CN112694719A - Resin composition, preparation method thereof and metal substrate - Google Patents
Resin composition, preparation method thereof and metal substrate Download PDFInfo
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- CN112694719A CN112694719A CN202011590887.6A CN202011590887A CN112694719A CN 112694719 A CN112694719 A CN 112694719A CN 202011590887 A CN202011590887 A CN 202011590887A CN 112694719 A CN112694719 A CN 112694719A
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- resin composition
- epoxy resin
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- resin
- high thermal
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- 239000011342 resin composition Substances 0.000 title claims abstract description 62
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 45
- 239000002184 metal Substances 0.000 title claims abstract description 45
- 239000000758 substrate Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title abstract description 4
- 239000003822 epoxy resin Substances 0.000 claims abstract description 46
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 46
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 33
- 239000000843 powder Substances 0.000 claims abstract description 27
- 150000002500 ions Chemical class 0.000 claims abstract description 23
- 239000000463 material Substances 0.000 claims description 25
- 239000010410 layer Substances 0.000 claims description 24
- 239000012790 adhesive layer Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- 230000017525 heat dissipation Effects 0.000 claims description 12
- 239000012752 auxiliary agent Substances 0.000 claims description 10
- 229910052582 BN Inorganic materials 0.000 claims description 9
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- 239000002516 radical scavenger Substances 0.000 claims description 9
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 8
- 239000002270 dispersing agent Substances 0.000 claims description 8
- 229920001971 elastomer Polymers 0.000 claims description 8
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 6
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 6
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 238000000498 ball milling Methods 0.000 claims description 5
- 238000001179 sorption measurement Methods 0.000 claims description 5
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims description 4
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 239000007822 coupling agent Substances 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 239000011888 foil Substances 0.000 claims description 4
- 238000007731 hot pressing Methods 0.000 claims description 4
- 229920003986 novolac Polymers 0.000 claims description 4
- 239000004843 novolac epoxy resin Substances 0.000 claims description 4
- 239000005011 phenolic resin Substances 0.000 claims description 4
- JRQJLSWAMYZFGP-UHFFFAOYSA-N 1,1'-biphenyl;phenol Chemical compound OC1=CC=CC=C1.C1=CC=CC=C1C1=CC=CC=C1 JRQJLSWAMYZFGP-UHFFFAOYSA-N 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- 125000002723 alicyclic group Chemical group 0.000 claims description 3
- 239000004305 biphenyl Substances 0.000 claims description 3
- 235000010290 biphenyl Nutrition 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 2
- 150000008064 anhydrides Chemical class 0.000 claims description 2
- 229920001568 phenolic resin Polymers 0.000 claims description 2
- 239000002131 composite material Substances 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 239000011889 copper foil Substances 0.000 description 10
- 238000009413 insulation Methods 0.000 description 8
- 238000012545 processing Methods 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 4
- 150000001450 anions Chemical class 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 230000032683 aging Effects 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000010292 electrical insulation Methods 0.000 description 2
- 238000009775 high-speed stirring Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000013034 phenoxy resin Substances 0.000 description 1
- 229920006287 phenoxy resin Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
- C08L63/04—Epoxynovolacs
-
- 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
- B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
-
- 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
- B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
-
- 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
- B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
- B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B9/041—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different 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
- B32B2255/00—Coating on the layer surface
- B32B2255/06—Coating on the layer surface on metal 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
- B32B2255/00—Coating on the layer surface
- B32B2255/26—Polymeric coating
-
- 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
- B32B2255/00—Coating on the layer surface
- B32B2255/28—Multiple coating on one surface
-
- 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
- B32B2307/206—Insulating
-
- 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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
-
- 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
- C08K3/38—Boron-containing compounds
- C08K2003/382—Boron-containing compounds and nitrogen
- C08K2003/385—Binary compounds of nitrogen with boron
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Insulated Metal Substrates For Printed Circuits (AREA)
Abstract
The invention belongs to the technical field of polymer composite materials, and particularly relates to a resin composition, a preparation method thereof and a metal substrate. Wherein the resin composition comprises high thermal conductive powder, epoxy resin, a curing agent and an ion trapping agent; wherein, the electrical conductivity of the high thermal conductive powder is not more than 40 mu s/cm, and the content of free ions is not more than 30 ppm. According to the invention, through controlling the conductivity and the free ion content of the high-thermal-conductivity powder and combining the ion capture agent, the resin composition has excellent insulating property, and the CAF-resistant metal substrate applied by the resin composition has excellent CAF-resistant performance.
Description
Technical Field
The invention belongs to the technical field of polymer composite materials, and particularly relates to a resin composition, a preparation method thereof and a metal substrate.
Background
With the high-speed development of the new energy automobile industry, the global demand of new energy automobiles is increasing, the automation degree is also increasing, and concepts such as automatic driving and quick charging are gradually realized. Therefore, the requirements on the matched electric control module and charging pile module are higher and higher.
In the traditional application, the metal-based copper-clad plate is widely applied due to the excellent heat dissipation capacity, but the metal-based copper-clad plate is mainly applied in the fields of common illumination, television backlight and the like, and the actual requirement on heat conduction is mainly 0.9-1.8W/m.K; the working voltage in the above fields is generally not high, and there is no high specification requirement for the insulation property and CAF resistance property of the material. On the contrary, in order to reduce the cost, the materials are not strictly screened by more plate factories; in order to meet the requirement of mass and high-efficiency production of customers, toughening materials such as nitrile rubber are added into the metal substrate to improve the processing window, so that the Tg of the material is relatively low; the formula design does not manage and control metal ions, chloride ions and other anions and cations, the resistance is generally lower than 3G omega under the condition of humidity and heat of 80-150 mu m, the attenuation is fast after the accelerated aging at 85 ℃/85% RH1000cycle, and the CAF resistance performance is weaker.
In recent years, the metal substrate with high thermal conductivity is also widely applied to new energy electronic control, battery management systems and new energy charging pile modules, and the importance of the module function is more and more prominent. However, electric automobiles drive for a long time, charging piles are frequently charged and discharged, and high-temperature and humid outdoor environments put higher requirements on the performance grade and the weather resistance of the materials. For the heat-conducting metal substrate, in addition to the requirement of the PCB, the heat-conducting metal substrate is required to have more excellent heat dissipation capability and electrical insulation property, and have longer stability in temperature, humidity and bias voltage, wherein, the accelerated aging test of 85 ℃/85% RH needs to satisfy more than 3000 cycles, and the attenuation amplitude cannot exceed 10%, which is often difficult to satisfy by the conventional aluminum substrate.
Disclosure of Invention
Based on the above disadvantages and shortcomings of the prior art, an object of the present invention is to solve at least one or more of the above problems of the prior art, in other words, to provide a resin composition, a method for preparing the same, and a metal substrate satisfying one or more of the above requirements.
In order to achieve the purpose, the invention adopts the following technical scheme:
a resin composition comprises high thermal conductive powder, epoxy resin, curing agent and ion trapping agent;
wherein, the electrical conductivity of the high thermal conductive powder is not more than 40 mu s/cm, and the content of free ions is not more than 30 ppm.
Preferably, the epoxy resin comprises a first epoxy resin and a second epoxy resin, and the first epoxy resin comprises at least one of bisphenol A type epoxy resin and bisphenol F type epoxy resin; the second epoxy resin includes at least one of o-cresol novolac type epoxy resin, dicyclopentadiene type novolac epoxy resin, alicyclic epoxy resin, biphenyl type epoxy resin. The first epoxy resin is used as the base resin, so that the resin composition filled with the high-thermal-conductivity powder has good fluidity.
Preferably, the curing agent is a high Tg curing agent, and at least one of anhydride, diaminodiphenyl sulfone and biphenyl phenol type phenolic resin is selected.
Preferably, the resin composition also comprises a toughening material, and the chlorine content of the toughening material is not more than 600 ppm. The brittleness of the resin composition after curing is not beneficial to PCB processing, the higher the Tg is, the more serious the brittleness is, the brittleness can be improved after the toughening material is added, and the processability of the PCB is improved.
Preferably, the high thermal conductivity powder comprises one or more of aluminum oxide, silicon nitride and boron nitride, and the D50 particle size of the high thermal conductivity powder is 0.03-40 μm.
Preferably, the resin composition further comprises an auxiliary agent, wherein the weight ratio of the high thermal conductive powder to the epoxy resin to the curing agent to the ion scavenger to the auxiliary agent is 500-700: 70-100: 20-90: 1-4: 1-7; wherein, the auxiliary agent comprises a silane coupling agent, a dispersant and a flatting agent, and the silane coupling agent: dispersing agent: the weight ratio of the flatting agent is 0.1-5: 0.1-3: 0.1 to 3.
The present invention also provides a method for preparing the resin composition according to any one of the above embodiments, comprising the steps of:
(1) mixing epoxy resin, a curing agent and an ion trapping agent to obtain a mixed rubber material;
(2) adding high-thermal-conductivity powder into the mixed rubber material, and respectively carrying out stirring, ball milling, defoaming, magnetic bar adsorption and filtering to obtain a resin composition;
(3) the viscosity of the resin composition is adjusted to 1800-2500 mPas by a solvent.
The invention also provides a metal substrate which is provided with the high-thermal-conductivity adhesive layer prepared from the resin composition in any scheme.
As a preferred scheme, the metal substrate comprises a heat dissipation metal layer, a high heat conduction adhesive layer and a metal foil layer, and the three are formed by hot pressing; wherein, the surface of the heat dissipation metal layer is processed by a coupling agent.
Preferably, the high thermal conductive adhesive layer is formed by coating the resin composition on the metal foil layer for multiple times.
Compared with the prior art, the invention has the beneficial effects that:
(1) the resin composition of the present invention has high Tg, high heat resistance, excellent heat conductivity and electrical insulation properties;
(2) the resin composition has high crosslinking density and good heat resistance after being cured;
(3) in a high Tg epoxy system, the invention emphasizes the control of the ion level in the resin composition, and selects low-chlorine toughened resin and low-sodium heat-conducting filler; the mixture is subjected to high-speed dispersion, ball milling, defoaming, magnetic bar adsorption, filtering and other processes to ensure that the heat-conducting filler is uniformly dispersed without impurities and agglomerated powder, the heat conductivity coefficient of the cured resin composition is more than or equal to 3.0W/m.K, and the high insulation property is ensured; the addition of the ion scavenger ensures the long-term insulation reliability of the material under the damp and hot conditions, and the cured resin composition has excellent insulation property (more than 5G omega), so that the metal substrate has excellent CAF resistance;
(4) the invention reduces the microscopic defects of pinholes, air holes and the like of the resin composition glue layer by coating for many times;
(5) the coupling agent treatment on the surface of the heat dissipation metal layer improves the compatibility between the high heat conduction adhesive layer and the heat dissipation metal layer, enhances the stability of the metal substrate under the condition of 85 ℃/85% RH, has good CAF resistance, stable and reliable insulating capability and high heat dissipation and heat resistance.
Detailed Description
The technical solution of the present invention is further explained by the following specific examples.
The resin composition of each embodiment of the invention comprises the following components in parts by weight: 500-700 parts of high-thermal-conductivity powder, 70-100 parts of epoxy resin, 5-10 parts of toughening resin, 20-90 parts of curing agent, 1-4 parts of ion scavenger and 1-7 parts of auxiliary agent; in particular, the component contents referred to in the respective examples may be selected within the respective ranges.
The weight part of the high heat conduction powder is lower than or higher than the proportion, which can affect the main performance of the resin composition; the lower weight part can cause the thermal conductivity coefficient of the cured resin composition to not meet the design requirement, namely more than or equal to 3.0W/m.K; the higher weight part can lead to higher inorganic substance filling volume, and the epoxy resin can not be well infiltrated to lead to the reduction of the insulation property of the metal substrate.
Wherein, the electrical conductivity of the high heat-conducting powder is not more than 40 mu s/cm, and the content of free ions is not more than 30ppm, and the resin composition has excellent insulating property (more than 5G omega) and CAF resistance by controlling the electrical conductivity and the content of the free ions of the high heat-conducting powder and combining with an ion catcher.
The high-thermal-conductivity powder comprises one or more of aluminum oxide, silicon nitride and boron nitride, and the D50 particle size of the high-thermal-conductivity powder is 0.03-40 mu m.
Specifically, the alumina is preferably spherical alumina, the D50 particle size of the alumina is 0.03-25 μm, and the sodium ion content of the alumina is controlled to be not more than 30 ppm; more preferably, the sodium ion content of the alumina is controlled to be < 20 ppm.
The D50 particle size of the silicon nitride is 3-5 μm, and the content of free ions in the silicon nitride is controlled to be not more than 30 ppm;
the boron nitride is flaky boron nitride or spheroidal boron nitride, the D50 particle size of the boron nitride is 7-40 μm, and the content of free ions in the boron nitride is controlled to be not more than 30 ppm.
In addition, the epoxy resin is a combination type epoxy resin, and comprises a first epoxy resin and a second epoxy resin to form a high heat-resistant epoxy resin system.
Wherein the first epoxy resin comprises at least one of bisphenol A type epoxy resin and bisphenol F type epoxy resin, and is used as a basic epoxy component of the resin composition, so that the resin composition filled with a high proportion of heat-conducting filler has good fluidity.
The second epoxy resin includes at least one of o-cresol novolac type epoxy resin, dicyclopentadiene type novolac epoxy resin, alicyclic epoxy resin, biphenyl type epoxy resin.
The toughening material comprises at least one of core-shell rubber, carboxyl-terminated modified epoxy resin and phenoxy resin; in addition, the chlorine content of the toughening resin is controlled to be less than 600 ppm. The brittleness of the resin composition after curing is not beneficial to PCB processing, the higher the Tg is, the more serious the brittleness is, the brittleness can be improved after the toughening material is added, and the processability of the PCB is improved. Wherein, whether the toughening material is added or not can be determined according to the actual PCB processing condition.
The ion scavenger includes at least one of an anion scavenger and a cation scavenger. The method is used for controlling the content of anions and cations in a resin composition system and ensuring the long-term insulation reliability of the material under the damp and hot conditions.
As the curing agent, a high Tg curing agent is preferable, including at least one of acid anhydride, diaminodiphenyl sulfone, biphenyl phenol type phenol resin. The curing agent with high Tg is adopted to ensure the high Tg performance of the resin composition.
Wherein, the auxiliary agent comprises a silane coupling agent, a dispersant and a flatting agent, and the silane coupling agent: dispersing agent: the weight ratio of the flatting agent is 0.1-5: 0.1-3: 0.1 to 3. More preferably, the silane coupling agent: dispersing agent: the weight ratio of the leveling agent is 4: 2: 1.
in a preferred embodiment, the resin composition may further comprise an accelerator, wherein the accelerator is one or more of 2-methylimidazole and 2-ethyl-4-methylimidazole, and the accelerator mainly functions to control the gel time of the resin composition and reduce the activation energy required by the reaction.
In addition, the resin composition also comprises a solvent, wherein the solvent is one or more of butanone, xylene, N-dimethylformamide and ethylene glycol monomethyl ether, and is used for assisting in dispersing the high-thermal-conductivity powder and adjusting the viscosity of the resin composition.
Accordingly, a method of preparing a resin composition of an embodiment of the present invention includes the steps of:
(1) mixing and stirring epoxy resin, toughening resin, a curing agent, an ion capturing agent and an auxiliary agent to obtain a mixed rubber material;
(2) adding high-thermal-conductivity powder into the mixed rubber material, and respectively carrying out high-speed stirring, ball milling, low-speed defoaming, magnetic bar adsorption and filtering to obtain a resin composition;
(3) the viscosity of the resin composition is adjusted to 1800-2500 mPas by a solvent.
Wherein the high-speed stirring mode is 1500 rpm in a high-speed shearing machine, and the time is 30 minutes; the ball milling mode is that the zirconium oxide ball mill rotates at 500 revolutions per minute in a forward rotation mode and rotates in a reverse rotation mode for 30 minutes respectively so as to ensure that no heat-conducting filler is agglomerated and improve the defect of rapid sedimentation; the low-speed defoaming is 400 revolutions per minute in a blade stirrer, and the low-speed defoaming is 20 minutes so as to ensure that the resin composition has no obvious micro bubbles.
The magnetic bar adsorption can obviously improve the CAF resistance of the metal substrate.
Wherein the solvent is one or more of butanone, xylene, N-dimethylformamide and ethylene glycol monomethyl ether.
In addition, the metal substrate of the embodiment of the invention takes a metal-based copper-clad plate as an example for detailed description, and comprises a heat-dissipation metal layer, a high-heat-conductivity adhesive layer and a copper foil layer which are processed by the resin composition, and three layers are superposed and hot-pressed for forming. In addition, the metal substrate may be a single-layer plate.
Specifically, the copper foil layer is an electronic-grade purple copper foil, the thickness is 0.012-0.5 mm, the thickness range does not influence the performance, and only the production capacity is shown;
the heat dissipation metal layer can be an anodic aluminum oxide plate, an anodic aluminum oxide alloy plate and a brown copper plate, the thickness is 0.2-5.0 mm, the thickness range does not influence the performance, and only the production capacity is shown;
in addition, the heat dissipation metal layer needs to be surface-treated. Specifically, the surface is subjected to spraying and drying treatment by 0.2% of coupling agent, so that the CAF resistance is obviously improved.
Specifically, the processing process of the metal-based copper-clad plate of the embodiment of the invention is as follows:
(4) coating the resin composition obtained in the step (3) on a roughened surface of a copper foil layer through a scraper with a specific gap, standing at normal temperature, and then putting into an oven for drying and pre-curing to obtain a high-thermal-conductivity adhesive layer/copper foil layer with the thickness of 40-100 microns; wherein the drying mode is to place the mixture for 5 minutes at normal temperature and bake the mixture for 5 minutes at 150 ℃.
(5) Carrying out secondary coating on the 40-100 mu m high-thermal-conductivity adhesive layer/copper foil layer according to the same process to obtain an 80-200 mu m high-thermal-conductivity adhesive layer/copper foil layer;
(6) placing a 80-200 mu m high-thermal-conductivity adhesive layer/copper foil layer on the heat-dissipation metal layer, and hot-pressing the copper foil/adhesive layer/copper foil layer by a vacuum press at 180-220 ℃ and 15-40Kg/cm2And (4) performing hot-pressing curing for 100-220 min to obtain the high-Tg CAF-resistant metal-based copper-clad plate.
The high thermal conductive adhesive layer is formed by coating the resin composition on the substrate by two times, three times, four times, five times, or the like.
The advantages of the resin composition and the metal-based copper-clad plate are shown by the comparison of specific examples and comparative examples.
The specific raw materials are as follows:
(F) high thermal conductivity powder:
(F1) spherical low-sodium alumina
(F2) Silicon nitride
(F3) Boron nitride
Ordinary alumina, conductivity 60 mus/cm
(A) Epoxy resin:
(A1) bisphenol A epoxy resin
(A2) O-cresol novolac type epoxy resin
(A3) Dicyclopentadiene type novolac epoxy resin
(B) Core-shell rubber
(C) Curing agent:
(C1) diamino diphenyl sulfone
(C2) Phenol-phenol type phenol resin
Dicyandiamide, low Tg
(D) Auxiliary agent:
(D1) silane coupling agent
(D2) Dispersing agent
(D3) Leveling agent
(E) An ion scavenger:
(E1) anion scavenger
(E2) Cation trapping agent
The raw materials and process conditions of examples 1 to 5 and comparative examples 1 to 7 can be referred to above, and the ratios and process parameters are the same for each example and comparative example except for the differences in the ratios and processes mentioned in table 1. The specific raw materials and process changes are shown in table 1:
TABLE 1 raw materials and Process conditions for examples 1 to 5 and comparative examples 1 to 7
The resin compositions and metal-based copper clad laminates prepared in the above examples 1 to 5 and comparative examples 1 to 7 were subjected to performance tests, as shown in table 2.
TABLE 2 results of the Performance test of the above examples 1 to 5 and comparative examples 1 to 7
From the test results, the thermal conductivity of the resin compositions of examples 1 to 5 and comparative examples 1, 3, 4, 5, 6 and 7 was more than 3.0W/m.K, indicating that the resin compositions had higher thermal conductivity; in contrast, in comparative example 2, the addition ratio of the high thermal conductivity powder was low, and the thermal conductivity was only 1.8W/mK.
The materials of examples 1-5 and comparative examples 3, 4, 5, 6 and 7 have high crosslinking density, Tg values are all larger than 180 ℃, and the materials do not have abnormality when continuously floating tin for 30min at 300 ℃, thereby showing that the heat resistance is excellent.
The metal-based copper-clad plates of examples 1-5 have excellent insulation resistance, resistance stability under the condition of 85 ℃/85% RH, and excellent CAF resistance; the comparative examples 1 to 7 are inferior to the examples of the present invention in both insulation resistance and CAF resistance.
In conclusion, the resin composition has the thermal conductivity coefficient of more than or equal to 3.0W/m.K and excellent thermal conductivity; and the Tg of the resin composition is more than 180 ℃ in DSC test after curing, and the material has high internal crosslinking density and strong heat resistance; the metal substrate has the resistance value of more than 5G omega tested in the environment of 85 ℃/85% RH, and the resistance attenuation rate of less than 10% after 3000 cycles accelerated aging, and has excellent CAF resistance. Therefore, the resin composition and the high-Tg CAF-resistant metal substrate have excellent basic characteristics and long-term weather durability, can ensure the stability of an electronic module, particularly have great significance in the field of new energy application, and provide a material solution for the field of new energy application.
The foregoing has outlined rather broadly the preferred embodiments and principles of the present invention and it will be appreciated that those skilled in the art may devise variations of the present invention that are within the spirit and scope of the appended claims.
Claims (10)
1. A resin composition is characterized by comprising high heat-conducting powder, epoxy resin, a curing agent and an ion trapping agent;
wherein, the electrical conductivity of the high thermal conductive powder is not more than 40 mu s/cm, and the content of free ions is not more than 30 ppm.
2. The resin composition as claimed in claim 1, wherein the epoxy resin comprises a first epoxy resin and a second epoxy resin, the first epoxy resin comprising at least one of a bisphenol a type epoxy resin and a bisphenol F type epoxy resin; the second epoxy resin includes at least one of o-cresol novolac type epoxy resin, dicyclopentadiene type novolac epoxy resin, alicyclic epoxy resin, biphenyl type epoxy resin.
3. The resin composition of claim 1, wherein the curing agent is a high Tg curing agent selected from at least one of an anhydride, diamino diphenyl sulfone, and a biphenyl phenol type phenolic resin.
4. The resin composition of claim 1, further comprising a toughening material, wherein the toughening material has a chlorine content of not greater than 600 ppm.
5. The resin composition as claimed in claim 1, wherein the high thermal conductivity powder comprises one or more of alumina, silicon nitride and boron nitride, and the D50 particle size of the high thermal conductivity powder is 0.03-40 μm.
6. The resin composition as claimed in claim 1, further comprising an auxiliary agent, wherein the weight ratio of the high thermal conductive powder, the epoxy resin, the curing agent, the ion scavenger and the auxiliary agent is 500-700: 70-100: 20-90: 1-4: 1-7; wherein, the auxiliary agent comprises a silane coupling agent, a dispersant and a flatting agent, and the silane coupling agent: dispersing agent: the weight ratio of the flatting agent is 0.1-5: 0.1-3: 0.1 to 3.
7. A process for producing a resin composition according to any one of claims 1 to 6, comprising the steps of:
(1) mixing epoxy resin, a curing agent and an ion trapping agent to obtain a mixed rubber material;
(2) adding high-thermal-conductivity powder into the mixed rubber material, and respectively carrying out stirring, ball milling, defoaming, magnetic bar adsorption and filtering to obtain a resin composition;
(3) the viscosity of the resin composition is adjusted to 1800-2500 mPas by a solvent.
8. A metal substrate characterized by having a high thermal conductive adhesive layer made of the resin composition according to any one of claims 1 to 7.
9. The metal substrate as claimed in claim 8, comprising a heat-dissipating metal layer, a high thermal conductive adhesive layer and a metal foil layer, which are formed by hot pressing; wherein, the surface of the heat dissipation metal layer is processed by a coupling agent.
10. The metal substrate as claimed in claim 8, wherein the high thermal conductive adhesive layer is formed by coating the resin composition on the metal foil layer a plurality of times.
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