CN110126391A - A kind of high thermal conductivity graphene oxide copper-clad plate and preparation method thereof - Google Patents
A kind of high thermal conductivity graphene oxide copper-clad plate and preparation method thereof Download PDFInfo
- Publication number
- CN110126391A CN110126391A CN201910491676.8A CN201910491676A CN110126391A CN 110126391 A CN110126391 A CN 110126391A CN 201910491676 A CN201910491676 A CN 201910491676A CN 110126391 A CN110126391 A CN 110126391A
- Authority
- CN
- China
- Prior art keywords
- parts
- graphene oxide
- thermal conductivity
- high thermal
- clad plate
- 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
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/061—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of metal
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B38/00—Ancillary operations in connection with laminating processes
- B32B38/0004—Cutting, tearing or severing, e.g. bursting; Cutter details
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
-
- 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
- C08G59/18—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
-
- 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
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/02—Composition of the impregnated, bonded or embedded layer
- B32B2260/021—Fibrous or filamentary layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/04—Impregnation, embedding, or binder material
- B32B2260/046—Synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/10—Inorganic fibres
- B32B2262/101—Glass fibres
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
- B32B2307/204—Di-electric
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/302—Conductive
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
Abstract
The invention discloses a kind of high thermal conductivity graphene oxide copper-clad plates and preparation method thereof, the high thermal conductivity graphene oxide copper-clad plate includes that the insulating medium layer between two layers of copper foil layer and two layers of copper foil layer is constituted, the insulating medium layer is by 40~50 parts of epoxy resin, 1.8~3 parts of curing agent dicyandiamide, 30~40 parts of solvent DMF, thermal conducting agent and 5~10 parts of fire retardant graphene oxide, promotor 1,1, the E grade glass cloth of 2~3 parts of 2,2- tetrahydroxy benzene ethane, the four glycidol ether rubber cements prepared and silanization is prepared；The preparation method of the high thermal conductivity graphene oxide copper-clad plate is the following steps are included: raw material preparation, be stirred, glass cloth processing, glass cloth gluing processing, cut-parts lamination, pressing cutting processing.The thermal coefficient of high thermal conductivity graphene oxide copper-clad plate produced by the present invention is improved from original 0.1W/mK to 5.88W/mK, yield strength improves 2.95%, glass transition temperature is also improved from traditional 140 DEG C of epoxy substrate to 170 DEG C, and dielectric loss performance is good in high frequency.
Description
Technical field
Technical field of copper clad laminate of the present invention, especially a kind of high thermal conductivity graphene oxide copper-clad plate and preparation method thereof.
Background technique
Copper-clad plate is using insulating paper, glass fabric or the leaching of other fibrous materials with resin, one or both sides coated with
Copper foil is the basic material for being PCB through a kind of board-like material, referred to as copper-clad laminate made of hot pressing, when it is as more
Laminate produce when also known as core plate.
At this stage with the fast development of microelectronics integrated technology and package technique, the body of electronic component and logic circuit
Product is smaller and smaller, and working frequency sharply increases, and the operating ambient temperature of component is higher and higher, in order to guarantee electronic component
It reliably works normally for a long time, heat-sinking capability just becomes the restraining factors of its service life length, therefore highly thermally conductive polymeric
Based composites are in many manufacturing industry and high-tech such as electrical equipment and electrical, microelectronics, Electronic Packaging, LED encapsulation, Aeronautics and Astronautics
Field plays an important role, and the thermal conductivity of most polymers material is very low, can not be directly used as Heat Conduction Material, so needing
By the way that thermal conductivity material is added, increase its thermal conductivity, graphene due to its excellent thermal coefficient, thermal coefficient and diamond with
And other common thermal conductivity nanoparticles such as carbon nanotube, simultaneous oxidation graphene have insulating properties since its hydridization is destroyed
It can, it is possible to serve as insulating materials nano heat-conductive filler well.So the invention proposes a kind of high thermal conductivity graphenes to cover
Copper sheet and preparation method thereof is studied by adding graphene oxide to improve the heating conduction of conventional epoxy type copper-clad plate.
Summary of the invention
In order to overcome the insufficient defect of conventional epoxy type copper-clad plate thermal conductivity in the prior art, the present invention provides a kind of high lead
Thermal oxide graphene copper-clad plate and preparation method thereof.
The technical solution adopted by the present invention to solve the technical problems is: a kind of high thermal conductivity graphene oxide copper-clad plate and its
Preparation method, the high thermal conductivity graphene oxide copper-clad plate include the dielectric between two layers of copper foil layer and two layers of copper foil layer
Layer constitute, the insulating medium layer by block 1.8~3 parts of 40~50 parts of epoxy resin, curing agent dicyandiamide, solvent DMF 30
5~10 parts of~40 parts, thermal conducting agent and fire retardant graphene oxide, four glycidol ether of promotor 1,1,2,2- tetrahydroxy benzene ethane
The E grade glass cloth of 2~3 parts of rubber cements prepared and silanization is prepared；The system of the high thermal conductivity graphene oxide copper-clad plate
Preparation Method the following steps are included:
Raw material preparation: step 1 weighs 1.8~3 parts of 40~50 parts of epoxy resin, curing agent dicyandiamide, the solvent of sealing end
5~10 parts of DMF30~40 part, thermal conducting agent and fire retardant graphene oxide, promotor 1,1,2,2- tetrahydroxy benzene ethane four shrink
2~3 parts of glycerin ether spare；
Step 2 is stirred: the above-mentioned epoxy resin blocked and appropriate curing agent dicyandiamide, solvent DMF, thermally conductive
Agent and fire retardant graphene oxide, four glycidol ether material of promotor 1,1,2,2- tetrahydroxy benzene ethane are added in stirred tank and mix
Close uniformly stand-by at rubber cement, 30~40min of mixing time, 25~40 DEG C of whipping temp, 800~1200r/min of mixing speed；
Glass cloth processing: the E grade glass cloth of model 1080 is carried out silanization treatment by step 3；
Step 4, glass cloth gluing processing: at the resulting uniformly mixed rubber cement impregnation silanization of above-mentioned steps two
The E grade glass cloth of reason is impregnated with 30~60min of time, is later arranged in impregnation in 90~100 DEG C of drying unit and toasts
2~4h；
Cut-parts lamination: step 4 resulting impregnation piece is carried out cut-parts processing according to regulation size, later by 2 by step 5
~6 impregnation pieces cut out carry out lamination processing；
Pressing cutting processing: step 6 is pressed, when pressing after certain thickness copper foil is mixed on the good two sides of lamination
Temperature be 200 DEG C, pressure 4.9MPa, 90~120min of time, taken out after pressing is good, after temperature drops to room temperature by
Defined requirement cuts in blocks.
Above-mentioned a kind of high thermal conductivity graphene oxide copper-clad plate and preparation method thereof, the ring of the epoxy resin after the sealing end
Oxygen equivalent is 420~430g/Eq.
Above-mentioned a kind of high thermal conductivity graphene oxide copper-clad plate and preparation method thereof, the solvent DMF are to pass through anhydrous nothing
Anhydrous and oxygen-free grade DMF prepared by oxygen equipment.
Above-mentioned a kind of high thermal conductivity graphene oxide copper-clad plate and preparation method thereof, individual copper foil described in the step 6
With a thickness of 20~100um.
Above-mentioned a kind of high thermal conductivity graphene oxide copper-clad plate and preparation method thereof, what the cut-parts in the step 5 were handled
Torn size in size and step 6 carries out cutting processing according to specific practical application request.
Above-mentioned a kind of high thermal conductivity graphene oxide copper-clad plate and preparation method thereof, the thermal conducting agent and fire retardant aoxidize stone
The preparation process of black alkene are as follows: under the protection of inert gas, the 250mL reaction flask of clean dried is taken to be placed in ice-water bath, be added
After the appropriate concentrated sulfuric acid, while being stirred, 2g graphite powder and 1g sodium nitrate solid is successively added, then 6g Gao Meng is added by several times
Sour potassium is warming up to 35~40 DEG C after stirring 30~60min under conditions of temperature is lower than 20 DEG C, continues to stir 30min, slowly
Appropriate amount of deionized water is added, stirs 20~30min, the hydrogen peroxide of 0.5~2mL is added to restore remaining oxidant, gained is molten
Liquid is glassy yellow, is filtered while hot, and successively repetitive cycling is washed using 5% HCl solution and deionized water, until without sulphur in filtrate
Until acid ion is detected, gained after washing is then obtained into filter cake and is placed in flask, the ultrasound of 60~90min is then passed through
Processing obtains graphene oxide.
Compared with prior art, the present invention has following helpfulness technical effect:
The invention proposes a kind of high thermal conductivity graphene oxide copper-clad plate and preparation method thereof, obtained high thermal conductivity oxidation
The thermal coefficient of graphene copper-clad plate is improved from original 0.1W/mK to 5.88W/mK, and heating conduction is greatly mentioned
Height, yield strength improve 2.95%, and glass transition temperature is also improved from traditional 140 DEG C of epoxy substrate to 170 DEG C, and product
In high frequency, dielectric loss performance is good.
Specific embodiment
Technical solution in order to enable those skilled in the art to better understand the present invention, With reference to embodiment to this
Invention elaborates.
[embodiment 1]
A kind of high thermal conductivity graphene oxide copper-clad plate and preparation method thereof, the high thermal conductivity graphene oxide copper-clad plate includes
Insulating medium layer between two layers of copper foil layer and two layers of copper foil layer is constituted, and the insulating medium layer is by the epoxy resin 40 that blocks
Part, 1.8 parts of curing agent dicyandiamide, 30 parts of solvent DMF, thermal conducting agent and 5 parts of fire retardant graphene oxide, promotor 1,1,2,2- tetra-
The E grade glass cloth of 2 parts of four glycidol ether of the hydroxy phenyl ethane rubber cements prepared and silanization is prepared；The high thermal conductivity oxygen
The preparation method of graphite alkene copper-clad plate the following steps are included:
Step 1, raw material preparation: weigh 1.8 parts of 40 parts of epoxy resin, the curing agent dicyandiamide of sealing end, 30 parts of solvent DMF,
5 parts of thermal conducting agent and fire retardant graphene oxide, 2 parts of four glycidol ethers of promotor 1,1,2,2- tetrahydroxy benzene ethane it is spare；
Step 2 is stirred: the above-mentioned epoxy resin blocked and appropriate curing agent dicyandiamide, solvent DMF, thermally conductive
Agent and fire retardant graphene oxide, four glycidol ether material of promotor 1,1,2,2- tetrahydroxy benzene ethane are added in stirred tank and mix
Close uniformly stand-by at rubber cement, mixing time 40min, 25 DEG C of whipping temp, mixing speed 800r/min；
Glass cloth processing: the E grade glass cloth of model 1080 is carried out silanization treatment by step 3；
Step 4, glass cloth gluing processing: at the resulting uniformly mixed rubber cement impregnation silanization of above-mentioned steps two
The E grade glass cloth of reason is impregnated with time 30min, is later arranged in impregnation in 90 DEG C of drying unit and carries out baking 4h；
Cut-parts lamination: step 4 resulting impregnation piece is carried out cut-parts processing according to regulation size, later by 3 by step 5
It opens the impregnation piece cut out and carries out lamination processing；
Pressing cutting processing: step 6 is pressed, when pressing after certain thickness copper foil is mixed on the good two sides of lamination
Temperature be 200 DEG C, pressure 4.9MPa, time 90min, taken out after pressing is good, by regulation after temperature drops to room temperature
Requirement cut it is in blocks.
Further, the epoxide equivalent of the epoxy resin after the sealing end is 420g/Eq.
Further, the solvent DMF is the anhydrous and oxygen-free grade DMF prepared by anhydrous and oxygen-free equipment.
Further, individual copper foil described in the step 6 with a thickness of 20um.
Further, the preparation process of the thermal conducting agent and fire retardant graphene oxide are as follows: under the protection of inert gas,
Take the 250mL reaction flask of clean dried to be placed in ice-water bath, be added after the appropriate concentrated sulfuric acid, while being stirred, successively plus
Enter 2g graphite powder and 1g sodium nitrate solid, then 6g potassium permanganate is added by several times, under conditions of temperature is lower than 20 DEG C, stirring
It is warming up to 40 DEG C after 30min, continues to stir 30min, is slowly added to appropriate amount of deionized water, stir 20min, the double of 0.5mL are added
For oxygen water to restore remaining oxidant, acquired solution is glassy yellow, is filtered while hot, and successively repetitive cycling uses 5% HCl solution
It is washed with deionized water, until sulfate radical-free ion is detected in filtrate, gained after washing is then obtained into filter cake and is placed in
In flask, graphene oxide then is obtained by the ultrasonic treatment of 60min.
[embodiment 2]
A kind of high thermal conductivity graphene oxide copper-clad plate and preparation method thereof, the high thermal conductivity graphene oxide copper-clad plate includes
Insulating medium layer between two layers of copper foil layer and two layers of copper foil layer is constituted, and the insulating medium layer is by the epoxy resin 45 that blocks
Part, 2.4 parts of curing agent dicyandiamide, 35 parts of solvent DMF, thermal conducting agent and 7 parts of fire retardant graphene oxide, promotor 1,1,2,2- tetra-
The E grade glass cloth of 2.5 parts of four glycidol ether of the hydroxy phenyl ethane rubber cements prepared and silanization is prepared；The high thermal conductivity
The preparation method of graphene oxide copper-clad plate the following steps are included:
Step 1, raw material preparation: weigh 2.4 parts of 45 parts of epoxy resin, the curing agent dicyandiamide of sealing end, 35 parts of solvent DMF,
7 parts of thermal conducting agent and fire retardant graphene oxide, 2.5 parts of four glycidol ethers of promotor 1,1,2,2- tetrahydroxy benzene ethane it is spare；
Step 2 is stirred: the above-mentioned epoxy resin blocked and appropriate curing agent dicyandiamide, solvent DMF, thermally conductive
Agent and fire retardant graphene oxide, four glycidol ether material of promotor 1,1,2,2- tetrahydroxy benzene ethane are added in stirred tank and mix
Close uniformly stand-by at rubber cement, mixing time 35min, 32 DEG C of whipping temp, mixing speed 1000r/min；
Glass cloth processing: the E grade glass cloth of model 1080 is carried out silanization treatment by step 3；
Step 4, glass cloth gluing processing: at the resulting uniformly mixed rubber cement impregnation silanization of above-mentioned steps two
The E grade glass cloth of reason is impregnated with time 40min, is later arranged in impregnation in 95 DEG C of drying unit and carries out baking 3h；
Cut-parts lamination: step 4 resulting impregnation piece is carried out cut-parts processing according to regulation size, later by 2 by step 5
~6 impregnation pieces cut out carry out lamination processing；
Pressing cutting processing: step 6 is pressed, when pressing after certain thickness copper foil is mixed on the good two sides of lamination
Temperature be 200 DEG C, pressure 4.9MPa, time 100min, taken out after pressing is good, by regulation after temperature drops to room temperature
Requirement cut it is in blocks.
Further, the epoxide equivalent of the epoxy resin after the sealing end is 425g/Eq.
Further, the solvent DMF is the anhydrous and oxygen-free grade DMF prepared by anhydrous and oxygen-free equipment.
Further, individual copper foil described in the step 6 with a thickness of 60um.
Further, the preparation process of the thermal conducting agent and fire retardant graphene oxide are as follows: under the protection of inert gas,
Take the 250mL reaction flask of clean dried to be placed in ice-water bath, be added after the appropriate concentrated sulfuric acid, while being stirred, successively plus
Enter 2g graphite powder and 1g sodium nitrate solid, then 6g potassium permanganate is added by several times, under conditions of temperature is lower than 20 DEG C, stirring
It is warming up to 38 DEG C after 40min, continues to stir 30min, is slowly added to appropriate amount of deionized water, stir 25min, the double of 1.0mL are added
For oxygen water to restore remaining oxidant, acquired solution is glassy yellow, is filtered while hot, and successively repetitive cycling uses 5% HCl solution
It is washed with deionized water, until sulfate radical-free ion is detected in filtrate, gained after washing is then obtained into filter cake and is placed in
In flask, graphene oxide then is obtained by the ultrasonic treatment of 75min.
[embodiment 3]
A kind of high thermal conductivity graphene oxide copper-clad plate and preparation method thereof, the high thermal conductivity graphene oxide copper-clad plate includes
Insulating medium layer between two layers of copper foil layer and two layers of copper foil layer is constituted, and the insulating medium layer is by the epoxy resin 50 that blocks
Part, 3 parts of curing agent dicyandiamide, 40 parts of solvent DMF, thermal conducting agent and 10 parts of fire retardant graphene oxide, promotor 1,1,2,2- tetra-
The E grade glass cloth of 3 parts of four glycidol ether of the hydroxy phenyl ethane rubber cements prepared and silanization is prepared；The high thermal conductivity oxygen
The preparation method of graphite alkene copper-clad plate the following steps are included:
Raw material preparation: step 1 weighs 3 parts of 50 parts of epoxy resin, the curing agent dicyandiamide of sealing end, 40 parts of solvent DMF, leads
10 parts of thermit powder and fire retardant graphene oxide, 3 parts of four glycidol ethers of promotor 1,1,2,2- tetrahydroxy benzene ethane it is spare；
Step 2 is stirred: the above-mentioned epoxy resin blocked and appropriate curing agent dicyandiamide, solvent DMF, thermally conductive
Agent and fire retardant graphene oxide, four glycidol ether material of promotor 1,1,2,2- tetrahydroxy benzene ethane are added in stirred tank and mix
Close uniformly stand-by at rubber cement, mixing time 40min, 25 DEG C of whipping temp, mixing speed 1200r/min；
Glass cloth processing: the E grade glass cloth of model 1080 is carried out silanization treatment by step 3；
Step 4, glass cloth gluing processing: at the resulting uniformly mixed rubber cement impregnation silanization of above-mentioned steps two
The E grade glass cloth of reason is impregnated with time 30min, is later arranged in impregnation in 100 DEG C of drying unit and carries out baking 2h；
Cut-parts lamination: step 4 resulting impregnation piece is carried out cut-parts processing according to regulation size, later by 2 by step 5
~6 impregnation pieces cut out carry out lamination processing；
Pressing cutting processing: step 6 is pressed, when pressing after certain thickness copper foil is mixed on the good two sides of lamination
Temperature be 200 DEG C, pressure 4.9MPa, time 120min, taken out after pressing is good, by regulation after temperature drops to room temperature
Requirement cut it is in blocks.
Further, the epoxide equivalent of the epoxy resin after the sealing end is 430g/Eq.
Further, the solvent DMF is the anhydrous and oxygen-free grade DMF prepared by anhydrous and oxygen-free equipment.
Further, individual copper foil described in the step 6 with a thickness of 100um.
Further, the preparation process of the thermal conducting agent and fire retardant graphene oxide are as follows: under the protection of inert gas,
Take the 250mL reaction flask of clean dried to be placed in ice-water bath, be added after the appropriate concentrated sulfuric acid, while being stirred, successively plus
Enter 2g graphite powder and 1g sodium nitrate solid, then 6g potassium permanganate is added by several times, under conditions of temperature is lower than 20 DEG C, stirring
It is warming up to 35 DEG C after 60min, continues to stir 30min, is slowly added to appropriate amount of deionized water, stir 30min, the double of 1.8mL are added
For oxygen water to restore remaining oxidant, acquired solution is glassy yellow, is filtered while hot, and successively repetitive cycling uses 5% HCl solution
It is washed with deionized water, until sulfate radical-free ion is detected in filtrate, gained after washing is then obtained into filter cake and is placed in
In flask, graphene oxide then is obtained by the ultrasonic treatment of 60~90min.
The heat conductive flame-retarding mechanism of the graphene oxide are as follows: there are when the temperature difference between the object contacted with each other, heat can be from
The high part of temperature is shifted to the low part of temperature, finally reaches that temperature is consistent, and in the thermally conductive main logical of solid interior
The thermally conductive carrier such as photon, electronics, phonon is crossed to complete, and metal material and the thermal conduction mechanism of nonmetallic materials are entirely different, by
Contain a large amount of free electron in metal inside, it is thermally conductive that thermally conductive, phonon is mainly completed by the collision between free electron
Effect it is very little, and nonmetallic materials are different, and internal free electron is few, and heat transfer mainly passes through the vibration of lattice phonon
It is dynamic to carry out transmitting heat, add appropriate thermal conducting agent graphene oxide in nonmetallic materials, thermal conducting agent particle and lattice phonon that
This, which contacts with each other, forms thermally conductive chain or thermal conductive network, so that substrate heating conduction be promoted to obtain biggish improvement, corresponding high score
Sub- thermal conductivity of material improves, and has active influence to its flame retardant property, when the surface of heat transfer to polymer material,
Heat can be transmitted to quickly elsewhere by higher thermal conductivity, part or surface temperature be reduced, thus in certain journey
It is set to have fire-retardant effect on degree.
Above embodiments are only exemplary embodiment of the present invention, are not used in the limitation present invention, protection scope of the present invention
It is defined by the claims.Those skilled in the art can within the spirit and scope of the present invention make respectively the present invention
Kind modification or equivalent replacement, this modification or equivalent replacement also should be regarded as being within the scope of the present invention.
Claims (4)
1. a kind of high thermal conductivity graphene oxide copper-clad plate and preparation method thereof, it is characterised in that: the high thermal conductivity graphene oxide
Copper-clad plate includes that insulating medium layer between two layers of copper foil layer and two layers of copper foil layer is constituted, and the insulating medium layer is by blocking
40~50 parts of epoxy resin, 1.8~3 parts of curing agent dicyandiamide, 30~40 parts of solvent DMF, thermal conducting agent and fire retardant graphite oxide
The E of 5~10 parts of alkene, 2~3 parts of four glycidol ethers of the promotor 1,1,2,2- tetrahydroxy benzene ethane rubber cements prepared and silanization
Grade glass cloth is prepared；The preparation method of the high thermal conductivity graphene oxide copper-clad plate the following steps are included:
Raw material preparation: step 1 weighs 1.8~3 parts of 40~50 parts of epoxy resin, curing agent dicyandiamide, the solvent DMF 30 of sealing end
5~10 parts of~40 parts, thermal conducting agent and fire retardant graphene oxide, four glycidol ether of promotor 1,1,2,2- tetrahydroxy benzene ethane
2~3 parts spare；
Step 2 is stirred: the above-mentioned epoxy resin blocked and appropriate curing agent dicyandiamide, solvent DMF, thermal conducting agent is simultaneous
It is equal that mixing in stirred tank is added in fire retardant graphene oxide, four glycidol ether material of promotor 1,1,2,2- tetrahydroxy benzene ethane
It is even stand-by at rubber cement, 30~40min of mixing time, 25~40 DEG C of whipping temp, 800~1200r/min of mixing speed；
Glass cloth processing: the E grade glass cloth of model 1080 is carried out silanization treatment by step 3；
Glass cloth gluing processing: step 4 uses the E of the resulting uniformly mixed rubber cement impregnation silanization treatment of above-mentioned steps two
Grade glass cloth, be impregnated with 30~60min of time, impregnation is arranged in later in 90~100 DEG C of drying unit carry out baking 2~
4h；
Cut-parts lamination: step 4 resulting impregnation piece is carried out cut-parts processing according to regulation size, later by 2~6 by step 5
The impregnation piece cut out carries out lamination processing；
Pressing cutting processing: step 6 is pressed, temperature when pressing after certain thickness copper foil is mixed on the good two sides of lamination
Degree is 200 DEG C, pressure 4.9MPa, 90~120min of time, is taken out after pressing is good, by regulation after temperature drops to room temperature
Requirement cut it is in blocks.
2. a kind of high thermal conductivity graphene oxide copper-clad plate according to claim 1 and preparation method thereof, which is characterized in that institute
The epoxide equivalent of epoxy resin after stating sealing end is 420~430g/Eq.
3. a kind of high thermal conductivity graphene oxide copper-clad plate according to claim 1 and preparation method thereof, which is characterized in that institute
Stating solvent DMF is the anhydrous and oxygen-free grade DMF prepared by anhydrous and oxygen-free equipment.
4. a kind of high thermal conductivity graphene oxide copper-clad plate according to claim 1 and preparation method thereof, which is characterized in that institute
State individual copper foil described in step 6 with a thickness of 20~100um.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910491676.8A CN110126391A (en) | 2019-06-06 | 2019-06-06 | A kind of high thermal conductivity graphene oxide copper-clad plate and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910491676.8A CN110126391A (en) | 2019-06-06 | 2019-06-06 | A kind of high thermal conductivity graphene oxide copper-clad plate and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110126391A true CN110126391A (en) | 2019-08-16 |
Family
ID=67580612
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910491676.8A Pending CN110126391A (en) | 2019-06-06 | 2019-06-06 | A kind of high thermal conductivity graphene oxide copper-clad plate and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110126391A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110804278A (en) * | 2019-11-15 | 2020-02-18 | 昆山兆科电子材料有限公司 | Preparation method of heat-conducting insulating epoxy film and application of heat-conducting insulating epoxy film to flexible aluminum-based copper-clad plate |
| CN113667196A (en) * | 2021-07-28 | 2021-11-19 | 江门市宏儒电子科技有限公司 | Epoxy type copper-clad plate base material and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105001597A (en) * | 2015-08-12 | 2015-10-28 | 哈尔滨理工大学 | Needle-shaped nanometer aluminium oxide/graphene oxide/epoxy resin composite and preparation method |
| CN105062002A (en) * | 2015-08-12 | 2015-11-18 | 哈尔滨理工大学 | Three-phase composited epoxy resin nanocomposite material and preparation method |
| CN105838028A (en) * | 2016-03-25 | 2016-08-10 | 金安国纪科技（杭州）有限公司 | High-heat-conductive resin composition and preparation method thereof |
| CN109111694A (en) * | 2018-07-06 | 2019-01-01 | 黄河科技学院 | The production and stress measuring method of glass fiber reinforced epoxy resin plate |
-
2019
- 2019-06-06 CN CN201910491676.8A patent/CN110126391A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105001597A (en) * | 2015-08-12 | 2015-10-28 | 哈尔滨理工大学 | Needle-shaped nanometer aluminium oxide/graphene oxide/epoxy resin composite and preparation method |
| CN105062002A (en) * | 2015-08-12 | 2015-11-18 | 哈尔滨理工大学 | Three-phase composited epoxy resin nanocomposite material and preparation method |
| CN105838028A (en) * | 2016-03-25 | 2016-08-10 | 金安国纪科技（杭州）有限公司 | High-heat-conductive resin composition and preparation method thereof |
| CN109111694A (en) * | 2018-07-06 | 2019-01-01 | 黄河科技学院 | The production and stress measuring method of glass fiber reinforced epoxy resin plate |
Non-Patent Citations (1)
| Title |
|---|
| 陈冠刚: "一种添加氧化石墨烯的高导热环氧型覆铜板", 《印刷电路信息》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110804278A (en) * | 2019-11-15 | 2020-02-18 | 昆山兆科电子材料有限公司 | Preparation method of heat-conducting insulating epoxy film and application of heat-conducting insulating epoxy film to flexible aluminum-based copper-clad plate |
| CN113667196A (en) * | 2021-07-28 | 2021-11-19 | 江门市宏儒电子科技有限公司 | Epoxy type copper-clad plate base material and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2016078432A1 (en) | Modified aluminium oxide composite material, copper-coated substrate and preparation method thereof | |
| Ge et al. | Effect of hexagonal boron nitride on the thermal and dielectric properties of polyphenylene ether resin for high-frequency copper clad laminates | |
| TW200846398A (en) | Prepreg, multilayer printed wiring board and electronic parts using same | |
| JP5040092B2 (en) | Low dielectric loss tangent resin varnish with excellent stability and wiring board material using the same | |
| CN110126391A (en) | A kind of high thermal conductivity graphene oxide copper-clad plate and preparation method thereof | |
| WO2015180206A1 (en) | Thermoset resin sandwiched pre-preg body, manufacturing method and copper clad plate | |
| JP4277123B2 (en) | Resin composition for printed wiring board, prepreg, laminated board, and printed wiring board using the same | |
| JP2003532747A (en) | Low viscosity acrylate monomers, formulations containing them and uses thereof | |
| JPH05182518A (en) | Low dielectric-constant composite laminate filled with molecular porous aerogel | |
| CN104497357B (en) | Hybrid particulates and preparation method thereof, insulating composite material | |
| CN103965624A (en) | Halogen-free resin composition, and prepreg and laminated board prepared from same | |
| CN106280469A (en) | The high-fire-resistance thermostable heat-conductive silicon rubber thermal interface material of a kind of LED and preparation method | |
| CN114836004B (en) | Heat-conducting and insulating epoxy resin composite material and preparation method and application thereof | |
| CN110258170A (en) | A kind of Nano silver grain modification hexagonal boron nitride/aramid nano-fiber heat-conductive composite material preparation method | |
| CN114591580A (en) | Fluorine-containing resin mixture, prepreg and high-heat-conductivity high-frequency copper-clad plate | |
| CN106280468A (en) | A kind of LED porous carbon microsphere/paraffin composite heat-conducting silicon rubber thermal interface material and preparation method | |
| CN106189243A (en) | The high abrasion heat-conducting silicon rubber thermal interfacial material of a kind of poly-Dopamine modification and preparation method | |
| CN106221227A (en) | A kind of LED high-performance heat-conducting silicon rubber thermal interfacial material and preparation method | |
| CN112175354A (en) | Heat-resistant epoxy resin composition, lead-free high-Tg copper-clad plate and preparation method thereof | |
| CN106471056B (en) | Varnish containing epoxy resin, the varnish containing composition epoxy resin, prepreg, resin sheet, plywood, printed circuit board, semiconductor device | |
| CN106243727A (en) | A kind of LED is acidified carbon nano tube modified high thermal conductive silicon rubber thermal interfacial material and preparation method | |
| KR20010100797A (en) | Radiation curing resin composition, producing method thereof, and product using it | |
| CN115125634B (en) | Method for preparing high-thermal-conductivity electromagnetic shielding polyarylether composite fiber based on electrostatic spinning technology, polyarylether composite material and application | |
| CN112272450B (en) | High-heat-conductivity composite PCB substrate and preparation method thereof | |
| CN109504020A (en) | A kind of flame-resistant electronic composite substrate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| 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: 20190816 |