 1 It is：Step 2）Middle potassium permanganate feed postition adds for gradation component.
  3. 3. it is used for the preparation method of the high thermal conductivity conductive adhesive of high-power LED encapsulation, its feature as claimed in claim 1 It is：Step 4）Described in hydrochloric acid solution be hydrochloric acid and distilled water volume ratio 1:10 solution.
  4. 4. it is used for the preparation method of the high thermal conductivity conductive adhesive of high-power LED encapsulation, its feature as claimed in claim 1 It is：The silver powder particle diameter is 30 microns and the arbitrary proportion combination of 5 micron grain sizes.
  5. 5. it is used for the preparation method of the high thermal conductivity conductive adhesive of high-power LED encapsulation, its feature as claimed in claim 1 It is：By 5 parts of 3,4- epoxycyclohexyls formic acid esters, 30 parts of bisphenol A epoxide resin, core-shell tougheners Kane Ace@MX-125:4 Part is added sequentially in double-planet power mixing kettle, opens revolution stirring and high speed is scattered, under the conditions of temperature is 25 DEG C, stirring 1h, 8 parts of self-control functionalization graphene material is added, stirs 1h, add 42.5 parts of conductive silver powder, stirring 30min adds Ai Dike 10 parts of latent curing agent EH-4360S, 1h is stirred, add 0.5 part of aerosil, stir 1h, it is true to open vacuum pumping Empty 1h, vacuum pressure 0.0988MPa, produce the high thermal conductivity conductive adhesive for high-power LED encapsulation；The revolution Speed of agitator is 20r/min, and scattered rotating speed is 800r/min at a high speed；
    The self-control functionalization graphene material follows the steps below：
    1）Prepare crystalline flake graphite alkene solution：The 105.8g concentrated sulfuric acids are added into dry 500ml round-bottomed flasks, are put into 2~8 DEG C of ice In water-bath, 1.25gNaNO is added3With 2.5g crystalline flake graphite alkene, 1h is stirred, obtains solution；
    1.25g potassium permanganate is divided 5 times and is added to step 1）In the solution of gained, 2h is stirred in 2~8 DEG C of ice-water baths, is heated up To 35 DEG C of reaction 4h, deionized water 115ml is added dropwise, is warming up to 98 DEG C and keeps, reacts 30min；
    3）0.35L50 DEG C of water and 6.25ml 30% hydrogenperoxide steam generator are sequentially added, to dispersion liquid color by brown stain to be bright Yellow；
    4）Filter while hot, precipitation is washed with 0.6L hydrochloric acid solutions；
    5）Dialysis：By step 4）Precipitation after washing loads bag filter, is put into deionized water and dialyses, to the aobvious neutrality of dialyzate；
    6）Ultrasonic wave：By step 5）Precipitation 0.26g is added in 100ml deionized waters, and ultrasonic 3h, is produced under 200W power Graphene oxide dispersion；
    7）The preparation of functionalization graphene solution：Weigh 2.35g benzidine to be dissolved in 30ml absolute ethyl alcohol, obtain mixed liquor, will Mixed liquor and step 6）Graphene oxide dispersion be added to together in conical flask, temperature be 90 DEG C under conditions of flow back 10h, add 0.5ml hydrazine hydrates and continue the 10h that flows back；
    8）Functionalization graphene extracts：Filtered with the polypropylene filter film that aperture is 0.22 μm, filter residue 3 is washed with absolute ethyl alcohol It is secondary, after filter residue and drying, obtain benzidine functionalization graphene.
CN201710917074.5A 2017-09-30 2017-09-30 A kind of preparation method of high thermal conductivity conductive adhesive for high-power LED encapsulation Pending CN107513359A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710917074.5A CN107513359A (en) 2017-09-30 2017-09-30 A kind of preparation method of high thermal conductivity conductive adhesive for high-power LED encapsulation

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710917074.5A CN107513359A (en) 2017-09-30 2017-09-30 A kind of preparation method of high thermal conductivity conductive adhesive for high-power LED encapsulation

Publications (1)

Publication Number Publication Date
CN107513359A true CN107513359A (en) 2017-12-26

Family

ID=60727123

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710917074.5A Pending CN107513359A (en) 2017-09-30 2017-09-30 A kind of preparation method of high thermal conductivity conductive adhesive for high-power LED encapsulation

Country Status (1)

Country Link
CN (1) CN107513359A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110223841A (en) * 2018-03-02 2019-09-10 三星电机株式会社 Multilayer ceramic electronic component
CN111533486A (en) * 2020-04-14 2020-08-14 新疆烯金石墨烯科技有限公司 Graphene modified resin packaging material and preparation method thereof

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104262588A (en) * 2014-09-12 2015-01-07 湖南大学 Graphene oxide-based curing agent as well as preparation and use thereof

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104262588A (en) * 2014-09-12 2015-01-07 湖南大学 Graphene oxide-based curing agent as well as preparation and use thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
付长璟: "《石墨烯的制备、结构及应用》", 30 June 2017, 哈尔滨工业大学出版社 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110223841A (en) * 2018-03-02 2019-09-10 三星电机株式会社 Multilayer ceramic electronic component
US11393629B2 (en) 2018-03-02 2022-07-19 Samsung Electro-Mechanics Co., Ltd. Multilayer ceramic electronic component including an external electrode having a graphene platelet
CN111533486A (en) * 2020-04-14 2020-08-14 新疆烯金石墨烯科技有限公司 Graphene modified resin packaging material and preparation method thereof

Similar Documents

Publication Publication Date Title
Fu et al. Thermal conductivity enhancement with different fillers for epoxy resin adhesives
CN110128792B (en) Thermal interface composite material and preparation method and application thereof
CN106700113B (en) A kind of transparent heating film and preparation method thereof
Zhang et al. A study on the resistivity and mechanical properties of modified nano-Ag coated Cu particles in electrically conductive adhesives
CN107036741B (en) A kind of preparation method of the graphene-based pressure sensor of selfreparing
CN107655598A (en) Flexibility stress sensor based on CNT and nano silver wire composite conductive thin film
WO2017133120A1 (en) Frame sealing adhesive, liquid crystal panel, liquid crystal display and preparation method
CN109135685A (en) A kind of insulating heat-conductive nano material and its preparation and application based on liquid metal
CN102382554A (en) Heat preservation and insulation heavy duty anti-corrosion coating with low thermal conductivity and preparation method thereof
CN107513359A (en) A kind of preparation method of high thermal conductivity conductive adhesive for high-power LED encapsulation
Ekrem et al. Improving electrical and mechanical properties of a conductive nano adhesive
CN105139920B (en) A kind of conductive particle and preparation method thereof, conducting resinl, display device
CN107342117B (en) Anisotropic conductive film and preparation method thereof
CN104993041A (en) LED flip chip die-bonding conductive adhesive structure and mounting method thereof
CN110408083A (en) It is a kind of using bacteria cellulose as high-heat-conductive composite material of matrix and preparation method thereof
WO2021142752A1 (en) Organic silicon resin conductive adhesive, and preparation method therefor and application thereof
CN103642319A (en) Aqueous conductive ink
CN107163710A (en) A kind of graphene fluorine carbon metal paint and preparation method thereof
CN106634862A (en) Thermal conductive gel and preparation method thereof
KR20100088494A (en) Insulating conductive ball for anisotropic conductive film and fabrication method thereof
CN103805118B (en) Compound conductive adhesive for electronic packaging and preparation method thereof
CN102807838A (en) Double-component electric conduction adhesive and preparation method thereof
Duan et al. Modulus matching strategy of ultra-soft electrically conductive silicone composites for high performance electromagnetic interference shielding
CN103666318B (en) A kind of Self-repair conductive adhesive and preparation method thereof
CN107474770A (en) A kind of one pack system high heat conductive insulating structural adhesive and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20171226