WO2022181291A1 - ポリイミド樹脂組成物及び金属ベース基板 - Google Patents
ポリイミド樹脂組成物及び金属ベース基板 Download PDFInfo
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- WO2022181291A1 WO2022181291A1 PCT/JP2022/004379 JP2022004379W WO2022181291A1 WO 2022181291 A1 WO2022181291 A1 WO 2022181291A1 JP 2022004379 W JP2022004379 W JP 2022004379W WO 2022181291 A1 WO2022181291 A1 WO 2022181291A1
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- Prior art keywords
- polyimide resin
- filler
- resin composition
- group
- less
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 194
- 239000009719 polyimide resin Substances 0.000 title claims abstract description 191
- 239000000203 mixture Substances 0.000 title claims abstract description 80
- 229910052751 metal Inorganic materials 0.000 title claims description 62
- 239000002184 metal Substances 0.000 title claims description 62
- 239000000758 substrate Substances 0.000 title claims description 54
- 239000000945 filler Substances 0.000 claims abstract description 71
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 27
- 125000001142 dicarboxylic acid group Chemical group 0.000 claims abstract description 21
- 150000002484 inorganic compounds Chemical class 0.000 claims abstract description 13
- 229910010272 inorganic material Inorganic materials 0.000 claims abstract description 13
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 10
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 10
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims abstract description 10
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims abstract description 9
- 239000000347 magnesium hydroxide Substances 0.000 claims abstract description 9
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims abstract description 9
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims abstract description 8
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000011347 resin Substances 0.000 claims description 34
- 229920005989 resin Polymers 0.000 claims description 34
- 125000000962 organic group Chemical group 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 7
- 239000000243 solution Substances 0.000 description 41
- 239000002245 particle Substances 0.000 description 35
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 24
- 238000000034 method Methods 0.000 description 24
- 239000000843 powder Substances 0.000 description 21
- 125000004432 carbon atom Chemical group C* 0.000 description 19
- 229920005575 poly(amic acid) Polymers 0.000 description 18
- 238000000576 coating method Methods 0.000 description 15
- 239000011248 coating agent Substances 0.000 description 13
- 125000001183 hydrocarbyl group Chemical group 0.000 description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 11
- 229910052802 copper Inorganic materials 0.000 description 11
- 239000010949 copper Substances 0.000 description 11
- 125000004018 acid anhydride group Chemical group 0.000 description 10
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 10
- 239000011342 resin composition Substances 0.000 description 10
- 150000004985 diamines Chemical class 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 8
- 239000011800 void material Substances 0.000 description 8
- 239000012298 atmosphere Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000003960 organic solvent Substances 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- -1 alicyclic hydrocarbon Chemical class 0.000 description 6
- QQGYZOYWNCKGEK-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)oxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC=2C=C3C(=O)OC(C3=CC=2)=O)=C1 QQGYZOYWNCKGEK-UHFFFAOYSA-N 0.000 description 5
- 125000001931 aliphatic group Chemical group 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 239000003822 epoxy resin Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 229920000647 polyepoxide Polymers 0.000 description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- 150000008064 anhydrides Chemical class 0.000 description 4
- 239000012300 argon atmosphere Substances 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 125000001841 imino group Chemical group [H]N=* 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- 239000004642 Polyimide Substances 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 239000003495 polar organic solvent Substances 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910052582 BN Inorganic materials 0.000 description 2
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000004450 alkenylene group Chemical group 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 125000000304 alkynyl group Chemical group 0.000 description 2
- 125000004419 alkynylene group Chemical group 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 125000000732 arylene group Chemical group 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 150000007942 carboxylates Chemical group 0.000 description 2
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 2
- 239000007771 core particle Substances 0.000 description 2
- 238000002788 crimping Methods 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- 125000002993 cycloalkylene group Chemical group 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- 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 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 125000005647 linker group Chemical group 0.000 description 2
- 125000002950 monocyclic group Chemical group 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 125000003367 polycyclic group Chemical group 0.000 description 2
- 238000002360 preparation method Methods 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
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910000679 solder Inorganic materials 0.000 description 2
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 125000004434 sulfur atom Chemical group 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- XKBRJCSVQIUYGX-UHFFFAOYSA-N 3-[5-(3-aminophenoxy)pentoxy]aniline Chemical compound NC1=CC=CC(OCCCCCOC=2C=C(N)C=CC=2)=C1 XKBRJCSVQIUYGX-UHFFFAOYSA-N 0.000 description 1
- QHHKLPCQTTWFSS-UHFFFAOYSA-N 5-[2-(1,3-dioxo-2-benzofuran-5-yl)-1,1,1,3,3,3-hexafluoropropan-2-yl]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)(C(F)(F)F)C(F)(F)F)=C1 QHHKLPCQTTWFSS-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 238000007611 bar coating method Methods 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000011246 composite particle Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000007607 die coating method Methods 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical group FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- 238000007602 hot air drying Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
- C08G73/105—Polyimides containing oxygen in the form of ether bonds in the main chain with oxygen only in the diamino moiety
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
- C08G73/1053—Polyimides containing oxygen in the form of ether bonds in the main chain with oxygen only in the tetracarboxylic moiety
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- 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
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/032—Organic insulating material consisting of one material
- H05K1/0346—Organic insulating material consisting of one material containing N
-
- 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
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
- H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
-
- 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
- H05K1/03—Use of materials for the substrate
- H05K1/05—Insulated conductive substrates, e.g. insulated metal substrate
-
- 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
- H05K1/03—Use of materials for the substrate
- H05K1/05—Insulated conductive substrates, e.g. insulated metal substrate
- H05K1/056—Insulated conductive substrates, e.g. insulated metal substrate the metal substrate being covered by an organic insulating layer
-
- 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
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/222—Magnesia, i.e. magnesium oxide
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/001—Conductive additives
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
-
- 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
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/01—Dielectrics
- H05K2201/0137—Materials
- H05K2201/0154—Polyimide
Definitions
- the present invention relates to a polyimide resin composition and a metal base substrate.
- a metal base substrate is known as one of the substrates for mounting electronic components such as semiconductor elements and LEDs.
- a metal base substrate is a laminate in which a metal substrate, an insulating film, and a metal circuit layer are laminated in this order. Electronic components are mounted on the metal circuit layer via solder.
- the heat generated in the electronic component is transmitted to the metal substrate through the insulating film and radiated from the metal substrate to the outside.
- the insulating film of the metal base substrate is generally made of an insulating composition containing a resin with excellent insulation and voltage resistance and a filler with excellent thermal conductivity.
- a resin with excellent insulation and voltage resistance and a filler with excellent thermal conductivity.
- Polyimide resins, polyamide resins, polyamideimide resins, epoxy resins, silicone resins, and the like are used as resins for insulating films.
- fillers for insulating films aluminum oxide particles, aluminum hydroxide particles, magnesium oxide particles, magnesium hydroxide particles, aluminum nitride particles, silica particles, silicon carbide particles, titanium oxide particles, boron nitride particles and the like are used. (Patent Documents 1 to 5).
- a metal base substrate is manufactured, for example, by forming an insulating film on a metal substrate and then thermocompression bonding the insulating film and the metal circuit layer.
- a method of forming an insulating film on a metal substrate for example, a method of applying a resin solution in which a filler is dispersed onto the substrate and drying the obtained coating film is used.
- voids may occur between the resin and the filler when the coating film is dried. If voids are generated between the resin and the filler in the insulating film, heat is difficult to conduct through the void portions, and thus the thermal conductivity of the insulating film may decrease.
- the withstand voltage of the insulating film may be lowered, for example, dielectric breakdown of the insulating film may easily occur due to partial discharge occurring in the void portion.
- the present invention has been made in view of the above circumstances, and is a resin composition containing a filler and a resin, which is less likely to generate voids and has excellent thermal conductivity and voltage resistance, and A metal base substrate using this resin composition as an insulating film is provided.
- a resin composition of one embodiment of the present invention contains a resin and a filler dispersed in the resin,
- the resin includes a polyimide resin having a dicarboxylic acid group or an acid anhydride group of a dicarboxylic acid group at both ends, and the filler has, on the surface, aluminum oxide, aluminum hydroxide, magnesium oxide, and magnesium hydroxide.
- a polyimide resin composition containing at least one selected inorganic compound is containing at least one selected inorganic compound.
- the polyimide resin contained in the base material resin has a dicarboxylic acid group or an acid anhydride group of a dicarboxylic acid group at both ends, and the filler has aluminum oxide on the surface. , aluminum hydroxide, magnesium oxide, and magnesium hydroxide.
- the bonding strength between the resin and the filler is increased, and voids are less likely to form between the two. Therefore, the polyimide resin composition having the above structure has improved thermal conductivity and withstand voltage.
- the polyimide resin may be a compound represented by the following general formula (1) or general formula (2).
- the bonding strength between the polyimide resin and the filler becomes stronger, and more voids are generated between the two. become difficult.
- R1 represents a tetravalent organic group
- R2 represents a divalent organic group
- S is 10 or more and 200 or less calculated from the number average molecular weight. Represents a number within the range of .
- the number average molecular weight of the said polyimide resin may be set as the structure which exists in the range of 5000-50000. In this case, since the number average molecular weight of the polyimide resin is in the range of 5000 or more and 50000 or less, the fluidity of the polyimide resin is controlled and defects hardly occur during resin-metal bonding.
- the content of the filler may be in the range of 60% by mass or more and 90% by mass or less.
- the filler content is in the range of 60% by mass or more and 90% by mass or less, so the thermal conductivity is reliably improved.
- the proportion of the polyimide resin in the resin may be in the range of 66% by mass or more and 100% by mass or less.
- the resin contains a polyimide resin having a dicarboxylic acid group or an acid anhydride group of a dicarboxylic acid group at both ends within the above range, the bonding strength between the resin and the filler is further enhanced.
- a metal base substrate according to another aspect of the present invention (hereinafter referred to as “the metal base substrate of the present invention") is a metal base substrate in which a metal substrate, an insulating film, and a metal circuit layer are laminated in this order,
- the insulating film is characterized by being made of the polyimide resin composition described above. According to the metal base substrate having this configuration, since the insulating film composed of the above polyimide resin composition is arranged between the metal substrate and the metal circuit layer, it is excellent in thermal conductivity and voltage resistance. .
- a resin composition containing a filler and a resin which is less likely to generate voids and has excellent thermal conductivity and voltage resistance, and the resin composition used as an insulating film It becomes possible to provide a metal base substrate.
- a polyimide resin composition and a metal base substrate which are one embodiment of the present invention, will be described with reference to the attached drawings.
- FIG. 1 is a schematic cross-sectional view of a polyimide resin composition that is one embodiment of the present invention.
- the polyimide resin composition 10 of this embodiment includes a polyimide resin 11 and fillers 12 dispersed in the polyimide resin 11 .
- the content of the filler 12 of the polyimide resin composition 10 is preferably in the range of 60% by mass or more and 90% by mass or less, and is particularly in the range of 70% by mass or more and 88% by mass or less. preferable.
- the content of the filler 12 based on mass may be 80% by mass or more and 85% by mass or less.
- the content of the filler 12 of the polyimide resin composition 10 is preferably in the range of 40% by volume or more and 80% by volume or less on a volume basis, and is in the range of 45% by volume or more and 75% by volume or less. is particularly preferred.
- the content of the filler 12 based on the volume of the filler 12 may be 50% by volume or more and 65% by volume or less.
- Polyimide resin 11 is a base material (matrix resin) of polyimide resin composition 10 .
- the polyimide resin 11 has a dicarboxylic acid group or an acid anhydride group of a dicarboxylic acid group at both ends. Therefore, the polyimide resin 11 has a high affinity with inorganic compounds such as aluminum oxide, aluminum hydroxide, magnesium oxide, and magnesium hydroxide, and easily chemically bonds with these.
- the polyimide resin 11 may be a compound represented by the following general formula (1) or general formula (2).
- R1 represents a tetravalent organic group
- R2 represents a divalent organic group
- S is 10 or more and 200 or less calculated from the number average molecular weight. represents the number of
- the tetravalent organic group represented by R1 is a tetravalent aromatic hydrocarbon group obtained by removing four hydrogen atoms from an aromatic hydrocarbon, or a tetravalent aromatic hydrocarbon group obtained by removing four hydrogen atoms from an alicyclic hydrocarbon. It may be a valence alicyclic hydrocarbon group.
- Aromatic hydrocarbons include monocyclic aromatics, fused polycyclic aromatics, and non-fused polycyclic aromatics in which two monocyclic aromatics are linked together directly or by a bridging group.
- the alicyclic hydrocarbon may have from 4 to 8 carbon atoms.
- the tetravalent organic group represented by R1 may be, for example, groups represented by the following general formulas (3) to (6).
- X represents a cross-linking group.
- the bridging group may be a divalent hydrocarbon group, an oxygen atom, a sulfur atom, a carbonyl group, a sulfonyl group, an imino group, or a combination of these groups.
- the divalent hydrocarbon group is, for example, an aliphatic group having 1 to 10 carbon atoms (alkylene group, alkenylene group, alkynylene group), a cycloalkylene group having 4 to 10 carbon atoms, an arylene group, or these It may be a combination of groups.
- a divalent aliphatic group and an imino group may have a substituent.
- Examples of the substituent include a monovalent hydrocarbon group, a fluorocarbon group in which a monovalent hydrocarbon group is substituted with fluorine, an alkoxy group having 1 to 10 carbon atoms, and an —OCOCH 3 group.
- Monovalent hydrocarbon groups include, for example, aliphatic groups having 1 to 10 carbon atoms (alkyl groups, alkenyl groups, alkynyl groups), cycloalkyl groups having 4 to 10 carbon atoms, and 6 to 6 carbon atoms. 10 aryl groups and aralkyl groups having 7 to 10 carbon atoms may also be used.
- the bridging group represented by X may be, for example, groups represented by the following formulas (7) to (13).
- the divalent organic group represented by R2 preferably has a methylene chain.
- the methylene chain preferably has 3 or more carbon atoms.
- the divalent organic group may be a group in which a methylene chain and a divalent linking group are combined.
- a divalent linking group includes a divalent hydrocarbon group, an oxygen atom, a sulfur atom, a carbonyl group, a sulfonyl group, an imino group, a —(Si(R3R4)—O) n — group (wherein R3 and R4 each independently represents an alkyl group having 1 to 10 carbon atoms, and n represents a number within the range of 1 to 30.) or a group combining these groups may be .
- Divalent hydrocarbon groups include, for example, aliphatic groups having 1 to 10 carbon atoms (alkylene groups, alkenylene groups, alkynylene groups), cycloalkylene groups having 4 to 10 carbon atoms, and 6 to 6 carbon atoms. It may be 10 arylene groups or a combination of these groups.
- a divalent hydrocarbon group and an imino group may have a substituent. Examples of substituents include monovalent hydrocarbon groups.
- Monovalent hydrocarbon groups include, for example, aliphatic groups having 1 to 10 carbon atoms (alkyl groups, alkenyl groups, alkynyl groups), cycloalkyl groups having 4 to 20 carbon atoms, and 6 to 6 carbon atoms. 10 aryl groups and aralkyl groups having 7 to 20 carbon atoms may be used.
- the divalent organic group represented by R2 may be, for example, a group represented by the following general formulas (14) to (15). Moreover, the divalent organic group represented by R2 may be, for example, a hydrocarbon group derived from dimer diamine having a methylene chain. The hydrocarbon group derived from dimer diamine has a number of carbon atoms in the range of 20 to 50, and the number of hydrogen atoms is (m ⁇ 2-6) or more and (m ⁇ 2) or less, where m is the number of carbon atoms. may be within the range.
- p represents a number within the range of 3 or more and 10 or less.
- q and r each independently represent a number within the range of 3 or more and 8 or less, and n represents a number within the range of 1 or more and 30 or less.
- the polyimide resin 11 can be produced by a method comprising, for example, a step of reacting a tetracarboxylic dianhydride and a diamine in an organic solvent to produce a polyamic acid, and a step of imidating the polyamic acid.
- a compound represented by the following general formula (16) may be used as the tetracarboxylic dianhydride.
- a compound represented by the following general formula (17) may be used as the diamine.
- R1 is the same as in general formulas (1) and (2) above.
- R2 is the same as in general formulas (1) and (2) above.
- a polar organic solvent may be used as the organic solvent.
- polar organic solvents include N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAC), N-methyl-2-pyrrolidone (NMP), cyclohexanone.
- the organic solvent, the tetracarboxylic dianhydride and the diamine may be stirred and mixed to react the tetracarboxylic dianhydride and the diamine to generate the polyamic acid.
- the reaction temperature may be, for example, within the range of 10°C or higher and 100°C or lower.
- the reaction atmosphere may be an air atmosphere or an inert gas atmosphere (eg, argon, nitrogen).
- the dicarboxylic acid groups or the acid anhydride groups present at both ends thereof are derived from the raw material tetracarboxylic dianhydride.
- the amount of tetracarboxylic dianhydride in the organic solvent may be greater than that of diamine.
- the mixing ratio of tetracarboxylic dianhydride to diamine in the organic solvent may be in the range of 1.005 or more and 1.2 or less.
- a method of heating the polyamic acid solution or a method of adding an imidization catalyst to the polyamic acid solution can be used.
- the heating temperature may be in the range of 100°C or higher and 300°C or lower.
- an imidization catalyst an amine compound conventionally used as an imidization catalyst, such as an aliphatic amine, an alicyclic amine, or an aromatic amine, can be used as the imidization catalyst.
- the number average molecular weight of the polyimide resin 11 is preferably in the range of 5000 or more and 50000 or less, and particularly preferably in the range of 8000 or more and 30000 or less. Although not particularly limited, the polyimide resin 11 may have a number average molecular weight of 10,000 or more and 15,000 or less.
- the filler 12 has, on its surface, at least one inorganic compound selected from the group consisting of aluminum oxide, aluminum hydroxide, magnesium oxide, and magnesium hydroxide.
- the presence of the above inorganic compound on the surface of the filler 12 increases the bonding strength between the polyimide resin 11 and the filler 12, making it difficult for voids to form between them.
- the filler may be a single particle containing only one of the above inorganic compounds, or may be a composite particle in which two or more of the above inorganic compounds are combined. Further, the filler 12 may be a coated particle obtained by partially or entirely coating the surface of the core particle with one or more of the above inorganic compounds.
- core particles for example, aluminum nitride particles, silica particles, silicon carbide particles, titanium oxide particles, and boron nitride particles can be used. These particles may be used singly or in combination of two or more.
- the filler 12 is composed of a component different from the inorganic compound and part of its surface is coated with the inorganic compound, at least 50% or more of the filler surface is coated with the inorganic compound.
- the coverage rate (area coverage rate) on the particle surface can be obtained by fixing 10 or more fillers to a tape or the like and measuring the area for each composition by SEM and EDX.
- the filler 12 preferably has an average particle size within the range of 0.1 ⁇ m or more and 20 ⁇ m or less.
- the thermal conductivity of the resin composition is improved.
- the average particle size of the filler 12 is less likely to form aggregated particles and is less likely to settle, so that the filler 12 can be easily dispersed uniformly in the polyimide resin 11 .
- the average particle size of the filler 12 is preferably in the range of 0.3 ⁇ m or more and 20 ⁇ m or less.
- the polyimide resin composition 10 can be produced, for example, by a method including a preparation step of preparing a filler-dispersed polyimide resin solution and a molding step of applying the filler-dispersed polyimide resin solution and drying the resulting coating film. .
- the filler-dispersed polyimide resin solution may be prepared, for example, as follows. First, polyimide resin 11 is dissolved in an organic solvent to obtain a polyimide resin solution. As the organic solvent, for example, a polar organic solvent used in the production of polyimide resin may be used. Next, the polyimide solution and the filler 12 are mixed to obtain a mixture. Then, the mixture is subjected to dispersion treatment to disperse the filler 12 in the solution of the polyimide resin 11 . As the dispersing treatment, ultrasonic dispersing treatment, dispersing treatment by a ball mill, and treatment for dispersing particles by colliding raw materials jetted under high pressure with each other can be used.
- dispersing treatment ultrasonic dispersing treatment, dispersing treatment by a ball mill, and treatment for dispersing particles by colliding raw materials jetted under high pressure with each other can be used.
- a spin coating method for applying the filler-dispersed polyimide resin solution
- a bar coating method for a knife coating method, a roll coating method, a blade coating method, a die coating method, a gravure coating method, a dip coating method, or the like
- a method for drying the coating film methods such as heat drying, hot air drying, and reduced pressure drying can be used.
- the drying temperature is preferably 100° C. or higher and not higher than the thermal decomposition temperature of the polyimide resin. By heating to 100° C. or higher, the bonding strength between the polyimide resin and the filler becomes stronger.
- the polyimide resin 11 which is the base material, has a dicarboxylic acid group or an acid anhydride group of a dicarboxylic acid group at both ends, and a filler Since 12 has an inorganic compound such as aluminum oxide, aluminum hydroxide, magnesium oxide, or magnesium hydroxide on the surface, the polyimide resin 11 and the filler 12 have high affinity with each other and are easily chemically bonded. Therefore, the bonding strength between the polyimide resin 11 and the filler 12 is increased, and voids are less likely to be generated between them. Therefore, the polyimide resin composition 10 of the present embodiment has improved thermal conductivity and withstand voltage.
- the bonding strength between the polyimide resin 11 and the filler 12 is higher. becomes stronger, and voids are less likely to be generated between them.
- the number average molecular weight of the polyimide resin 11 is within the range of 5000 or more and 50000 or less, the hardness and flexibility of the polyimide resin 11 are well balanced and difficult to deform. Therefore, the thermal conductivity and withstand voltage of the polyimide resin composition 10 are stable over a long period of time.
- the content of the filler 12 is within the range of 60% by mass or more and 90% by mass or less, the thermal conductivity is reliably improved.
- FIG. 2 is a schematic cross-sectional view of a metal base substrate that is one embodiment of the present invention.
- the metal base substrate 20 is a laminate in which a metal substrate 21, an insulating film 22, and a metal circuit layer 23 are laminated in this order.
- the metal substrate 21 is a member that serves as the base of the metal base substrate 20 .
- a copper plate, an aluminum plate, or a laminated plate thereof can be used as the metal substrate 21 .
- the insulating film 22 is a member for insulating the metal substrate 21 and the metal circuit layer 23 .
- the insulating film 22 is composed of the polyimide resin composition 10 shown in FIG. For this reason, the same reference numerals are used and detailed descriptions thereof are omitted.
- the metal circuit layer 23 is formed in a circuit pattern.
- An electronic component is bonded via solder or the like onto the metal circuit layer 23 formed in the circuit pattern.
- solder or the like As a material for the metal circuit layer 23, copper, aluminum, gold, or the like can be used.
- Examples of electronic components mounted on the metal circuit layer 23 are not particularly limited, and include semiconductor elements, resistors, capacitors, crystal oscillators, and the like.
- semiconductor elements include MOSFET (Metal-oxide-semiconductor field effect transistor), IGBT (Insulated Gate Bipolar Transistor), LSI (Large Scale Integration), LED (light emitting diode), LED chip, LED-CSP (LED-Chip Size Package).
- the metal base substrate 20 of this embodiment includes an insulating film forming process of forming an insulating film 22 on one surface of a metal substrate 21 and a metal circuit layer press-bonding process of press-bonding a metal circuit layer 23 onto the insulating film 22 . and a method comprising the steps of:
- the insulating film 22 can be formed, for example, by applying a filler-dispersed polyimide resin solution to one surface of the metal substrate 21 and then drying the resulting coating film.
- the method for preparing the filler-dispersed polyimide resin solution, the method for applying the filler-dispersed polyimide resin solution, and the method for drying the coating film are the same as in the method for producing the polyimide resin composition 10 described above.
- the metal circuit layer 23 is, for example, laminated on the insulating film 22, and then crimped by applying pressure in the lamination direction while heating the obtained laminate. can be done.
- the heating temperature is preferably 200° C. or higher, particularly preferably 250° C. or higher.
- the upper limit of the heating temperature is lower than the thermal decomposition temperature of the polyimide resin 11, preferably lower than the thermal temperature by 30°C.
- the pressure during pressurization is preferably in the range of 1 MPa or more and 30 MPa or less, and particularly preferably in the range of 3 MPa or more and 25 MPa or less.
- the crimping time varies depending on the heating temperature and pressure, but is generally 10 minutes or more and 180 minutes or less.
- the insulating film 22 composed of the polyimide resin composition 10 described above is arranged between the metal substrate 21 and the metal circuit layer 23. Therefore, it is excellent in thermal conductivity and withstand voltage.
- the present invention is not limited to this, and can be modified as appropriate without departing from the technical idea of the invention.
- a polyimide resin 11 having a dicarboxylic acid group or a dicarboxylic acid anhydride group at both ends was used alone.
- the resin composition 10 may contain other resins.
- other resins for example, polyimide resins and epoxy resins having an amine group on at least one end can be used.
- the content of the polyimide resin 11 having a dicarboxylic acid group or a dicarboxylic acid anhydride group at both ends is in the range of 66% by mass or more and 100% by mass or less. is preferred.
- the polyimide resin composition 10 is used as the insulating layer of the metal base substrate 20 , but the application of the polyimide resin composition 10 is not limited to this.
- the polyimide resin composition 10 may be used, for example, as an insulating film for an insulating conductor covered with an insulating film such as an enameled wire.
- the obtained polyamic acid solution was transferred to an evaporating dish and dried and baked in the order of 50° C. for 24 hours, 200° C. for 5 hours, and 250° C. for 30 minutes under a reduced pressure atmosphere.
- a polyimide resin A having dicarboxylic anhydride terminals was obtained.
- the molar ratio of 6FDA/PMDD in the mixed solution is 1.05.
- the obtained polyimide resin A had a number average molecular weight of 11,000.
- Example of the present invention except that 4 g of polyimide resin A and 2 g of polyimide resin B were added to 10 g of DMF, and the amount of aluminum oxide powder added was set to the amount described in Table 1 below.
- a filler-dispersed polyimide resin solution was prepared in the same manner as in 1.
- the resin contained in the filler-dispersed polyimide resin solution has a content of 66.7% of a polyimide resin (polyimide resin A) having dicarboxylic anhydride at both ends, and a polyimide resin having amine groups at both ends (polyimide resin The content of B) is 33.3% by mass.
- Invention Example 7 Filler-dispersed polyimide in the same manner as in Invention Example 1, except that magnesium oxide powder (average particle size: 10 ⁇ m) was added instead of aluminum oxide powder in an amount corresponding to the content described in Table 1 below. A resin solution was prepared.
- Invention Example 8 Filler dispersion was carried out in the same manner as in Invention Example 1, except that instead of aluminum oxide powder, aluminum hydroxide powder (average particle size: 3 ⁇ m) was added in an amount corresponding to the content shown in Table 1 below. A polyimide resin solution was prepared.
- the content of polyimide resin (polyimide resin A) having dicarboxylic acid anhydride at both ends is 97% by mass, and the content of epoxy resin is 3% by mass.
- Example of the present invention except that 5 g of polyimide resin B was added instead of polyimide resin A to 10 g of DMF, and the amount of aluminum oxide powder added was set to the content described in Table 1 below.
- a filler-dispersed polyimide resin solution was prepared in the same manner as in 1.
- Example of the present invention except that 1 g of polyimide resin D was added instead of polyimide resin A to 10 g of DMF, and the amount of aluminum oxide powder added was set to the amount described in Table 1 below.
- a filler-dispersed polyimide resin solution was prepared in the same manner as in 1.
- the filler-dispersed polyimide resin solution is spin-coated at a rotational speed of 500 rpm on a copper substrate of 50 mm long ⁇ 50 mm wide ⁇ 1 mm thick to obtain a coating film of 20 ⁇ m thick.
- the obtained coating film is heated at a temperature of 100° C. for 3 hours and dried to form a polyimide resin composition film containing a filler, thereby obtaining a copper substrate with a polyimide resin composition film.
- the resulting polyimide resin composition film is observed with an optical microscope to count the number of filler aggregates having a particle size of 0.1 mm or more.
- the number of aggregates per 1 cm 2 of the polyimide resin composition film is determined as A when it is 3 or less, B when it is 4 or more and 10 or less, and C when it is 11 or more. did.
- a PTFE (polytetrafluoroethylene) plate having a size of 50 mm long ⁇ 50 mm wide ⁇ 1 mm thick is coated with a filler-dispersed polyimide resin solution using a bar coater to obtain a coating film having a thickness of 100 ⁇ m.
- the obtained coating film is heated at a temperature of 100° C. for 30 minutes, then heated at a temperature of 150° C. for 30 minutes, and dried to form a polyimide resin composition film containing a filler.
- the obtained polyimide resin composition film is peeled off from the PTFE plate and embedded with a resin. A section of the resin-filled polyimide resin composition film is exposed by CP processing.
- a cross section of the exposed polyimide resin composition film is observed using an SEM (scanning electron microscope).
- the area occupied by voids is measured with respect to the cross-sectional area of 100 ⁇ m 2 of the polyimide resin composition film, and the occupation ratio is calculated.
- a void is defined as a region that exists between the polyimide resin and the filler and is neither polyimide nor filler.
- the minimum void area is 0.01 ⁇ m 2 .
- thermo conductivity A 50 mm long ⁇ 50 mm wide ⁇ 1 mm thick copper substrate is coated with the filler-dispersed polyimide resin solution using a bar coater to obtain a coating film of 100 ⁇ m thick.
- the obtained coating film is heated at a temperature of 100° C. for 3 hours and dried to form a polyimide resin composition film containing a filler, thereby obtaining a copper substrate with a polyimide resin composition film.
- the thermal conductivity of the polyimide resin composition film is measured by a laser flash method using LFA477 Nanoflash manufactured by NETZSCH-Geratebau GmbH.
- the withstand voltage of the polyimide resin composition film is measured using a multifunctional safety tester 7440 manufactured by Keisoku Giken Co., Ltd.
- a copper substrate with a polyimide resin composition film is obtained in the same manner as in the measurement of the thermal conductivity.
- An electrode ( ⁇ 6 mm) is arranged on the surface of the polyimide resin composition film of the copper substrate with the polyimide resin composition film.
- the copper substrate of the polyimide resin composition film-coated copper substrate and the electrodes arranged on the surface of the polyimide resin composition film are each connected to a power supply, and the voltage is increased to 6000 V in 30 seconds.
- the voltage at which the current flowing between the copper substrate and the electrode reached 5000 ⁇ A was defined as the withstand voltage of the polyimide resin composition film.
- the film thickness is measured with a micrometer, and the withstand voltage per film thickness is calculated by subtracting the film thickness from the withstand voltage.
- Inventive Examples 1 to 10 containing either aluminum oxide powder, aluminum hydroxide powder, magnesium oxide powder, or magnesium hydroxide powder as a filler, using a polyimide resin having a dicarboxylic acid group or an acid anhydride group thereof at both ends.
- the polyimide resin composition film formed using the filler-dispersed polyimide resin solution of No. 2 was excellent in filler dispersibility, had a low void occupation rate, and had high thermal conductivity and withstand voltage. This is because the affinity between the dicarboxylic acid groups or acid anhydride groups at both ends of the polyimide resin and the filler is high, and defects are less likely to occur between the polyimide resin and the filler.
- the terminal dicarboxylic anhydride groups of the polyimide resin are easily hydrolyzed by water adsorbed on the aluminum oxide particles or moisture in the air to form dicarboxylic acid groups.
- a dicarboxylic acid group reacts with a hydroxyl group on the aluminum oxide particles to generate two carboxylate groups.
- the two carboxylate groups produced are stabilized by bidentate cross-linking with respect to two aluminum atoms, respectively, and the polyimide resin is immobilized on the surface of the aluminum oxide particles. Heating at 100° C. or higher is preferable for the progress of the bidentate cross-linking reaction.
- a resin composition containing a filler and a resin which is less likely to generate voids and has excellent thermal conductivity and voltage resistance, and a metal base substrate using the resin composition as an insulating film. becomes possible.
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Abstract
Description
本願は、2021年2月25日に、日本に出願された特願2021-028910号に基づき優先権を主張し、その内容をここに援用する。
このような構成とされた金属ベース基板では、電子部品にて発生した熱は、絶縁膜を介して金属基板に伝達され、金属基板から外部に放熱される。
この場合、ポリイミド樹脂が下記の一般式(1)又は一般式(2)で表される化合物であるので、ポリイミド樹脂とフィラーとの接合力がより強くなり、両者の間にボイドがより生成しにくくなる。
この場合、ポリイミド樹脂の数平均分子量が、5000以上50000以下の範囲内にあるので、ポリイミド樹脂の流動性が制御され、樹脂-金属接合時の不良が生じにくい。
この場合、フィラーの含有量が60質量%以上90質量%以下の範囲内にあるので、熱伝導率が確実に向上する。
この場合、樹脂が両末端にジカルボン酸基又はジカルボン酸基の酸無水物基を有するポリイミド樹脂を上記の範囲で含むので、樹脂とフィラーとの接合力がさらに強くなる。
この構成の金属ベース基板によれば、金属基板と金属回路層との間に、上述のポリイミド樹脂組成物から構成される絶縁膜が配置されているので、熱伝導性と耐電圧性とに優れる。
図1は、本発明の一実施形態であるポリイミド樹脂組成物の概略断面図である。
図1に示すように、本実施形態であるポリイミド樹脂組成物10は、ポリイミド樹脂11と、ポリイミド樹脂11に分散されているフィラー12とを含む。ポリイミド樹脂組成物10のフィラー12の含有量は、質量基準で、60質量%以上90質量%以下の範囲内にあることが好ましく、70質量%以上88質量%以下の範囲内にあることが特に好ましい。特に限定されないが、質量基準でのフィラー12の含量は、80質量%以上85質量%以下であってもよい。
また、ポリイミド樹脂組成物10のフィラー12の含有量は、体積基準で、40体積%以上80体積%以下の範囲内にあることが好ましく、45体積%以上75体積%以下の範囲内にあることが特に好ましい。特に限定されないが、フィラー12の体積基準でのフィラー12の含量は、50体積%以上65体積%以下であってもよい。
ポリイミド樹脂11は、ポリイミド樹脂組成物10の母材(マトリックス樹脂)である。ポリイミド樹脂11は、両末端にジカルボン酸基又はジカルボン酸基の酸無水物基を有する。このため、ポリイミド樹脂11は、酸化アルミニウム、水酸化アルミニウム、酸化マグネシウム、水酸化マグネシウムなどの無機化合物に対して親和性が高く、これらと化学的に結合しやすい。
ポリイミド樹脂11は、下記の一般式(1)又は一般式(2)で表される化合物であってもよい。
一般式(6)において、Xは、架橋基を表す。架橋基は、2価の炭化水素基、酸素原子、硫黄原子、カルボニル基、スルホニル基、イミノ基、又はこれらの基を組み合わせた基であってもよい。2価の炭化水素基は、例えば、炭素原子数が1~10の脂肪族基(アルキレン基、アルケニレン基、アルキニレン基)、炭素原子数が4~10のシクロアルキレン基、アリーレン基、又はこれらを組み合わせた基であってもよい。2価の脂肪族基及びイミノ基は置換基を有していてもよい。置換基の例としては、1価の炭化水素基、1価の炭化水素基をフッ素で置換したフッ化炭素基、炭素原子数が1~10のアルコキシ基、-OCOCH3基を挙げることができる。1価の炭化水素基は、例えば、炭素原子数が1~10の脂肪族基(アルキル基、アルケニル基、アルキニル基)、炭素原子数が4~10のシクロアルキル基、炭素原子数が6~10のアリール基、炭素原子数が7~10のアラルキル基であってもよい。Xで表される架橋基は、例えば、下記の式(7)~(13)で表される基であってもよい。
一般式(15)において、q及びrは、それぞれ独立して3以上8以下の範囲内にある数を表し、nは、1以上30以下の範囲内にある数を表す。
フィラー12は、表面に、酸化アルミニウム、水酸化アルミニウム、酸化マグネシウム、水酸化マグネシウムからなる群より選ばれる少なくとも一種の無機化合物を有する。フィラー12の表面に、上記の無機化合物が存在することによって、ポリイミド樹脂11とフィラー12との接合力が強くなり、両者の間にボイドが生成しにくくなる。フィラーは、上記の無機化合物の一種のみを含む単体粒子であってもよいし、上記の無機化合物の二種以上を組み合わせた複合粒子であってもよい。また、フィラー12は、核粒子の表面の一部もしくは全部を上記の無機化合物の一種もしくは二種以上で被覆した被覆粒子であってもよい。核粒子としては、例えば、窒化アルミニウム粒子、シリカ粒子、炭化珪素粒子、酸化チタン粒子、窒化硼素粒子を用いることができる。これらの粒子は、一種を単独で使用してもよいし、二種以上を組み合わせて使用してもよい。
フィラー12が、前記無機化合物とは異なるの成分からなり、その表面の一部が前記無機化合物で被覆されたものである場合、少なくともフィラー表面の50%以上が前記無機化合物で被覆される。
上記被覆率は、10個以上のフィラーをテープ等に固定し、SEMおよびEDXによって組成ごとの面積を測定することで、粒子表面における被覆率(面積被覆率)を取得することができる。
次に、本実施形態のポリイミド樹脂組成物10の製造方法について説明する。
ポリイミド樹脂組成物10は、例えば、フィラー分散ポリイミド樹脂溶液を調製する調製工程と、フィラー分散ポリイミド樹脂溶液を塗布し、得られた塗布膜を乾燥する成形工程とを含む方法によって製造することができる。
図2は、本発明の一実施形態である金属ベース基板の概略断面図である。
金属ベース基板20は金属基板21と、絶縁膜22と、金属回路層23とがこの順で積層された積層体である。
本実施形態の金属ベース基板20は、例えば、金属基板21の一方の表面に絶縁膜22を成膜する絶縁膜形成工程と、絶縁膜22の上に金属回路層23を圧着する金属回路層圧着工程と、を含む方法によって製造することができる。
例えば、本実施形態では、ポリイミド樹脂組成物10に含まれる樹脂として、両末端にジカルボン酸基又はジカルボン酸基の酸無水物基を有するポリイミド樹脂11を単独で用いた例を説明したが、ポリイミド樹脂組成物10は、他の樹脂を含んでいてもよい。他の樹脂としては、例えば、少なくとも一方の末端にアミン基を有するポリイミド樹脂、エポキシ樹脂を用いることができる。ただし、ポリイミド樹脂組成物10に含まれる樹脂は、両末端にジカルボン酸基又はジカルボン酸基の酸無水物基を有するポリイミド樹脂11の含有量が66質量%以上100質量%以下の範囲内にあることが好ましい。
DMF(N,N-ジメチルホルムアミド、富士フイルム和光純薬株式会社製)100g中に、PMDD(3,3’-(ペンタメチレンジオキシ)ジアニリン、メルク株式社製)6.20gを加えて溶解し、次いで6FDA(4,4’-(ヘキサフルオロイソプロピリデン)ジフタル酸無水物、東京化成工業株式会社製)10.10gを加えた。その後、アルゴン雰囲気下、室温で72時間撹拌混合してポリアミック酸を生成させた。得られたポリアミック酸溶液を蒸発皿に移し、減圧雰囲気下で50℃の温度で24時間、200℃の温度で5時間、250℃の温度で30分間の順で、乾燥、焼成することで両末端がジカルボン酸無水物のポリイミド樹脂Aを得た。混合溶液中の6FDA/PMDDのモル比は1.05である。
得られたポリイミド樹脂Aの数平均分子量は、11000であった。
DMF100g中に、PMDD6.20gを加えて溶解し、次いで6FDA9.14gを加えた。その後、アルゴン雰囲気下、室温で72時間撹拌混合してポリアミック酸を生成させた。得られたポリアミック酸溶液を蒸発皿に移し、減圧雰囲気下で50℃の温度で24時間、200℃の温度で5時間、250℃の温度で30分間の順で、乾燥、焼成することで両末端がアミン基のポリイミド樹脂Bを得た。混合溶液中の6FDA/PMDDのモル比は0.95である。
得られたポリイミド樹脂Bの数平均分子量は、11000であった。
シクロヘキサノン100g中に、V551(Versamine551、BASFジャパン株式会社製)6.20gを加えて溶解し、次いで、ODPA(4,4’-オキシジフタル酸無水物、東京化成工業株式会社製)4.93gを加えた。その後、アルゴン雰囲気下、室温で72時間撹拌混合してポリアミック酸を生成させた。得られたポリアミック酸溶液を蒸発皿に移し、減圧雰囲気下で50℃の温度24時間、150℃の温度で5時間、乾燥、焼成することで両末端がジカルボン酸無水物基のポリイミド樹脂Cを得た。混合溶液中のODPA/V551のモル比は1.05である。
得られたポリイミド樹脂Cの数平均分子量は、11000であった。
シクロヘキサノン100g中に、V551を6.20g加えて溶解し、次いでODPA4.46gを加えた。その後、アルゴン雰囲気下、室温で72時間撹拌混合してポリアミック酸を生成させた。得られたポリアミック酸溶液を蒸発皿に移し、減圧雰囲気下で50℃の温度24時間、150℃の温度で5時間、乾燥、焼成することで両末端がアミン基のポリイミド樹脂Dを得た。混合溶液中のODPA/V551のモル比は0.95である。
得られたポリイミド樹脂Dの数平均分子量は、11000であった。
DMF10gに対してポリイミド樹脂Aを5g投入し、均一に溶解するまで撹拌した。
得られたポリイミド樹脂溶液に、酸化アルミニウム粉末(平均粒子径:3μm)をポリイミド樹脂Aと酸化アルミニウム粉末の合計量に対して、質量換算で60質量%(体積換算で35体積%)となるように投入し、マグネティックスターラーで撹拌した。得られた混合物を、スギノマシン社製スターバーストを用い、圧力50MPaの高圧噴射処理を10回繰り返すことにより分散処理を行なって、フィラー分散ポリイミド樹脂溶液を調製した。フィラー分散ポリイミド樹脂溶液に含まれる樹脂は、両末端がジカルボン酸無水物であるポリイミド樹脂(ポリイミド樹脂A)の含有量が100質量%である。
酸化アルミニウム粉末の投入量を、下記の表1に記載されている含有量となる量としたこと以外は、本発明例1と同様にしてフィラー分散ポリイミド樹脂溶液を調製した。
DMF10gに対して、ポリイミド樹脂Aを4gとポリイミド樹脂Bを2g投入し、酸化アルミニウム粉末の投入量を、下記の表1に記載されている含有量となる量としたこと以外は、本発明例1と同様にしてフィラー分散ポリイミド樹脂溶液を調製した。フィラー分散ポリイミド樹脂溶液に含まれる樹脂は、両末端がジカルボン酸無水物であるポリイミド樹脂(ポリイミド樹脂A)の含有量が66.7%であり、両末端がアミン基であるポリイミド樹脂(ポリイミド樹脂B)の含有量が33.3質量%である。
DMFの代わりにシクロヘキサノンを用い、シクロヘキサノン10gに対して、ポリイミド樹脂Aの代わりにポリイミド樹脂Cを1g投入し、酸化アルミニウム粉末の投入量を、下記の表1に記載されている含有量となる量としたこと以外は、本発明例1と同様にしてフィラー分散ポリイミド樹脂溶液を調製した。フィラー分散ポリイミド樹脂溶液に含まれる樹脂は、両末端がジカルボン酸無水物であるポリイミド樹脂(ポリイミド樹脂C)の含有量が100質量%である。
酸化アルミニウム粉末の代わりに酸化マグネシウム粉末(平均粒子径:10μm)を、下記の表1に記載されている含有量となる量で投入したこと以外は、本発明例1と同様にしてフィラー分散ポリイミド樹脂溶液を調製した。
酸化アルミニウム粉末の代わりに水酸化アルミニウム粉末(平均粒子径:3μm)を、下記の表1に記載されている含有量となる量で投入したこと以外は、本発明例1と同様にしてフィラー分散ポリイミド樹脂溶液を調製した。
DMF10gに対してポリイミド樹脂Aを4.85g投入し、均一に溶解するまで撹拌した。得られたポリイミド樹脂溶液に、エポキシ樹脂原料(JER-630、三菱ケミカル株式会社製)0.15gを加えた。さらに酸化アルミニウム粉末(平均粒子径:3μm)をポリイミド樹脂Aとエポキシ樹脂と酸化アルミニウム粉末の合計量に対して、質量換算で79質量%(体積換算で57体積%)となるように投入し、マグネティックスターラーで撹拌した。得られた混合物を、スギノマシン社製スターバーストを用い、圧力50MPaの高圧噴射処理を10回繰り返すことにより分散処理を行なって、フィラー分散ポリイミド樹脂溶液を調製した。フィラー分散ポリイミド樹脂溶液に含まれる樹脂は、両末端がジカルボン酸無水物であるポリイミド樹脂(ポリイミド樹脂A)の含有量が97質量%であり、エポキシ樹脂の含有量は3質量%である。
平均粒径3μmの酸化アルミニウム粉末の代わりに平均粒径0.7μmの酸化アルミニウム粉末を、下記の表1に記載されている含有量となる量で投入したこと以外は、本発明例1と同様にしてフィラー分散ポリイミド樹脂溶液を調製した。
DMF10gに対して、ポリイミド樹脂Aの代わりにポリイミド樹脂Bを5g投入し、酸化アルミニウム粉末の投入量を、下記の表1に記載されている含有量となる量としたこと以外は、本発明例1と同様にしてフィラー分散ポリイミド樹脂溶液を調製した。
酸化アルミニウム粉末の代わりにシリカ粉末(平均粒子径:0.7μm)を、下記の表1に記載されている含有量となる量で投入したこと以外は、本発明例1と同様にしてフィラー分散ポリイミド樹脂溶液を調製した。
DMF10gに対して、ポリイミド樹脂Aの代わりにポリイミド樹脂Dを1g投入し、酸化アルミニウム粉末の投入量を、下記の表1に記載されている含有量となる量としたこと以外は、本発明例1と同様にしてフィラー分散ポリイミド樹脂溶液を調製した。
本発明例1~10及び比較例1~3で得られたフィラー分散ポリイミド樹脂溶液を用いて、フィラーを含むポリイミド樹脂組成物膜を作製し、得られたポリイミド樹脂膜のフィラー分散性、ボイド占有率、熱伝導率、膜厚当たりの耐電圧を、下記の方法により評価した。その結果を、下記の表1に示す。
縦50mm×横50mm×厚さ1mmの銅基板上に、フィラー分散ポリイミド樹脂溶液を500rpmの回転速度でスピンコートして、厚さ20μmの塗布膜を得る。得られた塗布膜を100℃の温度で3時間加熱して乾燥することにより、フィラーを含むポリイミド樹脂組成物膜を成膜して、ポリイミド樹脂組成物膜付銅基板を得る。得られたポリイミド樹脂組成物膜を、光学顕微鏡を用いて観察して、粒径が0.1mm以上のフィラーの凝集体の個数を計測する。ポリイミド樹脂組成物膜1cm2あたりの凝集体の個数が、3個以下であった場合をAとし、4個以上10個以下であった場合をB、11個以上であった場合をCと判定した。
縦50mm×横50mm×厚さ1mmのPTFE(ポリテトラフルオロエチレン)板の上に、フィラー分散ポリイミド樹脂溶液を、バーコーターを用いて塗布して厚さ100μmの塗布膜を得る。得られた塗布膜を100℃の温度で30分間加熱した後150℃の温度で30分間加熱して、乾燥することにより、フィラーを含むポリイミド樹脂組成物膜を成膜する。得られたポリイミド樹脂組成物膜をPTFE板から剥離して、樹脂埋めする。
樹脂埋めしたポリイミド樹脂組成物膜を、CP加工によって断面を露出させる。次いで、露出したポリイミド樹脂組成物膜の断面を、SEM(走査型電子顕微鏡)を用いて観察する。ポリイミド樹脂組成物膜の断面積100μm2に対して、ボイドが占める面積を計測し、その占有率を算出する。
SEMでの観察対象となる断面において、ポリイミド樹脂とフィラーとの間に存在し、ポリイミドでもなくフィラーでもない領域をボイドとする。ボイドの最少面積は0.01μm2とする。
縦50mm×横50mm×厚さ1mmの銅基板上に、フィラー分散ポリイミド樹脂溶液を、バーコーターを用いて塗布して厚さ100μmの塗布膜を得る。得られた塗布膜を100℃の温度で3時間加熱して乾燥することにより、フィラーを含むポリイミド樹脂組成物膜を成膜して、ポリイミド樹脂組成物膜付銅基板を得る。
ポリイミド樹脂組成物膜の熱伝導率(ポリイミド樹脂組成物膜の厚さ方向の熱伝導率)は、NETZSCH-GeratebauGmbH製のLFA477 Nanoflashを用いて、レーザーフラッシュ法により測定する。
ポリイミド樹脂組成物膜の耐電圧は、株式会社計測技術研究所の多機能安全試験器7440を用いて測定する。
上記熱伝導率の測定と同様にして、ポリイミド樹脂組成物膜付銅基板を得る。ポリイミド樹脂組成物膜付き銅基板のポリイミド樹脂組成物膜の表面に電極(φ6mm)を配置する。ポリイミド樹脂組成物膜付銅基板の銅基板とポリイミド樹脂組成物膜の表面に配置した電極をそれぞれ電源に接続し、6000Vまで30秒で昇圧する。銅基板と電極との間に流れる電流値が5000μAになった時点の電圧をポリイミド樹脂組成物膜の耐電圧とした。マイクロメーターにより膜厚を計測し、耐電圧から膜厚を除することで膜厚当たりの耐電圧を算出する。
11 ポリイミド樹脂
12 フィラー
20 金属ベース基板
21 金属基板
22 絶縁膜
23 金属回路層
Claims (6)
- 樹脂と、前記樹脂に分散されているフィラーとを含み、
前記樹脂は、両末端にジカルボン酸基又はジカルボン酸基の酸無水物基を有するポリイミド樹脂を含み、
前記フィラーは、表面に、酸化アルミニウム、水酸化アルミニウム、酸化マグネシウム、水酸化マグネシウムからなる群より選ばれる少なくとも一種の無機化合物を有することを特徴とするポリイミド樹脂組成物。 - 前記ポリイミド樹脂の数平均分子量が、5000以上50000以下の範囲内にある請求項1又は請求項2に記載のポリイミド樹脂組成物。
- 前記フィラーの含有量が60質量%以上90質量%以下の範囲内にある請求項1から請求項3のいずれか一項に記載のポリイミド樹脂組成物。
- 前記樹脂において、前記ポリイミド樹脂の含有量が66質量%以上100質量%以下の範囲内にある請求項1から請求項4のいずれか一項に記載のポリイミド樹脂組成物。
- 金属基板と、絶縁膜と、金属回路層とがこの順で積層された金属ベース基板であって、
前記絶縁膜が請求項1から請求項5のいずれ一項に記載のポリイミド樹脂組成物からなることを特徴とする金属ベース基板。
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EP22759331.6A EP4299649A1 (en) | 2021-02-25 | 2022-02-04 | Polyimide resin composition and metal-based substrate |
US18/275,302 US20240117119A1 (en) | 2021-02-25 | 2022-02-04 | Polyimide resin composition and metal base substrate |
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- 2021-02-25 JP JP2021028910A patent/JP2022129993A/ja active Pending
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- 2022-02-04 US US18/275,302 patent/US20240117119A1/en active Pending
- 2022-02-04 WO PCT/JP2022/004379 patent/WO2022181291A1/ja active Application Filing
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Also Published As
Publication number | Publication date |
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US20240117119A1 (en) | 2024-04-11 |
EP4299649A1 (en) | 2024-01-03 |
JP2022129993A (ja) | 2022-09-06 |
TW202246389A (zh) | 2022-12-01 |
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