CN115139589A - High-thermal-conductivity copper-clad plate and preparation method thereof - Google Patents
High-thermal-conductivity copper-clad plate and preparation method thereof Download PDFInfo
- Publication number
- CN115139589A CN115139589A CN202210735325.9A CN202210735325A CN115139589A CN 115139589 A CN115139589 A CN 115139589A CN 202210735325 A CN202210735325 A CN 202210735325A CN 115139589 A CN115139589 A CN 115139589A
- Authority
- CN
- China
- Prior art keywords
- insulating layer
- copper
- layer
- conductivity
- epoxy resin
- 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.)
- Granted
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000011889 copper foil Substances 0.000 claims abstract description 36
- 239000003822 epoxy resin Substances 0.000 claims description 58
- 229920000647 polyepoxide Polymers 0.000 claims description 58
- 239000003292 glue Substances 0.000 claims description 51
- 239000003795 chemical substances by application Substances 0.000 claims description 38
- 239000012745 toughening agent Substances 0.000 claims description 34
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 30
- 229920005989 resin Polymers 0.000 claims description 25
- 239000011347 resin Substances 0.000 claims description 25
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 24
- 239000000843 powder Substances 0.000 claims description 23
- 239000002904 solvent Substances 0.000 claims description 20
- 239000011248 coating agent Substances 0.000 claims description 19
- 238000000576 coating method Methods 0.000 claims description 19
- 239000002994 raw material Substances 0.000 claims description 19
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 16
- 239000002313 adhesive film Substances 0.000 claims description 16
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 15
- 239000000945 filler Substances 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 14
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 12
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 12
- 238000004090 dissolution Methods 0.000 claims description 12
- 238000003475 lamination Methods 0.000 claims description 12
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- 230000001070 adhesive effect Effects 0.000 claims description 8
- -1 polyethylene Polymers 0.000 claims description 7
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 6
- 239000005062 Polybutadiene Substances 0.000 claims description 6
- 239000004698 Polyethylene Substances 0.000 claims description 6
- 150000008065 acid anhydrides Chemical class 0.000 claims description 6
- 230000001588 bifunctional effect Effects 0.000 claims description 6
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- 239000004814 polyurethane Substances 0.000 claims description 6
- 229920002635 polyurethane Polymers 0.000 claims description 6
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 6
- 238000009413 insulation Methods 0.000 claims description 5
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 4
- 239000011256 inorganic filler Substances 0.000 claims description 4
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 4
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- 229910021389 graphene Inorganic materials 0.000 claims description 3
- 238000005452 bending Methods 0.000 abstract description 17
- 229910052802 copper Inorganic materials 0.000 abstract description 10
- 239000010949 copper Substances 0.000 abstract description 10
- 230000017525 heat dissipation Effects 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 5
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- 230000000052 comparative effect Effects 0.000 description 13
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- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 229920001187 thermosetting polymer Polymers 0.000 description 5
- 239000004593 Epoxy Substances 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 239000011229 interlayer Substances 0.000 description 4
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 3
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- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- LLEASVZEQBICSN-UHFFFAOYSA-N 2-undecyl-1h-imidazole Chemical compound CCCCCCCCCCCC1=NC=CN1 LLEASVZEQBICSN-UHFFFAOYSA-N 0.000 description 2
- TYOXIFXYEIILLY-UHFFFAOYSA-N 5-methyl-2-phenyl-1h-imidazole Chemical compound N1C(C)=CN=C1C1=CC=CC=C1 TYOXIFXYEIILLY-UHFFFAOYSA-N 0.000 description 2
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
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- 238000007731 hot pressing Methods 0.000 description 2
- 239000011810 insulating material Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
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- 241000233855 Orchidaceae Species 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
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- 238000010586 diagram Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
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- 238000003825 pressing Methods 0.000 description 1
- 238000009824 pressure lamination Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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- 239000000454 talc Substances 0.000 description 1
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- 238000010998 test method Methods 0.000 description 1
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Images
Classifications
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- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
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- 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
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
- B32B15/092—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising epoxy resins
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- B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
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- B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
- C09J9/02—Electrically-conducting adhesives
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/0201—Thermal arrangements, e.g. for cooling, heating or preventing overheating
- H05K1/0203—Cooling of mounted components
- H05K1/0207—Cooling of mounted components using internal conductor planes parallel to the surface for thermal conduction, e.g. power planes
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
- H05K3/022—Processes for manufacturing precursors of printed circuits, i.e. copper-clad substrates
-
- 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
- B32B2038/0052—Other operations not otherwise provided for
- B32B2038/0076—Curing, vulcanising, cross-linking
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/302—Conductive
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- 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
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/546—Flexural strength; Flexion stiffness
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- 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
- B32B2457/08—PCBs, i.e. printed circuit boards
-
- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
-
- 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
- C08K3/28—Nitrogen-containing compounds
- C08K2003/282—Binary compounds of nitrogen with aluminium
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Physics & Mathematics (AREA)
- Fluid Mechanics (AREA)
- Mechanical Engineering (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Laminated Bodies (AREA)
Abstract
The invention belongs to the technical field of metal copper clad laminate manufacturing, and discloses a high-thermal-conductivity copper clad laminate and a preparation method thereof. This high heat conduction copper-clad plate includes: a first copper foil layer; the first insulating layer is coated on the first copper foil layer; the middle layer is coated on the first insulating layer; a second insulating layer coated on the intermediate layer; and a second copper foil layer covering the second insulating layer. The copper-clad plate with the specific combination structure, which is constructed by the invention, has excellent overall heat conductivity coefficient which is more than 75W/M.K, and can effectively improve the heat dissipation effect of the copper-clad plate; the high-heat-conductivity heat-conducting wire has good bending resistance, the bending resistance times are more than or equal to 15, the processing and bending assembly in any mode can be carried out for multiple times, the high-heat-conductivity heat-conducting wire has high heat-conducting performance and the capability of being processed and bent for multiple times, and the high-heat-conducting wire can be well applied to printed circuits and is suitable for industrial production.
Description
Technical Field
The invention belongs to the technical field of metal copper clad laminate manufacturing, and particularly relates to a high-thermal-conductivity copper clad laminate and a preparation method thereof.
Background
The Copper Clad Laminate is a plate-shaped composite material prepared by dipping electronic glass fiber cloth or other reinforced materials in resin liquid, coating Copper foil on one surface or two surfaces of the electronic glass fiber cloth or other reinforced materials, and performing hot pressing at a certain temperature and pressure, and is called as a Copper Clad Laminate (CCL), which is called as a Copper Clad Laminate for short. Copper-clad plates have gradually become the basic material for manufacturing Printed Circuit Boards (PCBs) due to their excellent heat dissipation capability. PCBs are one of the important components of the electronics industry, ranging from small to electronic watches, calculators, to computers, communications electronics, and military weapons systems, all using printed circuit boards as long as there are electronic components of integrated circuits.
The copper-clad plate is mainly used for conducting, insulating and supporting on the whole printed circuit board. The resin liquid in the copper-clad plate generally uses a thermosetting resin composition. Thermosetting resins are a large class of synthetic resins that undergo chemical reactions under heat and pressure or under the action of curing agents, ultraviolet light, etc., and are crosslinked and cured into insoluble and infusible substances. Thermosetting resin, a curing agent, an accelerator, a filler and the like form a thermosetting resin composition, the thermosetting resin composition is prepared into a resin glue solution to be applied to the production of prepreg, and the prepreg is subjected to hot pressing to obtain the copper clad laminate.
In order to provide the prepreg and the copper clad laminate with ultrahigh heat dissipation characteristics, the industry generally uses a metal base as a substrate, and a large amount of heat-conducting ceramic powder such as aluminum oxide, aluminum nitride and/or silicon carbide is added into an insulating layer, so as to achieve the purposes of quickly dissipating heat and reducing the temperature of an electronic circuit in a use state. However, with the increase of the amount of the heat conductive filler, the metal-based copper clad laminate cannot be applied to circuits requiring complicated processing conditions and assembling modes due to the problems of high hardness, incapability of bending and the like.
In recent years, the development of new energy vehicles is changing day by day, and the new energy vehicles have been promoted to the strategic level of energy transformation by the nation. The new energy vehicle thoroughly breaks the domination of the fuel vehicle in the market, and the core technology of the new energy vehicle is the rapid development and breakthrough in the aspects of charging and power storage, wherein the rapid charging technology and the large-capacity battery technology are important. Different from the states of other electrical appliances in the working process, the new energy vehicle is in the charging process, namely a charging device part or an electric storage device part, and the new energy vehicle is in a quick acting process, so that a large amount of heat is quickly accumulated, if the new energy vehicle cannot quickly dissipate heat to keep an electronic circuit component in a low-temperature state, the new energy vehicle can not normally operate due to circuit damage, and the new energy vehicle can cause circuit fire to form a major safety accident due to the fact that the new energy vehicle is in a heavy state.
For copper-clad plates applied to the field of new energy vehicles, domestic researchers have conducted many researches on such copper-clad plates. CN 111171771A discloses a bonding sheet and a preparation method thereof, wherein an epoxy modified high-thermal-conductivity glue solution is coated on a release film and then dried to obtain the bonding sheet which has excellent high-thermal-conductivity property, high elasticity and low modulus. According to the invention, the mode of compounding the high-thermal-conductivity oxide powder by the organic silicon modified resin is adopted, and although the thermal conductivity of the obtained insulating layer reaches 3.0W/MK, the overall thermal conductivity of the insulating layer is poor. Meanwhile, the aluminum plate is used as a substrate, and as a charging circuit device, an arc-shaped or bent circuit is often required, so that the application range of the design is limited, and the plastic formability is low.
CN 104629263A discloses a method for manufacturing a bending-resistant aluminum-based copper-clad plate, which adopts epoxy resin to compound amine curing agent, toughening agent and proper amount of heat-conducting ceramic powder, and the bending-resistant aluminum-based copper-clad plate is formed by coating and pressing. According to the invention, the epoxy resin is modified by using the components with excellent toughening effect such as nitrile rubber, chloroprene rubber or polyvinyl butyral, and although the insulating layer which is bending-resistant and convenient to process and assemble is formed, the main radiator of the epoxy resin is an aluminum plate, and the deformation resistance of the aluminum plate is greatly reduced after a long time, so that the aluminum plate cannot be bent for multiple times, and the epoxy resin is not suitable for being used in circuits in the charging industry.
In summary, there is a need to develop a copper-clad plate with ultra-high thermal conductivity and high heat dissipation performance, which can be processed and bent in any manner for many times.
Disclosure of Invention
The invention aims to overcome the technical defects that the copper-clad plate in the prior art cannot have high heat-conducting performance and can be processed and assembled in a bending mode at will, and provides the copper-clad plate which has ultrahigh heat-conducting coefficient and strong heat-radiating performance and can be processed and assembled in a bending mode for multiple times.
The invention provides a high-thermal-conductivity copper-clad plate, which comprises:
a first copper foil layer;
the first insulating layer is coated on the first copper foil layer;
the middle layer is coated on the first insulating layer;
a second insulating layer coated on the intermediate layer; and
the second copper foil layer is covered on the second insulating layer;
wherein the raw materials for forming the first insulating layer and the second insulating layer independently comprise the following components in parts by weight: 10 to 80 weight portions of epoxy resin A, 1 to 40 weight portions of curing agent B, 0.01 to 1 weight portion of accelerant C, 50 to 200 weight portions of filler D and 10 to 50 weight portions of toughener E; the thermal conductivity of the first insulating layer and the second insulating layer is 1-3W/MK independently;
the intermediate layer is formed by the following raw materials in parts by weight: 10 to 80 parts of epoxy resin F, 1 to 40 parts of curing agent G, 0.01 to 1 part of accelerator H, 50 to 500 parts of ultra-high conductivity inorganic powder I and 10 to 50 parts of toughener J; the heat conductivity coefficient of the intermediate layer is 100-200W/MK.
In a preferred embodiment, the first and second copper foil layers each independently have a thickness of 12 to 105 μm; the first insulating layer and the second insulating layer have a thickness of 50 to 200 μm independently of each other; the thickness of the intermediate layer is 100 to 1000 μm.
In a preferred embodiment, the epoxy resin a is a difunctional epoxy resin and/or a novolac epoxy resin; the curing agent B is at least one of dicyandiamide, 4-diaminodiphenyl sulfone, phenolic resin, acid anhydride and active ester; the accelerant C is an imidazole accelerant; the filler D is an inorganic filler; the toughening agent E is at least one of phenoxy resin, polyethylene modified resin, polyurethane modified resin and polybutadiene modified resin.
In a preferred embodiment, the epoxy resin F is a difunctional epoxy resin and/or a novolac epoxy resin; the curing agent G is at least one of dicyandiamide, 4-diaminodiphenyl sulfone, phenolic resin, acid anhydride and active ester; the accelerant H is an imidazole accelerant; the ultra-high conductivity inorganic powder I is at least one of insulating carbon powder, conductive carbon powder, graphene powder and modified conductive carbon powder; the toughening agent J is at least one of phenoxy resin, polyethylene modified resin, polyurethane modified resin and polybutadiene modified resin.
In a preferred embodiment, the raw materials for forming the first insulating layer and the second insulating layer each independently include, in parts by weight: 10 to 45 weight portions of epoxy resin A, 1 to 10 weight portions of curing agent B, 0.02 to 0.5 weight portion of accelerant C, 100 to 200 weight portions of filler D and 20 to 40 weight portions of toughener E.
In a preferred embodiment, the raw materials for forming the intermediate layer include, by weight: 10 to 45 weight portions of epoxy resin F, 1 to 10 weight portions of curing agent G, 0.02 to 0.5 weight portion of accelerant H, 300 to 500 weight portions of ultra-high conductivity inorganic powder I and 20 to 40 weight portions of toughener J.
The second purpose of the invention provides a preparation method of a high-thermal-conductivity copper-clad plate, which comprises the following steps:
s1: adding a curing agent B and an accelerator C into a solvent I for full dissolution, then sequentially adding an epoxy resin A, a filler D and a toughening agent E for full dissolution, and respectively independently obtaining a first insulating layer glue solution and a second insulating layer glue solution;
s2: adding a curing agent G and an accelerator H into a solvent II for full dissolution, and then sequentially adding an epoxy resin F, an ultrahigh-conductivity inorganic powder I and a toughening agent J for full dissolution to obtain an intermediate layer glue solution;
s3: coating the first insulation layer glue solution on the first copper foil layer and baking to obtain a first semi-cured glue film; coating the second insulating layer glue solution on the second copper foil layer and baking to obtain a second semi-cured glue film; coating the intermediate layer glue solution on a release film and baking to obtain an intermediate layer semi-cured glue film;
s4: and stripping the release film on the intermediate-layer semi-cured adhesive film, respectively coating one surface of the first semi-cured adhesive film coated with the first insulating layer adhesive solution and one surface of the second semi-cured adhesive film coated with the second insulating layer adhesive solution on the two side surfaces of the intermediate-layer semi-cured adhesive film stripped from the release film, and performing hot-press lamination through a hot press to obtain the high-thermal-conductivity copper-clad plate.
In a preferred embodiment, in step S1, the solvent I is at least one of acetone, butanone, cyclohexanone, ethylene glycol methyl ether, propylene glycol methyl ether and propylene glycol methyl ether acetate; in the step S1, the solid content of the first insulating layer glue solution is 65-75%; in the step S1, the solid content in the second insulating layer glue solution is 65-75%.
In a preferred embodiment, in step S2, the solvent II is at least one of acetone, butanone, cyclohexanone, ethylene glycol methyl ether, propylene glycol methyl ether, and propylene glycol methyl ether acetate; in the step S2, the solid content in the middle layer glue solution is 65-75%.
In a preferred embodiment, in step S3, the baking conditions include a temperature of 180 to 220 ℃ and a time of 10 to 20min.
In a preferred embodiment, in step S4, the heat and pressure lamination conditions include:
lamination temperature: heating to 220 ℃ at a heating rate of 1.0-3.0 ℃/min;
lamination pressure: applying full pressure when the material temperature is 80-100 ℃, wherein the full pressure is 280-320 psi;
during curing: controlling the material temperature at 220 ℃, and keeping the temperature for 120-150 min.
The invention has the beneficial technical effects that:
(1) According to the invention, the ultrahigh-conductivity inorganic powder with high thermal conductivity is added in the middle layer, the insulating layers with low thermal conductivity are respectively covered on the two sides of the middle layer, and finally the copper foil is covered on the insulating layers to construct the copper-clad plate with a specific combined structure, on the basis, the thermal conductivity of the insulating layers is controlled to be 1-3W/MK, and the thermal conductivity of the middle layer is controlled to be 100-200W/MK, so that the formed copper-clad plate not only has excellent overall thermal conductivity, the overall thermal conductivity is more than 75W/M.K, and the heat dissipation effect of the copper-clad plate is effectively improved; and the high-heat-conductivity heat-insulating material has good bending resistance, the bending resistance times are more than or equal to 15, the processing and bending assembly in any mode can be carried out for many times, and the high-heat-conductivity heat-insulating material has high heat-conducting performance and the capability of processing and bending assembly for many times.
(2) The electrical property of the high-thermal-conductivity copper-clad plate provided by the invention is not much different from that of the prior art, and meanwhile, the interlayer bonding force and the electrical property of the high-thermal-conductivity copper-clad plate completely meet the requirements of IPC-4101 Standard copper-clad laminate for printed circuits, so that the high-thermal-conductivity copper-clad plate provided by the invention can be well applied to printed circuits and is suitable for industrial production.
Drawings
Fig. 1 is a schematic structural diagram of a copper-clad plate.
Description of reference numerals:
10-first copper foil layer, 10 '-second copper foil layer, 20-first insulation layer, 20' -second insulation layer, 30-intermediate layer.
Detailed Description
The present invention will be described in detail below by way of examples.
It should be noted that, in the present invention, the terms "upper", "lower", and the like indicate the orientation or the positional relationship based on the orientation or the positional relationship shown in the drawings, which are only for the convenience of describing the present invention and simplifying the description, but do not indicate or imply that the product structure referred to must be in a specific orientation, and thus, should not be construed as limiting the present invention. Furthermore, the terms "first", "second", "solvent I", "solvent II", "epoxy resin a", "epoxy resin F", "curing agent B", "curing agent G", "accelerator C", "accelerator H", "toughener E" and "toughener J" are merely to distinguish between different objects and are not to be construed as indicating or implying a relative importance thereof.
The invention provides a high-thermal-conductivity copper-clad plate, as shown in fig. 1, each layered structure of the high-thermal-conductivity copper-clad plate comprises a first copper foil layer 10, a first insulating layer 20, an intermediate layer 30, a second insulating layer 20 'and a second copper foil layer 10' from bottom to top in sequence.
In the present invention, the first insulating layer 20 and the second insulating layer 20' are formed from raw materials, in parts by weight, each independently including: 10 to 80 parts of epoxy resin A, 1 to 40 parts of curing agent B, 0.01 to 1 part of accelerator C, 50 to 200 parts of filler D and 10 to 50 parts of toughener E. Preferably, the raw materials for forming the first insulating layer 20 and the second insulating layer 20' each independently include, in parts by weight: 10 to 45 weight portions of epoxy resin A, 1 to 10 weight portions of curing agent B, 0.02 to 0.5 weight portion of accelerant C, 100 to 150 weight portions of filler D and 20 to 40 weight portions of toughener E. The weight parts of the epoxy resin A can be 10 parts by weight, 15 parts by weight, 20 parts by weight, 25 parts by weight, 30 parts by weight, 35 parts by weight, 40 parts by weight, 45 parts by weight; the weight portion of the curing agent B can be 1 weight portion, 3 weight portions, 5 weight portions and 10 weight portions; the weight parts of accelerator C may be 0.02, 0.1, 0.2, 0.3, 0.4, 0.5; the weight parts of the filler D can be 100 parts by weight, 120 parts by weight, 140 parts by weight, 150 parts by weight; the weight portion of the toughening agent E can be 20 weight portions, 30 weight portions and 40 weight portions. The thermal conductivity of the first insulating layer 10 and the second insulating layer 10' may be 1 to 3W/MK, respectively and independently. Particularly preferably, when the first and second insulating layers 20 and 20 'have the same composition and content, the first and second insulating layers 20 and 20' have the same thermal conductivity, which may be 1W/MK, 1.5W/MK, 2W/MK, 2.5W/MK, 3W/MK.
In the present invention, the intermediate layer 30 is formed from the following raw materials in parts by weight: 10 to 80 parts of epoxy resin F, 1 to 40 parts of curing agent G, 0.01 to 1 part of accelerator H, 50 to 500 parts of ultra-high conductivity inorganic powder I and 10 to 50 parts of toughener J. Preferably, the intermediate layer 30 is formed from raw materials including, by weight: 10 to 45 weight portions of epoxy resin F, 1 to 10 weight portions of curing agent G, 0.02 to 0.5 weight portion of accelerant H, 300 to 500 weight portions of ultra-high conductivity inorganic powder I and 20 to 40 weight portions of toughener J. The weight parts of the epoxy resin F may be 10, 15, 20, 25, 30, 35, 40, 45 parts; the weight parts of the curing agent G can be 1 weight part, 3 weight parts, 5 weight parts and 10 weight parts; the weight parts of accelerator H may be 0.02 parts, 0.1 parts, 0.2 parts, 0.3 parts, 0.4 parts, 0.5 parts; the weight parts of the ultra-high conductivity inorganic powder I can be 300 parts by weight, 400 parts by weight, 500 parts by weight; the weight parts of the toughening agent J can be 20 parts, 30 parts and 40 parts. The intermediate layer 30 may have a thermal conductivity of 100 to 200W/MK, for example, 100W/MK, 150W/MK, 200W/MK.
As shown in fig. 1, in the present invention, the thicknesses of the first copper foil layer 10 and the second copper foil layer 10' are each independently 12 to 105 μm, and may be, for example, 12 μm, 25 μm, 35 μm, 45 μm, 55 μm, 65 μm, 75 μm, 85 μm, 95 μm, 105 μm; the thicknesses of the first insulating layer 20 and the second insulating layer 20' are each independently 50 to 200 μm, and may be, for example, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm, 100 μm, 110 μm, 120 μm, 130 μm, 140 μm, 150 μm, 160 μm, 170 μm, 180 μm, 190 μm, 200 μm; the thickness of the intermediate layer 30 is 100 to 1000. Mu.m, and may be, for example, 100. Mu.m, 200. Mu.m, 300. Mu.m, 400. Mu.m, 500. Mu.m, 600. Mu.m, 700. Mu.m, 800. Mu.m, 900. Mu.m, or 1000. Mu.m. Preferably, the first and second copper foil layers 10 and 10' are the same in thickness, and may be 35 μm; preferably, the first insulating layer 20 and the second insulating layer 20' are the same in thickness, and may be 100 μm; preferably, the thickness of the intermediate layer may be 400 μm.
In the invention, the epoxy resin A can be bifunctional epoxy resin and/or novolac epoxy resin; preferably, the bifunctional epoxy resin is a bisphenol a type epoxy resin and/or a biphenyl epoxy resin; preferably, the novolac epoxy resin is at least one of phenol novolac type epoxy resin, o-cresol novolac type epoxy resin, bisphenol a novolac type epoxy resin, and dicyclopentadiene phenol type epoxy resin. The curing agent B may be at least one of Dicyandiamide (DICY), 4-diaminodiphenyl sulfone (DDS), a phenol resin, an acid anhydride, and an active ester. The accelerant C can be an imidazole accelerant; preferably, the imidazole accelerator is at least one of 2-methylimidazole, 1-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecylimidazole and 2-phenyl-4-methylimidazole. The filler D may be an inorganic filler; preferably, the inorganic filler is at least one of alumina, magnesia, silicon carbide, silicon nitride, calcium silicate, calcium carbonate, clay, talc and mica. The toughening agent E can be at least one of phenoxy resin, polyethylene modified resin, polyurethane modified resin and polybutadiene modified resin.
In the invention, the epoxy resin F can be bifunctional epoxy resin and/or novolac epoxy resin; preferably, the bifunctional epoxy resin is a bisphenol a type epoxy resin and/or a biphenyl epoxy resin; preferably, the novolac epoxy resin is at least one of phenol novolac epoxy resin, o-cresol novolac epoxy resin, bisphenol a novolac epoxy resin, and dicyclopentadiene phenol epoxy resin. The curing agent G may be at least one of Dicyandiamide (DICY), 4-diaminodiphenyl sulfone (DDS), a phenol resin, an acid anhydride, and an active ester. The accelerant H can be an imidazole accelerant; preferably, the imidazole accelerator is at least one of 2-methylimidazole, 1-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecylimidazole and 2-phenyl-4-methylimidazole. The ultra-high conductivity inorganic powder I can be at least one of insulating carbon powder, conductive carbon powder, graphene powder and modified conductive carbon powder. The toughening agent J can be at least one of phenoxy resin, polyethylene modified resin, polyurethane modified resin and polybutadiene modified resin.
In the present invention, more preferably, the epoxy resin a and the epoxy resin F have the same specific chemical composition, and specific examples include, but are not limited to: macro-Chang GESN901 and/or Olin. More preferably, the curing agent B and the curing agent G have the same chemical composition, and specific examples include but are not limited to: dicyandiamide (DICY). More preferably, the accelerator C and the accelerator H have the same chemical composition, and specific examples include, but are not limited to: 2-methylimidazole. More preferably, specific examples of filler D include, but are not limited to: alumina (particle size of 1 to 10 μm, purity 99% or more) and/or aluminum nitride (particle size of 1 to 5 μm, purity 99% or more). More preferably, the specific chemical compositions of toughening agents E and J are the same, and specific examples include, but are not limited to: MEK solution (35% solids content). More preferably, specific examples of the ultra-high conductive inorganic powder I include, but are not limited to: conductive carbon powder. It should be noted that, when the specific chemical components of the epoxy resin a and the epoxy resin F are the same, the specific chemical components of the curing agent B and the curing agent G are the same, the specific chemical components of the accelerator C and the accelerator H are the same, and the specific chemical components of the toughener E and the toughener J are the same, in the subsequent experimental processes, to simplify the description, the epoxy resin F is directly represented by the epoxy resin a, the curing agent G is directly represented by the curing agent B, the accelerator H is directly represented by the accelerator C, and the toughener J is directly represented by the toughener E.
The second aspect of the invention provides a preparation method of a high-thermal-conductivity copper-clad plate, which comprises the following steps:
s1: adding a curing agent B and an accelerant C into a solvent I for full dissolution, then sequentially adding an epoxy resin A, a filler D and a toughening agent E for full dissolution, and respectively and independently obtaining a first insulating layer glue solution and a second insulating layer glue solution;
s2: adding a curing agent G and an accelerant H into a solvent II for full dissolution, and then sequentially adding an epoxy resin F, an ultrahigh-conductivity inorganic powder I and a toughening agent J for full dissolution to obtain an intermediate layer glue solution;
s3: coating the first insulation layer glue solution on the first copper foil layer and baking to obtain a first semi-cured glue film; coating the second insulating layer glue solution on the second copper foil layer and baking to obtain a second semi-cured glue film; coating the intermediate layer glue solution on a release film and baking to obtain an intermediate layer semi-cured glue film;
s4: and stripping the release film on the intermediate-layer semi-cured adhesive film, respectively coating one surface of the first semi-cured adhesive film coated with the first insulating layer adhesive solution and one surface of the second semi-cured adhesive film coated with the second insulating layer adhesive solution on the two side surfaces of the intermediate-layer semi-cured adhesive film stripped from the release film, and performing hot-press lamination through a hot press to obtain the high-thermal-conductivity copper-clad plate.
Preferably, in step S1, the solvent I is at least one of acetone, butanone, cyclohexanone, ethylene glycol methyl ether, propylene glycol methyl ether and propylene glycol methyl ether acetate; more preferably, specific examples of the solvent I include, but are not limited to: butanone. Preferably, in step S1, the solid content in the first insulating glue solution may be 65% to 75%, for example, 65%, 70%, 75%; preferably, in step S1, the solid content in the second insulating layer glue solution may be 65% to 75%, for example, 65%, 70%, 75%. More preferably, the first insulating layer glue solution and the second insulating layer glue solution have the same components, component contents and solid contents.
In the present invention, preferably, in step S2, the solvent II is at least one of acetone, butanone, cyclohexanone, ethylene glycol methyl ether, propylene glycol methyl ether, and propylene glycol methyl ether acetate; more preferably, specific examples of the solvent II include, but are not limited to: butanone. Preferably, in step S2, the solid content in the interlayer glue solution may be 65% to 75%, for example, 65%, 70%, 75%.
In the present invention, preferably, in step S3, the baking conditions include that the temperature may be 180 to 220 ℃, for example, 180 ℃, 200 ℃, 220 ℃; the time may be 10 to 20min, for example 10min, 15min, 20min.
In the present invention, preferably, in step S4, the heat press lamination conditions include:
lamination temperature: heating to 220 ℃ at a heating rate of 1.0-3.0 ℃/min; for example, the temperature rise rate may be 1.0 ℃/min, 1.5 ℃/min, 2.0 ℃/min, 2.5 ℃/min, 3.0 ℃/min.
Lamination pressure: full pressure is applied at a material temperature of 80-100 deg.C, and the full pressure can be 280-320 psi, such as 280psi, 290psi, 300psi, 310psi, 320psi.
During curing: controlling the material temperature at 220 deg.C, and maintaining for 120-150 min, such as 120min, 130min, 140min, and 150min.
Examples
Raw materials:
(A) The epoxy resin has an epoxy equivalent of 170-950 g/eq. The epoxy resin can be selected from the following two epoxy resins A-1 and A-2:
(A-1) Macro-Chang GESN901, epoxy equivalent 459g/eq;
(A-2) Olin, manufactured by Orchidaceae chemical industry, with a trade name of DER593, epoxy equivalent of 330g/eq;
(B) Curing agent: dicyandiamide;
(C) Accelerator (b): 2-phenylimidazole, available from chemical industries, inc. of four countries;
(D) Filling:
(D-1) alumina (particle size of 1 to 10 μm, purity 99% or more);
(D-2) aluminum nitride (particle diameter of 1 to 5 μm, purity 99% or more);
(E) A toughening agent: MEK solution (35% solids);
(I) Ultra-high conductivity inorganic powder: conductive carbon powder.
The preparation method of the high-thermal-conductivity copper-clad plate comprises the following steps:
s1: accurately weighing the raw material components, adding dicyandiamide and 2-phenylimidazole into a butanone solvent, stirring at a stirring speed of 50rpm until the dicyandiamide and 2-phenylimidazole are fully dissolved, sequentially adding Macro-Chang GESN901, olin, alumina, aluminum nitride and MEK solutions, stirring at a stirring speed of 200rpm until the macrochan GESN901, olin, alumina, aluminum nitride and MEK solutions are fully dissolved, finally adjusting the solid content of the solutions to 65% by using the butanone solvent, and preparing to obtain a first insulating layer glue solution and a second insulating layer glue solution.
S2: accurately weighing the raw material components, adding dicyandiamide and 2-phenylimidazole into butanone solvent, stirring at the stirring speed of 50rpm until the dicyandiamide and 2-phenylimidazole are fully dissolved, sequentially adding Macro-Chang GESN901, olin, conductive carbon powder and MEK solution, stirring at the stirring speed of 200rpm until the macrochan GESN901, olin, conductive carbon powder and MEK solution are fully dissolved, finally adjusting the solid content of the solution to 65% by using the butanone solvent, and preparing the interlayer glue solution.
S3: coating the first insulating layer glue solution obtained in the step S1 on a first copper foil layer, standing for 3min at normal temperature, then placing the first copper foil layer into a 200 ℃ oven for baking for 15min, and pre-curing to obtain a first semi-cured glue film with the thickness of 110 microns; coating the second insulating layer glue solution obtained in the step S1 on a second copper foil layer, standing for 3min at normal temperature, then placing the second copper foil layer into a 200 ℃ oven for baking for 15min, and pre-curing to obtain a second semi-cured glue film with the thickness of 110 microns; and (3) coating the intermediate layer glue solution obtained in the step (S2) on a release film, standing at normal temperature for 3min, then placing in a 200 ℃ oven for baking for 15min, and pre-curing to obtain an intermediate layer semi-cured glue film with the thickness of 420 microns.
S4: and stripping the release film on the intermediate-layer semi-cured adhesive film, respectively coating one surface of the first semi-cured adhesive film coated with the first insulating layer adhesive solution and one surface of the second semi-cured adhesive film coated with the second insulating layer adhesive solution on the two side surfaces of the intermediate-layer semi-cured adhesive film stripped from the release film, and performing hot-press lamination through a hot press to prepare the high-thermal-conductivity copper-clad plate with the copper foil coated on the two sides. The heating and pressurizing conditions are as follows: (1) temperature setting: heating to 220 ℃ at the heating rate of 3.0 ℃/min; (2) pressure setting: when the temperature of the material is raised to 100 ℃, full pressure is applied, and the full pressure is 300psi; (3) curing: controlling the material temperature at 220 ℃, and keeping the temperature for 120min.
Examples 1 to 3 and comparative examples 1 to 6
The copper-clad plate is prepared according to the preparation method of the high-thermal-conductivity copper-clad plate, wherein the specific mixture ratio (in parts by weight) of the raw materials A-1, A-2, B, C, D-1, D-2, E and I in the examples 1-3 is shown in the table 1.
Comparative examples 1 to 3 are compared with examples 1 to 3, except that comparative examples 1 to 3 have no intermediate layer and are prepared by: uniformly coating the prepared resin on a copper foil, baking and cooling the copper foil to be in a semi-cured state, and performing press molding on the glue surfaces of two semi-cured glue film coated copper foils; the other conditions were the same as in examples 1 to 3, and the specific raw material ratios (in parts by weight) of the respective proportions are shown in Table 1. Comparative examples 4 to 6 are compared with examples 1 to 3, except that the raw material ratios in comparative examples 4 to 6 are not within the ranges described above, the other preparation methods are the same as in examples 1 to 3, and the specific raw material ratios (in parts by weight) of each comparative example are shown in table 1.
Test method
Surface resistance: the above examples 1 to 3 and comparative examples 1 to 6 were measured using a resistance cell according to the IPC-TM-650, clause 2.5.17.1, and the results are shown in Table 2.
Volume resistance: the above examples 1 to 3 and comparative examples 1 to 6 were measured using a resistance cell according to the IPC-TM-650, clause 2.5.17.1, and the results are shown in Table 2.
Interlayer adhesion: the above examples 1 to 3 and comparative examples 1 to 6 were measured by a peel strength tester according to IPC-TM-650, clause 2.4.8.2, and the results are shown in Table 2.
Bending resistance: the above examples 1 to 3 and comparative examples 1 to 6 were measured by fpc bending resistance tester according to the standard IPC-4101, and the test results are shown in Table 2.
Thermal conductivity of the insulating layer: the above examples 1 to 3 and comparative examples 1 to 6 were measured using a thermal conductivity tester according to standard astm d-5470, and the test results are shown in table 2.
Intermediate layer thermal conductivity: the above examples 1 to 3 and comparative examples 1 to 6 were measured using a thermal conductivity tester according to standard astm d-5470, and the test results are shown in table 2.
Overall thermal conductivity: the above examples 1 to 3 and comparative examples 1 to 6 were measured using a thermal conductivity tester according to standard astm d-5470, and the test results are shown in table 2.
Test results
TABLE 2
As can be seen from the test results in Table 2, the invention constructs the copper-clad plate with a specific combination structure by adding the ultrahigh-conductivity inorganic powder with high thermal conductivity in the middle layer, respectively covering the insulating layers with low thermal conductivity on the two sides of the middle layer, and finally covering the copper foil on the insulating layers, on the basis, the thermal conductivity of the insulating layers is controlled to be 1-3W/MK, and the thermal conductivity of the middle layer is controlled to be 100-200W/MK, so that the formed copper-clad plate not only has excellent overall thermal conductivity, the overall thermal conductivity is more than 75W/M.K, and the heat dissipation effect of the copper-clad plate is effectively improved; in addition, the copper-clad plate prepared by the preparation method provided by the invention also has good bending resistance, the bending resistance times are more than or equal to 15 times, the copper-clad plate can be processed and bent in any mode for multiple times, and the copper-clad plate has high heat-conducting property and the capability of being processed and bent for multiple times and assembled randomly.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made in the above embodiments by those of ordinary skill in the art without departing from the principle and spirit of the present invention.
Claims (11)
1. The high-thermal-conductivity copper-clad plate is characterized by comprising:
a first copper foil layer;
the first insulating layer is coated on the first copper foil layer;
an intermediate layer coated on the first insulating layer;
a second insulating layer coated on the intermediate layer; and
the second copper foil layer is covered on the second insulating layer;
wherein the forming raw materials of the first insulating layer and the second insulating layer respectively and independently comprise the following components in parts by weight: 10 to 80 parts of epoxy resin A, 1 to 40 parts of curing agent B, 0.01 to 1 part of accelerator C, 50 to 200 parts of filler D and 10 to 50 parts of toughener E; the thermal conductivity of the first insulating layer and the second insulating layer is 1-3W/MK independently;
the forming raw materials of the middle layer comprise the following components in parts by weight: 10 to 80 weight portions of epoxy resin F, 1 to 40 weight portions of curing agent G, 0.01 to 1 weight portion of accelerant H, 50 to 500 weight portions of ultra-high conductivity inorganic powder I and 10 to 50 weight portions of flexibilizer J; the heat conductivity coefficient of the intermediate layer is 100-200W/MK.
2. The high thermal conductivity copper-clad plate according to claim 1, wherein the first copper foil layer and the second copper foil layer each independently have a thickness of 12 to 105 μm; the first insulating layer and the second insulating layer have a thickness of 50 to 200 μm independently of each other; the thickness of the intermediate layer is 100 to 1000 μm.
3. The high-thermal-conductivity copper-clad plate according to claim 1, wherein the epoxy resin A is a bifunctional epoxy resin and/or a novolac epoxy resin; the curing agent B is at least one of dicyandiamide, 4-diaminodiphenyl sulfone, phenolic resin, acid anhydride and active ester; the accelerant C is an imidazole accelerant; the filler D is an inorganic filler; the toughening agent E is at least one of phenoxy resin, polyethylene modified resin, polyurethane modified resin and polybutadiene modified resin.
4. The copper-clad plate with high thermal conductivity according to claim 1, wherein the epoxy resin F is a bifunctional epoxy resin and/or a novolac epoxy resin; the curing agent G is at least one of dicyandiamide, 4-diaminodiphenyl sulfone, phenolic resin, acid anhydride and active ester; the accelerant H is an imidazole accelerant; the ultra-high conductivity inorganic powder I is at least one of insulating carbon powder, conductive carbon powder, graphene powder and modified conductive carbon powder; the toughening agent J is at least one of phenoxy resin, polyethylene modified resin, polyurethane modified resin and polybutadiene modified resin.
5. The copper-clad plate with high thermal conductivity according to claim 1, wherein the raw materials for forming the first insulating layer and the second insulating layer independently comprise, in parts by weight: 10 to 45 weight portions of epoxy resin A, 1 to 10 weight portions of curing agent B, 0.02 to 0.5 weight portion of accelerant C, 100 to 200 weight portions of filler D and 20 to 40 weight portions of toughener E.
6. The copper-clad plate with high thermal conductivity according to claim 1, wherein the intermediate layer is formed from the following raw materials in parts by weight: 10 to 45 weight portions of epoxy resin F, 1 to 10 weight portions of curing agent G, 0.02 to 0.5 weight portion of accelerant H, 300 to 500 weight portions of ultra-high conductive inorganic powder I and 20 to 40 weight portions of toughener J.
7. A preparation method of the high thermal conductivity copper-clad plate of any one of claims 1 to 6, characterized in that the method comprises the following steps:
s1: adding a curing agent B and an accelerant C into a solvent I for full dissolution, then sequentially adding an epoxy resin A, a filler D and a toughening agent E for full dissolution, and respectively and independently obtaining a first insulating layer glue solution and a second insulating layer glue solution;
s2: adding a curing agent G and an accelerant H into a solvent II for full dissolution, and then sequentially adding an epoxy resin F, an ultrahigh-conductivity inorganic powder I and a toughening agent J for full dissolution to obtain an intermediate layer glue solution;
s3: coating the first insulation layer glue solution on the first copper foil layer and baking to obtain a first semi-cured glue film; coating the second insulating layer glue solution on the second copper foil layer and baking to obtain a second semi-cured glue film; coating the intermediate layer glue solution on a release film and baking to obtain an intermediate layer semi-cured glue film;
s4: and stripping the release film on the intermediate-layer semi-cured adhesive film, respectively coating one surface of the first semi-cured adhesive film coated with the first insulating layer adhesive solution and one surface of the second semi-cured adhesive film coated with the second insulating layer adhesive solution on the surfaces of two sides of the intermediate-layer semi-cured adhesive film stripped from the release film, and performing hot-press lamination through a hot press to prepare the high-thermal-conductivity copper-clad plate.
8. The method for preparing the high-thermal-conductivity copper-clad plate according to claim 7, wherein in the step S1, the solvent I is at least one of acetone, butanone, cyclohexanone, ethylene glycol methyl ether, propylene glycol methyl ether and propylene glycol methyl ether acetate; in the step S1, the solid content in the first insulating layer glue solution is 65-75%; in the step S1, the solid content in the second insulating layer glue solution is 65-75%.
9. The method for preparing the high-thermal-conductivity copper-clad plate according to claim 7, wherein in the step S2, the solvent II is at least one of acetone, butanone, cyclohexanone, ethylene glycol methyl ether, propylene glycol methyl ether and propylene glycol methyl ether acetate; in the step S2, the solid content in the middle layer glue solution is 65-75%.
10. The method for preparing the high-thermal-conductivity copper-clad plate according to claim 7, wherein in the step S3, the baking conditions include a temperature of 180-220 ℃ and a time of 10-20 min.
11. The method for preparing the high-thermal-conductivity copper-clad plate according to claim 7, wherein in step S4, the hot-press lamination conditions comprise:
lamination temperature: heating to 220 ℃ at a heating rate of 1.0-3.0 ℃/min;
lamination pressure: applying full pressure when the material temperature is 80-100 ℃, wherein the full pressure is 280-320 psi;
during curing: controlling the material temperature at 220 ℃, and keeping the temperature for 120-150 min.
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| CN115139589B (en) | 2024-03-19 |
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