CN109852294A - A kind of copper-clad plate mixed type heat-conducting glue and its manufacturing method - Google Patents
A kind of copper-clad plate mixed type heat-conducting glue and its manufacturing method Download PDFInfo
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- CN109852294A CN109852294A CN201910077192.9A CN201910077192A CN109852294A CN 109852294 A CN109852294 A CN 109852294A CN 201910077192 A CN201910077192 A CN 201910077192A CN 109852294 A CN109852294 A CN 109852294A
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- conducting glue
- type heat
- copper
- mixed type
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- 239000003292 glue Substances 0.000 title claims abstract description 55
- 238000004519 manufacturing process Methods 0.000 title abstract description 6
- -1 polyethylene terephthalate Polymers 0.000 claims abstract description 35
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 25
- 229920005989 resin Polymers 0.000 claims abstract description 24
- 239000011347 resin Substances 0.000 claims abstract description 24
- 229920005549 butyl rubber Polymers 0.000 claims abstract description 20
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 18
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 17
- 239000003960 organic solvent Substances 0.000 claims abstract description 16
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 14
- 239000004917 carbon fiber Substances 0.000 claims abstract description 14
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000004642 Polyimide Substances 0.000 claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 12
- 239000011521 glass Substances 0.000 claims abstract description 12
- 229920001721 polyimide Polymers 0.000 claims abstract description 12
- 229920000139 polyethylene terephthalate Polymers 0.000 claims abstract description 11
- 239000005020 polyethylene terephthalate Substances 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 229920002050 silicone resin Polymers 0.000 claims abstract description 11
- NCWQJOGVLLNWEO-UHFFFAOYSA-N methylsilicon Chemical compound [Si]C NCWQJOGVLLNWEO-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 8
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims description 32
- 238000003756 stirring Methods 0.000 claims description 25
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 16
- 229920002480 polybenzimidazole Polymers 0.000 claims description 15
- 238000002360 preparation method Methods 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 14
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 12
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 10
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 10
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 8
- 239000012046 mixed solvent Substances 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 5
- 235000019260 propionic acid Nutrition 0.000 claims description 5
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 5
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 5
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 4
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 4
- 229960001124 trientine Drugs 0.000 claims description 4
- 239000000835 fiber Substances 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 229910017435 S2 In Inorganic materials 0.000 claims 1
- 150000003851 azoles Chemical class 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 229920006389 polyphenyl polymer Polymers 0.000 claims 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 23
- 238000001723 curing Methods 0.000 description 15
- 239000000463 material Substances 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 6
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 230000017525 heat dissipation Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- IZOFRDJGAYUGTP-UHFFFAOYSA-N 3-(3,5-ditert-butyl-2-hydroxyphenyl)-n'-[3-(3,5-ditert-butyl-2-hydroxyphenyl)propanoyl]propanehydrazide Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC(CCC(=O)NNC(=O)CCC=2C(=C(C=C(C=2)C(C)(C)C)C(C)(C)C)O)=C1O IZOFRDJGAYUGTP-UHFFFAOYSA-N 0.000 description 1
- 239000004831 Hot glue Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000013006 addition curing Methods 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- MOVRNJGDXREIBM-UHFFFAOYSA-N aid-1 Chemical group O=C1NC(=O)C(C)=CN1C1OC(COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)COP(O)(=O)OC2C(OC(C2)N2C(NC(=O)C(C)=C2)=O)COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)COP(O)(=O)OC2C(OC(C2)N2C(NC(=O)C(C)=C2)=O)COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)COP(O)(=O)OC2C(OC(C2)N2C(NC(=O)C(C)=C2)=O)COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)COP(O)(=O)OC2C(OC(C2)N2C3=C(C(NC(N)=N3)=O)N=C2)CO)C(O)C1 MOVRNJGDXREIBM-UHFFFAOYSA-N 0.000 description 1
- 230000003026 anti-oxygenic effect Effects 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 239000004815 dispersion polymer Substances 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000005355 lead glass Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical class OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 206010063401 primary progressive multiple sclerosis Diseases 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses a kind of copper-clad plate mixed type heat-conducting glues and its manufacturing method, belong to heat-conducting glue field, the raw material including following mass fraction: 40~60 parts of hybrid resin, 10~25 parts of polyethylene glycol oxide, 10~25 parts of polyethylene terephthalate, 10~15 parts of polybutylene naphthalate, 0.1~5 part of polyimides, 1~3 part of dispersing aid, 0.1~1 part of carbon fiber, 15~45 parts of organic solvent, 1~2 part of nano-iron oxide, 1~2 part of devitrified glass, 0.5~2 part of antioxidant, 0.5~1 part of curing agent；The hybrid resin is poly- methyl silicon resin and butyl rubber compounds or poly- ethyl silicone resin and butyl rubber compounds, and the butyl rubber accounts for the 60%~80% of the hybrid resin gross mass.Copper-clad plate disclosed by the invention mixed type heat-conducting glue, thermal conductivity at least improve 3 times, and 102 Ω cm have at least dropped in resistivity, and bond shear strength at least improves 1.13MPa.
Description
Technical field
The present invention relates to heat-conducting glue fields, more particularly to a kind of copper-clad plate mixed type heat-conducting glue.
Background technique
Heat transfer is always an important process in electronics industry, and the operating temperature of component is often the weight of reliability
It will foundation.The especially assembling of microelectronics increasingly densification, working environment is sharply to high temperature direction change, heat dissipation problem
Just become vital Consideration in design of electronic products.Pass through thermally conductive gluing between all kinds of heat source generators and radiator
The heat dissipation design that agent carries out thermally conductive connection, such as semiconductor, power sourced electric, white domestic appliances and LED etc. industry is all this mostly
Sample.
Heat-conducting glue is a kind of functional product applied to bonding radiating element and other power consumption components, this
Adhesive tape usually has extremely strong adhesive strength, good adhesion strength and heating conduction, soft, compressible, is easy to be die cut, being divided into has
Substrate and without substrate.The defects of generally existing thermal coefficient of current heat-conducting glue is low, physical property is poor.
Summary of the invention
In order to overcome the drawbacks of the prior art, the copper-clad plate that the present invention has prepared a kind of good heat conduction effect is led with mixed type
Hot glue.
To achieve this purpose, the present invention adopts the following technical scheme:
Copper-clad plate provided by the invention mixed type heat-conducting glue, the raw material including following mass fraction: hybrid resin 40~
60 parts, 10~25 parts of polyethylene glycol oxide, 10~25 parts of polyethylene terephthalate, 10~15 parts of polybutylene naphthalate,
0.1~5 part of polyimides, 1~3 part of dispersing aid, 0.1~1 part of carbon fiber, 15~45 parts of organic solvent, nano-iron oxide 1
~2 parts, 1~2 part of devitrified glass, 0.5~2 part of antioxidant, 0.5~1 part of curing agent；The hybrid resin is poly- methyl silicon resin
With butyl rubber compounds or poly- ethyl silicone resin and butyl rubber compounds, and the butyl rubber accounts for the hybrid resin
The 60%~80% of gross mass.
In preferably technical solution of the invention, the curing agent is the mixture of polybenzimidazoles and diethylenetriamine,
Or the mixture for polybenzimidazoles and triethylene tetramine, and the quality of polybenzimidazoles accounts for the 20% of the curing agent gross mass
~50%.
In preferably technical solution of the invention, the organic solvent is mixed solvent, and the organic solvent is N- methyl-
The volume ratio of the mixed solvent of 2-Pyrrolidone and DMF, the n-methyl-2-pyrrolidone and the DMF are 8~10:1.
In preferably technical solution of the invention, the dispersing aid is polyvinylpyrrolidone.
In preferably technical solution of the invention, the antioxidant is four [β-(3,5- three-level butyl -4- hydroxy phenyl) third
Acid] pentaerythritol ester, N, N'- bis- [β-(3,5- di-tert-butyl-hydroxy phenyl) propionyl] hydrazine English, 2,8- di-t-butyl -4- first
One or both of base phenol.
The preparation method follows the steps below:
S1, Xiang Suoshu hybrid resin, the polyethylene glycol oxide, the polyethylene terephthalate, the poly- naphthalene diacid
It is separately added into the organic solvent in butanediol ester and the polyimides, respectively agitating and heating, cools down after 20~40min mixed
It closes, the antioxidant is added thereto, constant temperature stirs 5~10min, obtains antioxygen mixture A；
The dispersing aid is added in S2, Xiang Suoshu antioxygen mixture A and sequentially adds institute after constant temperature stirs 1~2min
Carbon fiber, the nano-iron oxide and the devitrified glass are stated, continues constant temperature and stirs 30~60min, be cooled to room temperature, obtain
To mixture B；
Sodium hydrate particle or sodium bicarbonate powder are added in S3, Xiang Suoshu mixture B, adjusts the mixture B's
The curing agent is added in pH, stirs 5~10min up to mixed type heat-conducting glue.
In preferably technical solution of the invention, in step sl, the agitating and heating, heating temperature range is not more than
80 DEG C are crossed, mixing speed is 800~1500r/min.
In preferably technical solution of the invention, in step S1 cooling mixing, temperature is down to 50 DEG C.
In preferably technical solution of the invention, in step s 2, the speed of constant temperature stirring is 3000~4500r/min,
Temperature is 50 ± 5 DEG C.
In preferably technical solution of the invention, in step s3, the range of the pH value is 7.5~8.5.
The invention has the benefit that
Copper-clad plate provided by the invention mixed type heat-conducting glue can be used as base using poly- methyl silicon resin and butyl rubber
Material, on the one hand can be improved high temperature resistant, the heating conduction of heat-conducting glue, on the other hand can reduce production cost；Add poly- naphthalene diacid
Butanediol ester can be very good to reduce high-molecular compound glass transition temperature and melting temperature, it is crisp to improve glue-line as plasticizer
Property, promote melt fluidity, makes glue film that there is flexibility；The devitrified glass of addition can effectively increase the electrical isolation of heat-conducting glue
Performance and thermal stability and ageing-resistant performance；The heating conduction of heat-conducting glue had both can be improved in the nano-iron oxide of addition, also
It can be used as catalyst, be catalyzed each high molecular polymer and further polymerize, to increase the viscosity and viscous glutinous effect of heat-conducting glue.
The manufacturing method of copper-clad plate provided by the invention mixed type heat-conducting glue is stirred using the different constant temperature of temperature several times
It mixes, can prevent material from failing at a certain temperature；Mixing speed is controlled within the scope of one, the bonding that product can be improved is cut
Shearing stress, finally by adding sodium hydrate particle or sodium bicarbonate powder for the pH value tune of material before curing agent is added
It saves in certain range, the performance that test measures heat-conducting glue within the scope of this pH is best, and uses preparation method of the invention
The heat-conducting glue of preparation, thermal conductivity at least improve 3 times, and 102 Ω cm have at least dropped in resistivity, and bond shear strength at least mentions
1.13MPa is risen.
Specific embodiment
To further illustrate the technical scheme of the present invention With reference to embodiment.
Embodiment 1
Copper-clad plate provided in this embodiment mixed type heat-conducting glue, the raw material including following mass fraction: hybrid resin is (poly-
Methyl silicon resin and butyl rubber compounds, and the butyl rubber accounts for the 60% of the hybrid resin gross mass) 40 parts, polyoxy
Change 10 parts of ethylene, 10 parts of polyethylene terephthalate, 15 parts of polybutylene naphthalate, 0.1 part of polyimides, dispersing aid
1 part of (polyvinylpyrrolidone), 0.1 part of carbon fiber, organic solvent (mixed solvent of n-methyl-2-pyrrolidone and DMF, institute
The volume ratio for stating n-methyl-2-pyrrolidone and the DMF is 8:1) 15 parts, it is 1 part of nano-iron oxide (nano iron oxide), micro-
2 parts of crystal glass, 0.5 part of antioxidant (four [β-(3,5- three-level butyl -4- hydroxy phenyl) propionic acid] pentaerythritol esters), curing agent
(mixture of polybenzimidazoles and diethylenetriamine, and the quality of polybenzimidazoles accounts for the 20% of the curing agent gross mass)
0.5 part.
Further, it should be noted that poly- methyl silicon resin heat resistance is high, antioxygenic property is strong, but price phase
To valuableness, poly- methyl silicon resin and butyl rubber can play adhesive effect separately as the base-material of heat-conducting glue, base-material, it is desirable that have good
Good adhesion and wetability, but poly- methyl silicon resin price is more expensive, the high temperature resistance of butyl rubber is poor, uses
This two kinds of mixtures are as base-material, can be with and by the control of the mass ratio of poly- methyl silicon resin in the range of 20%~40%
High temperature resistant, the heating conduction of heat-conducting glue are improved to the greatest extent.Interior increasing of the polybutylene naphthalate as heat-conducting glue of the present invention
Agent is moulded, can be very good to reduce high-molecular compound glass transition temperature and melting temperature, improve glue-line brittleness, promote melt-flow
Property, make glue film that there is flexibility.Polyimides is one of optimal high-molecular organic material of comprehensive performance, and high temperature resistant is up to 400 DEG C
More than, -200~300 DEG C of long-term use temperature range, partially without sharp melting point, high insulating property is added on a small quantity to of the invention
In heat-conducting glue, cooperates other components, can greatly enhance high temperature resistance of the invention while reducing production cost.Carbon
Fiber is to be piled up by organic fibers such as flake graphites along fiber axial direction, is obtained through carbonization and graphitization processing
Microcrystalline graphite material.Carbon fiber has many excellent performances, and the axial strength and modulus of carbon fiber are high, and density is low, compares performance
Height, no creep, superhigh temperature resistant under non-oxidizing atmosphere, fatigue durability is good, specific heat and electric conductivity between nonmetallic between metal, heat
The coefficient of expansion is small and has anisotropy, good corrosion resistance, and X-ray transparent is good.Good electrical and thermal conductivity performance, electromagnetic shielding
Property it is good etc..Solvent can reduce the molecular force between solid or liquid, since the polymer substance with glue is solid-state or sticky
Liquid, inconvenient subsequent operation is added suitable solvent, on the one hand can reduce the viscosity of base-material, convenient for subsequent handling into
Row, on the other hand can increase merging between base-material and other molecules and molecule activity ability, the solvent that the present invention uses is N-
N-methyl-2-2-pyrrolidone N and DMF (n,N-Dimethylformamide) mixed solvent, DMF is non-protonic polar solvent, is had to a variety of
Machine compound and inorganic compound have good solvability, are commonly called as alembroth, in the presence of alkali-free, acid, water, have good
Good chemical stability, cosolvent of the n-methyl-2-pyrrolidone as the base-material can be good at the viscosity for reducing base-material,
Be conducive to performed polymer dispersion, the viscosity of heat-conducting glue can be utmostly down to by cooperation of the two Jing Guo accounting is easier to the glutinous of construction
Degree.On the one hand nano iron oxide can cooperate carbon fiber that the heating conduction between heat-conducting glue and circuit board, another party can be improved
Face can be used as each high molecular polymer in heat-conducting glue and merge excellent catalyst, so that the heat-conducting glue heating conduction prepared is more
Add excellent.Devitrified glass, high mechanical strength, excellent insulating property is resistant to chemical etching, and thermal stability is good, can be with using temperature height
Effectively increase the electrical insulation capability and thermal stability and ageing-resistant performance of heat-conducting glue.Curing agent is that one kind can make monomer or low
Polymers is converted into the substance of linear high polymer or netted figure high polymer, and the present embodiment uses polybenzimidazoles and divinyl
The mixture of triamine has good chemical stability, thermal stability, mechanical property, Zi Run as curing agent, polybenzimidazoles
Slip and self-extinguishment.
Embodiment 2
Copper-clad plate provided in this embodiment mixed type heat-conducting glue, the raw material including following mass fraction: silicone resin (poly- second
Base silicone resin and butyl rubber compounds, and the butyl rubber accounts for the 70% of the hybrid resin gross mass) 50 parts, polyoxygenated
18 parts of ethylene, 25 parts of polyethylene terephthalate, 12 parts of polybutylene naphthalate, 2 parts of polyimides, dispersing aid are (poly-
Vinylpyrrolidone) 2 parts, 0.5 part of carbon fiber, organic solvent (mixed solvent of n-methyl-2-pyrrolidone and DMF, the N-
The volume ratio of N-methyl-2-2-pyrrolidone N and the DMF are 9:1) 30 parts, 1.5 parts of nano-iron oxide (nano ferriferrous oxide),
1.5 parts of devitrified glass, antioxidant (bis- [β-(3,5- di-tert-butyl-hydroxy phenyl) propionyl] the hydrazine English of N, N'- and the tertiary fourth of 2,8- bis-
The mixing of base -4- methylphenol, and bis- [β-(3,5- di-tert-butyl-hydroxy phenyl) propionyl] the hydrazine English of N, N'- account for the antioxidant
The 25% of gross mass) 1.2 parts, the curing agent (mixture of polybenzimidazoles and triethylene tetramine, and the quality of polybenzimidazoles accounts for
The 35% of the curing agent gross mass) 0.7 part.
It should be noted that poly- ethyl silicone resin is the copolymer in siloxane chain containing ethyl, ethyl number in polymer
With the ratio between silicon atom number most preferably 0.8~1.2.Antioxidant uses N, the bis- [β-(3,5- di-tert-butyl-hydroxy phenyl) third of N'-
Acyl] hydrazine English and 2,8- di-tert-butyl-4-methy phenol mixture works as N, the bis- [β-(3,5- di-tert-butyl-hydroxy phenyl) of N'-
Propionyl] quality of hydrazine English when accounting for the antioxidant gross mass 25%, can achieve best antioxidant effect.Four oxidation three of nanometer
Iron other than improving the conductive force of heat-conducting glue and having catalytic action, is gone back because wherein also including part two compared with nano iron oxide
The iron of valence is easier to be attached on high molecular polymer, and thermally conductive and catalytic effect is more preferable.
Embodiment 3
Copper-clad plate provided in this embodiment mixed type heat-conducting glue, the raw material including following mass fraction: silicone resin (poly- second
Base silicone resin and butyl rubber compounds, and the butyl rubber accounts for the 80% of the hybrid resin gross mass) 60 parts, polyoxygenated
25 parts of ethylene, 18 parts of polyethylene terephthalate, 10 parts of polybutylene naphthalate, 5 parts of polyimides, dispersing aid are (poly-
Vinylpyrrolidone) 3 parts, 1 part of carbon fiber, organic solvent (mixed solvent of n-methyl-2-pyrrolidone and DMF, the N- first
The volume ratio of base -2-Pyrrolidone and the DMF are 45 parts of 8~10:1), 2 parts of nano-iron oxide (nano iron oxide), crystallite
1 part of glass, antioxidant (four [β-(3,5- three-level butyl -4- hydroxy phenyl) propionic acid] pentaerythritol esters, N, the bis- [β-(3,5- of N'-
Di-tert-butyl-hydroxy phenyl) propionyl] hydrazine English, 2,8- di-tert-butyl-4-methy phenol, three's mass ratio most preferably 1:6:10)
2 parts, the curing agent (mixture of polybenzimidazoles and diethylenetriamine or triethylene tetramine, and the quality of polybenzimidazoles accounts for institute
State the 50% of curing agent gross mass) 1 part.
Embodiment 4
Copper-clad plate provided in this embodiment is followed the steps below with the preparation method of mixed type heat-conducting glue:
S1, Xiang Suoshu silicone resin, the polyethylene glycol oxide, the polyethylene terephthalate, the poly- naphthalene diacid fourth
The organic solvent is separately added into diol ester and the polyimides, respectively agitating and heating, mixing speed 800r/min,
Being heated to temperature is 79.8 DEG C, and cool down mixing after 40min, and the antioxidant is added thereto, and constant temperature stirs 5min, obtains antioxygen
Mixture A；
The dispersing aid is added in S2, Xiang Suoshu antioxygen mixture A, after constant temperature stirs 1min, sequentially adds described
Carbon fiber, the nano-iron oxide and the devitrified glass continue constant temperature and stir 60min, and constant temperature stirs during entire S2
The speed mixed is 3000r/min, and temperature is 46 ± 1 DEG C, is cooled to room temperature, obtains mixture B；
It is 7.5 that sodium hydrate particle is added in S3, Xiang Suoshu mixture B and adjusts the pH value of the mixture B, described in addition
Curing agent stirs 5min up to mixed type heat-conducting glue.
Embodiment 5
Copper-clad plate provided in this embodiment is followed the steps below with the preparation method of mixed type heat-conducting glue:
S1, Xiang Suoshu silicone resin, the polyethylene glycol oxide, polyethylene terephthalate, the poly- naphthalene diacid butanediol
The organic solvent is separately added into ester and the polyimides, agitating and heating, mixing speed 1100r/min add respectively
Heat to temperature is 79.6 DEG C, and cool down mixing after 30min, and the antioxidant is added thereto, and constant temperature stirs 7min, and it is mixed to obtain antioxygen
Close object A；
The dispersing aid is added in S2, Xiang Suoshu antioxygen mixture A and sequentially adds institute after constant temperature stirs 1.5min
Carbon fiber, the nano-iron oxide and the devitrified glass are stated, continues constant temperature and stirs 4min, constant temperature stirs during entire S2
The speed mixed is 3800r/min, and temperature is 49 ± 1 DEG C, is cooled to room temperature, obtains mixture B；
It is 8 that sodium hydrate particle is added in S3, Xiang Suoshu mixture B and adjusts the pH value of the mixture B, is added described solid
Agent stirs 7min up to mixed type heat-conducting glue.
Embodiment 6
Copper-clad plate provided in this embodiment is followed the steps below with the preparation method of mixed type heat-conducting glue:
S1, Xiang Suoshu silicone resin, the polyethylene glycol oxide, polyethylene terephthalate, the poly- naphthalene diacid butanediol
The organic solvent is separately added into ester and the polyimides, respectively agitating and heating, mixing speed 800r/min, heating
It is 79.9 DEG C to temperature, cool down mixing after 20min, and the antioxidant is added thereto, and constant temperature stirs 10min, and it is mixed to obtain antioxygen
Close object A；
The dispersing aid is added in S2, Xiang Suoshu antioxygen mixture A, after constant temperature stirs 2min, sequentially adds described
Carbon fiber, the nano-iron oxide and the devitrified glass continue constant temperature and stir 60min, and constant temperature stirs during entire S2
The speed mixed is 4500r/min, and temperature is 54 ± 1 DEG C, is cooled to room temperature, obtains mixture B；
The range that the pH value that sodium bicarbonate powder adjusts the mixture B is added in S3, Xiang Suoshu mixture B is 8.5, is added
Enter the curing agent, stirs 10min up to mixed type heat-conducting glue.
Comparative example 1
Copper-clad plate provided in this embodiment mixed type heat-conducting glue, the raw material including following mass fraction: butyl rubber 75
Part, 1 part of dispersing aid (polyvinylpyrrolidone), 15 parts of organic solvent (toluene), antioxidant (four [β-(3,5- three-level butyl-
4- hydroxy phenyl) propionic acid] pentaerythritol ester) 0.5 part, 0.5 part of curing agent (polybenzimidazoles).
Example 1 is into embodiment 3, the component of comparative example 1 uses embodiment 4 respectively, embodiment 5 and embodiment
6 preparation method, prepares heat-conducting glue sample, embodiment 1 with embodiment 4 to the sample that embodiment 6 is prepared be known as sample 1,
Sample 2 and sample 3, embodiment 2 are known as sample 4, sample 5 and sample 6 with embodiment 4 to the sample that embodiment 6 is prepared, and implement
Example 3 is known as sample 7, sample 8 and sample 9, the embodiment 4 of comparative example 1 with embodiment 4 to the sample that embodiment 6 is prepared
The sample prepared to embodiment 6 is known as sample 10, sample 11 and sample 12.
Sample 13: it using the raw material and corresponding raw material components in comparative example 1, is prepared using following preparation method:
Take 75 parts of butyl rubber, 1 part of polyvinylpyrrolidone, four [β-(3,5- three-level butyl -4- hydroxy phenyl) propionic acid] pentaerythrites
0.5 part of ester, 0.5 part of polybenzimidazoles be added in 15 parts of toluene, after 1.5~2h of high-speed stirred be derived sample 13.
Above-mentioned sample 13 tested viscosities of every kind of sample, thermal conductivity, resistivity and bonding into sample 13 is arbitrarily selected to cut
Shearing stress, medium viscosity are tested using national standard GB/T2794-2013 method, and Viscometer Model is the viscosimeter of NDJ-5S
(25 DEG C of test temperature), thermal conductivity is using the PPMS-9T type property test system of U.S. Quantum Design company at 25 DEG C
The thermal conductivity after adhesive solidifies is tested under standard environment.Resistivity measurement uses Beijing hat to survey EST121 type high resistance and surveys
Instrument is tried, the resistivity of solid after adhesive solidifies is tested under 25 DEG C of standard environments.Bond shear strength uses national standard GB/
The method of T7124-2008 is tested, and specific data are as shown in the table:
As can be seen from the table, using in the present invention raw material and the heat-conducting glue for preparing of preparation method relative to comparison
Embodiment 1, thermal conductivity at least improve 3 times, and resistivity has at least dropped 102Ω cm, bond shear strength at least improve
1.13MPa。
All raw materials are commercially available in the present invention, partially using preceding by grinding processing, after other are purchase
Directly use.
The present invention is described with reference to the preferred embodiments, and those skilled in the art know, of the invention not departing from
In the case where spirit and scope, various changes or equivalence replacement can be carried out to these features and embodiment.The present invention is not by this
The limitation of specific embodiment disclosed in place, other embodiments fallen into claims hereof belong to protection of the present invention
Range.
Claims (10)
1. a kind of copper-clad plate mixed type heat-conducting glue, which is characterized in that the raw material including following mass fraction: hybrid resin 40~
60 parts, 10~25 parts of polyethylene glycol oxide, 10~25 parts of polyethylene terephthalate, 10~15 parts of polybutylene naphthalate,
0.1~5 part of polyimides, 1~3 part of dispersing aid, 0.1~1 part of carbon fiber, 15~45 parts of organic solvent, nano-iron oxide 1
~2 parts, 1~2 part of devitrified glass, 0.5~2 part of antioxidant, 0.5~1 part of curing agent；The hybrid resin is poly- methyl silicon resin
With butyl rubber compounds or poly- ethyl silicone resin and butyl rubber compounds, and the butyl rubber accounts for the hybrid resin
The 60%~80% of gross mass.
2. copper-clad plate according to claim 1 mixed type heat-conducting glue, which is characterized in that the curing agent is polyphenyl and miaow
The mixture of azoles and diethylenetriamine, or be the mixture of polybenzimidazoles and triethylene tetramine, and the quality of polybenzimidazoles
Account for the 20%~50% of the curing agent gross mass.
3. copper-clad plate according to claim 1 mixed type heat-conducting glue, which is characterized in that the organic solvent is that mixing is molten
Agent, the organic solvent be n-methyl-2-pyrrolidone and DMF mixed solvent, the n-methyl-2-pyrrolidone with it is described
The volume ratio of DMF is 8~10:1.
4. copper-clad plate according to claim 1 mixed type heat-conducting glue, which is characterized in that the dispersing aid is polyethylene
Pyrrolidones.
5. copper-clad plate according to claim 1 mixed type heat-conducting glue, which is characterized in that the antioxidant be four [β-(3,
5- three-level butyl -4- hydroxy phenyl) propionic acid] pentaerythritol ester, N, the bis- [β-(3,5- di-tert-butyl-hydroxy phenyl) third of N'-
Acyl] hydrazine English, one or both of 2,8- di-tert-butyl-4-methy phenol.
6. a kind of preparation method of copper-clad plate described in any one of claim 1 to 5 mixed type heat-conducting glue, which is characterized in that
The preparation method follows the steps below:
S1, Xiang Suoshu hybrid resin, the polyethylene glycol oxide, the polyethylene terephthalate, the poly- naphthalene diacid fourth two
The organic solvent being separately added into alcohol ester and the polyimides, respectively agitating and heating, cool down mixing after 20~40min,
The antioxidant is added thereto, constant temperature stirs 5~10min, obtains antioxygen mixture A；
The dispersing aid is added in S2, Xiang Suoshu antioxygen mixture A and sequentially adds the carbon after constant temperature stirs 1~2min
Fiber, the nano-iron oxide and the devitrified glass continue constant temperature and stir 30~60min, be cooled to room temperature, mixed
Close object B；
Sodium hydrate particle or sodium bicarbonate powder are added in S3, Xiang Suoshu mixture B, adjusts the pH of the mixture B, adds
Enter the curing agent, stirs 5~10min up to mixed type heat-conducting glue.
7. the copper-clad plate according to claim 6 preparation method of mixed type heat-conducting glue, which is characterized in that stirred in step S1
It mixes in heating, not more than 80 DEG C of heating temperature range, mixing speed is 800~1500r/min.
8. the copper-clad plate according to claim 6 preparation method of mixed type heat-conducting glue, which is characterized in that dropped in step S1
In temperature mixing, temperature is down to 50 DEG C.
9. the copper-clad plate according to claim 6 preparation method of mixed type heat-conducting glue, which is characterized in that in step S2
In, the speed of constant temperature stirring is 3000~4500r/min, and temperature is 50 ± 5 DEG C.
10. the copper-clad plate according to claim 6 preparation method of mixed type heat-conducting glue, which is characterized in that in step S3
In, the range of the pH value is 7.5~8.5.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102925089A (en) * | 2012-11-21 | 2013-02-13 | 苏州赛伍应用技术有限公司 | Flexible heat-conducting resin, and prepreg and metal base copper clad laminate prepared from same |
| CN102993996A (en) * | 2011-09-14 | 2013-03-27 | 赵元成 | High-thermal-conductivity film for aluminum-based copper-coated plate, and preparation method thereof |
| CN107254262A (en) * | 2017-05-25 | 2017-10-17 | 钱龙风 | A kind of heat conduction film |
-
2019
- 2019-01-28 CN CN201910077192.9A patent/CN109852294B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102993996A (en) * | 2011-09-14 | 2013-03-27 | 赵元成 | High-thermal-conductivity film for aluminum-based copper-coated plate, and preparation method thereof |
| CN102925089A (en) * | 2012-11-21 | 2013-02-13 | 苏州赛伍应用技术有限公司 | Flexible heat-conducting resin, and prepreg and metal base copper clad laminate prepared from same |
| CN107254262A (en) * | 2017-05-25 | 2017-10-17 | 钱龙风 | A kind of heat conduction film |
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Denomination of invention: A mixed thermal conductive adhesive for copper clad plate and its manufacturing method Effective date of registration: 20230215 Granted publication date: 20210511 Pledgee: Yichun Rural Commercial Bank Co.,Ltd. Pledgor: JIANGXI PROVINCE HANGYU NEW MATERIAL Co.,Ltd. Registration number: Y2023980032737 |
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Denomination of invention: A mixed thermal conductive adhesive for copper clad panels and its manufacturing method Granted publication date: 20210511 Pledgee: Yichun Rural Commercial Bank Co.,Ltd. Pledgor: JIANGXI PROVINCE HANGYU NEW MATERIAL Co.,Ltd. Registration number: Y2024980005775 |