JP5665449B2 - Metal-clad laminate and thermally conductive polyimide film - Google Patents
Metal-clad laminate and thermally conductive polyimide film Download PDFInfo
- Publication number
- JP5665449B2 JP5665449B2 JP2010209232A JP2010209232A JP5665449B2 JP 5665449 B2 JP5665449 B2 JP 5665449B2 JP 2010209232 A JP2010209232 A JP 2010209232A JP 2010209232 A JP2010209232 A JP 2010209232A JP 5665449 B2 JP5665449 B2 JP 5665449B2
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- Japan
- Prior art keywords
- polyimide resin
- resin layer
- metal
- clad laminate
- layer
- Prior art date
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- 229920001721 polyimide Polymers 0.000 title claims description 274
- 239000010410 layer Substances 0.000 claims description 263
- 239000009719 polyimide resin Substances 0.000 claims description 202
- 229910052751 metal Inorganic materials 0.000 claims description 54
- 239000002184 metal Substances 0.000 claims description 54
- 239000011231 conductive filler Substances 0.000 claims description 51
- 239000000945 filler Substances 0.000 claims description 35
- 239000011347 resin Substances 0.000 claims description 20
- 229920005989 resin Polymers 0.000 claims description 20
- 239000002245 particle Substances 0.000 claims description 19
- 230000009477 glass transition Effects 0.000 claims description 17
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims description 14
- 229910052582 BN Inorganic materials 0.000 claims description 10
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 10
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000004642 Polyimide Substances 0.000 claims description 8
- 239000000853 adhesive Substances 0.000 claims description 8
- 230000001070 adhesive effect Effects 0.000 claims description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 8
- 239000002356 single layer Substances 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 5
- 239000000395 magnesium oxide Substances 0.000 claims description 5
- 125000000962 organic group Chemical group 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 47
- 239000011889 copper foil Substances 0.000 description 44
- 229920005575 poly(amic acid) Polymers 0.000 description 39
- 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 33
- 230000017525 heat dissipation Effects 0.000 description 17
- 230000015572 biosynthetic process Effects 0.000 description 15
- 238000003786 synthesis reaction Methods 0.000 description 14
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 11
- 239000012790 adhesive layer Substances 0.000 description 11
- 150000004985 diamines Chemical class 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
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- 238000010438 heat treatment Methods 0.000 description 9
- -1 siloxane diamine Chemical class 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 7
- 150000004984 aromatic diamines Chemical group 0.000 description 7
- 230000000704 physical effect Effects 0.000 description 7
- 238000002156 mixing Methods 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- XUSNPFGLKGCWGN-UHFFFAOYSA-N 3-[4-(3-aminopropyl)piperazin-1-yl]propan-1-amine Chemical compound NCCCN1CCN(CCCN)CC1 XUSNPFGLKGCWGN-UHFFFAOYSA-N 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 229920005992 thermoplastic resin Polymers 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 150000008065 acid anhydrides Chemical class 0.000 description 4
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 description 4
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- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- QYIMZXITLDTULQ-UHFFFAOYSA-N 4-(4-amino-2-methylphenyl)-3-methylaniline Chemical group CC1=CC(N)=CC=C1C1=CC=C(N)C=C1C QYIMZXITLDTULQ-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 3
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 2
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 2
- WUPRYUDHUFLKFL-UHFFFAOYSA-N 4-[3-(4-aminophenoxy)phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(OC=2C=CC(N)=CC=2)=C1 WUPRYUDHUFLKFL-UHFFFAOYSA-N 0.000 description 2
- KMKWGXGSGPYISJ-UHFFFAOYSA-N 4-[4-[2-[4-(4-aminophenoxy)phenyl]propan-2-yl]phenoxy]aniline Chemical compound C=1C=C(OC=2C=CC(N)=CC=2)C=CC=1C(C)(C)C(C=C1)=CC=C1OC1=CC=C(N)C=C1 KMKWGXGSGPYISJ-UHFFFAOYSA-N 0.000 description 2
- ZHBXLZQQVCDGPA-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)sulfonyl]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(S(=O)(=O)C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 ZHBXLZQQVCDGPA-UHFFFAOYSA-N 0.000 description 2
- LTPBRCUWZOMYOC-UHFFFAOYSA-N Beryllium oxide Chemical compound O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 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
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- QQSBWCNELOEITJ-UHFFFAOYSA-N dibenzofuran-3,7-diamine Chemical compound NC1=CC=C2C3=CC=C(N)C=C3OC2=C1 QQSBWCNELOEITJ-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- UBGIFSWRDUBQIC-UHFFFAOYSA-N perylene-2,3,8,9-tetracarboxylic acid Chemical compound C1=CC2=C(C(O)=O)C(C(=O)O)=CC(C=3C4=C5C=C(C(C(O)=O)=C4C=CC=3)C(O)=O)=C2C5=C1 UBGIFSWRDUBQIC-UHFFFAOYSA-N 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000013585 weight reducing agent Substances 0.000 description 2
- YTCGLFCOUJIOQH-UHFFFAOYSA-N 1,3,4-oxadiazole-2,5-diamine Chemical compound NC1=NN=C(N)O1 YTCGLFCOUJIOQH-UHFFFAOYSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- RILDMGJCBFBPGH-UHFFFAOYSA-N 1,4,5,8-tetrachloronaphthalene-2,3,6,7-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(Cl)=C2C(Cl)=C(C(O)=O)C(C(=O)O)=C(Cl)C2=C1Cl RILDMGJCBFBPGH-UHFFFAOYSA-N 0.000 description 1
- XMXCPDQUXVZBGQ-UHFFFAOYSA-N 2,3,6,7-tetrachloronaphthalene-1,4,5,8-tetracarboxylic acid Chemical compound ClC1=C(Cl)C(C(O)=O)=C2C(C(=O)O)=C(Cl)C(Cl)=C(C(O)=O)C2=C1C(O)=O XMXCPDQUXVZBGQ-UHFFFAOYSA-N 0.000 description 1
- ZVDSMYGTJDFNHN-UHFFFAOYSA-N 2,4,6-trimethylbenzene-1,3-diamine Chemical group CC1=CC(C)=C(N)C(C)=C1N ZVDSMYGTJDFNHN-UHFFFAOYSA-N 0.000 description 1
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- SDWGBHZZXPDKDZ-UHFFFAOYSA-N 2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic acid Chemical compound C1=C(Cl)C(C(O)=O)=C2C(C(=O)O)=CC(Cl)=C(C(O)=O)C2=C1C(O)=O SDWGBHZZXPDKDZ-UHFFFAOYSA-N 0.000 description 1
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- JZWGLBCZWLGCDT-UHFFFAOYSA-N 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic acid Chemical compound ClC1=CC(C(O)=O)=C2C(C(=O)O)=CC(Cl)=C(C(O)=O)C2=C1C(O)=O JZWGLBCZWLGCDT-UHFFFAOYSA-N 0.000 description 1
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- JRBJSXQPQWSCCF-UHFFFAOYSA-N 3,3'-Dimethoxybenzidine Chemical compound C1=C(N)C(OC)=CC(C=2C=C(OC)C(N)=CC=2)=C1 JRBJSXQPQWSCCF-UHFFFAOYSA-N 0.000 description 1
- NUIURNJTPRWVAP-UHFFFAOYSA-N 3,3'-Dimethylbenzidine Chemical group C1=C(N)C(C)=CC(C=2C=C(C)C(N)=CC=2)=C1 NUIURNJTPRWVAP-UHFFFAOYSA-N 0.000 description 1
- SMDGQEQWSSYZKX-UHFFFAOYSA-N 3-(2,3-dicarboxyphenoxy)phthalic acid Chemical compound OC(=O)C1=CC=CC(OC=2C(=C(C(O)=O)C=CC=2)C(O)=O)=C1C(O)=O SMDGQEQWSSYZKX-UHFFFAOYSA-N 0.000 description 1
- GWHLJVMSZRKEAQ-UHFFFAOYSA-N 3-(2,3-dicarboxyphenyl)phthalic acid Chemical compound OC(=O)C1=CC=CC(C=2C(=C(C(O)=O)C=CC=2)C(O)=O)=C1C(O)=O GWHLJVMSZRKEAQ-UHFFFAOYSA-N 0.000 description 1
- JPOCTPGABIRZFY-UHFFFAOYSA-N 3-(2,3-dicarboxyphenyl)sulfanylphthalic acid Chemical compound OC(=O)C1=CC=CC(SC=2C(=C(C(O)=O)C=CC=2)C(O)=O)=C1C(O)=O JPOCTPGABIRZFY-UHFFFAOYSA-N 0.000 description 1
- NDXGRHCEHPFUSU-UHFFFAOYSA-N 3-(3-aminophenyl)aniline Chemical group NC1=CC=CC(C=2C=C(N)C=CC=2)=C1 NDXGRHCEHPFUSU-UHFFFAOYSA-N 0.000 description 1
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-UHFFFAOYSA-N 0.000 description 1
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- ICNFHJVPAJKPHW-UHFFFAOYSA-N 4,4'-Thiodianiline Chemical compound C1=CC(N)=CC=C1SC1=CC=C(N)C=C1 ICNFHJVPAJKPHW-UHFFFAOYSA-N 0.000 description 1
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- QGRZMPCVIHBQOE-UHFFFAOYSA-N 4,8-dimethyl-1,2,3,5,6,7-hexahydronaphthalene-1,2,5,6-tetracarboxylic acid Chemical compound OC(=O)C1C(C(O)=O)CC(C)=C2C(C(O)=O)C(C(O)=O)CC(C)=C21 QGRZMPCVIHBQOE-UHFFFAOYSA-N 0.000 description 1
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Description
本発明は、熱伝導特性に優れる絶縁層を有し、放熱基板や回路基板に好適に使用される金属張積層体及び熱伝導性ポリイミドフィルムに関するものである。 The present invention relates to a metal-clad laminate and a heat conductive polyimide film that have an insulating layer having excellent heat conduction characteristics and are suitably used for a heat dissipation board and a circuit board.
近年、携帯電話に代表される電子機器の小型化、軽量化に対する要求が高まってきており、それに伴い機器の小型化、軽量化に有利なフレキシブル回路基板が電子技術分野において広く使用されるようになってきている。その中でもポリイミド樹脂を絶縁層とするフレキシブル回路基板は、その耐熱性、耐薬品性などが良好なことから従来から広く用いられている。 In recent years, there has been an increasing demand for downsizing and weight reduction of electronic devices typified by mobile phones, and accordingly, flexible circuit boards that are advantageous for downsizing and weight reduction of devices are widely used in the electronic technology field. It has become to. Among them, a flexible circuit board using a polyimide resin as an insulating layer has been widely used since its heat resistance and chemical resistance are good.
ところで、最近の電子機器の小型化により、回路の集積度は上がってきており、情報処理の高速化とも相まって、機器内に生じる熱の放熱手段が注目されている。 By the way, with the recent miniaturization of electronic devices, the degree of circuit integration has increased, and in conjunction with the speeding up of information processing, heat dissipation means for heat generated in the device has attracted attention.
また、地球温暖化を始めとする環境問題への意識の高まりにより、環境負荷が低くかつ省エネルギーな製品が強く求められるようになっている。その代表例として、白熱灯に代わりＬＥＤ照明の急速な普及が挙げられるが、ＬＥＤ照明の性能を充分に発揮させるためには、使用時に発生する熱を効率的に逃がすことが重要となっている。 In addition, with the growing awareness of environmental issues such as global warming, there is a strong demand for products with low environmental impact and energy saving. A typical example is the rapid spread of LED lighting in place of incandescent lamps, but in order to fully demonstrate the performance of LED lighting, it is important to efficiently release the heat generated during use. .
そこで、加工性に富み、放熱性に優れたフレキシブル回路基板を提供するために、絶縁層を構成するポリイミドフィルムに関し、厚み方向の熱伝導率を向上させる検討がなされている（特許文献１）。また、熱伝導性フィラーを含有する熱伝導性ポリイミドフィルムに関して、シロキサンジアミンから誘導されるポリイミドに熱伝導性フィラーを分散させたポリイミドフィルム複合材料も提案されている（特許文献２）。 Then, in order to provide the flexible circuit board which is rich in workability and was excellent in heat dissipation, about the polyimide film which comprises an insulating layer, examination which improves the thermal conductivity of the thickness direction is made | formed (patent document 1). Moreover, the polyimide film composite material which disperse | distributed the heat conductive filler to the polyimide induced | guided | derived from siloxane diamine is also proposed regarding the heat conductive polyimide film containing a heat conductive filler (patent document 2).
しかし、上記従来技術のポリイミドフィルムの厚み方向の熱伝導率では、例えばＬＥＤ照明に使用するには放熱基板としての性能が不足しており、改善の必要があった。また、一般に、銅箔などの金属層に樹脂層を積層して金属張積層体を作製する場合、通常、金属層と樹脂層との間にエポキシ系接着剤や熱可塑性樹脂による接着層を設ける必要がある。この接着層の介在は、金属層（導体層）に生じる熱の放熱をさらに低下させる要因になるばかりでなく、実用的な基板として使用する場合に求められる耐熱性、屈曲性などの諸特性の低下を招く。 However, the thermal conductivity in the thickness direction of the above-described conventional polyimide film is insufficient in performance as a heat dissipation substrate for use in, for example, LED lighting, and needs to be improved. In general, when a metal-clad laminate is produced by laminating a resin layer on a metal layer such as copper foil, an adhesive layer made of an epoxy adhesive or a thermoplastic resin is usually provided between the metal layer and the resin layer. There is a need. The interposition of this adhesive layer not only causes a further decrease in heat dissipation generated in the metal layer (conductor layer), but also has various characteristics such as heat resistance and flexibility required for use as a practical substrate. Incurs a decline.
また、ポリイミド樹脂の熱伝導性を改善するため、熱伝導性フィラーを配合した特定の構造単位を有するポリイミド樹脂層と、このポリイミド樹脂層よりもガラス転移温度が低いポリイミド樹脂層を積層した熱伝導性ポリイミドフィルムが提案されている（特許文献３）。さらに、熱伝導性フィラーとして、平均長径が０．１〜１５μｍの板状フィラーと、平均粒径が０．０５〜１０μｍの球状フィラーとを所定比率で組み合わせて配合した高熱伝導性ポリイミドフィルムの提案もなされている（特許文献４）。 In addition, in order to improve the thermal conductivity of the polyimide resin, a thermal conductivity in which a polyimide resin layer having a specific structural unit containing a thermally conductive filler and a polyimide resin layer having a glass transition temperature lower than that of the polyimide resin layer are laminated. A conductive polyimide film has been proposed (Patent Document 3). Furthermore, as a thermally conductive filler, a proposal of a highly thermally conductive polyimide film in which a plate-like filler having an average major axis of 0.1 to 15 μm and a spherical filler having an average particle diameter of 0.05 to 10 μm are combined in a predetermined ratio. (Patent Document 4).
上記特許文献３で提案されたフレキシブル基板用積層体や熱伝導性ポリイミドフィルムは、熱伝導性を有するものであるが、金属層との接着強度を保つために、金属層との間に熱伝導性フィラーを配合していないポリイミド樹脂層を接着層として介在させている。そのため、接着層の厚みに応じて熱伝導性が低下していく懸念があり、その点で改善の余地が残されていた。また、特許文献４に示されているものも、熱伝導性フィラーを含有する樹脂層は本質的に金属層との接着力が十分でないため、これを確保するためには接着層を設けることが必要であった。 The laminate for a flexible substrate and the thermally conductive polyimide film proposed in Patent Document 3 have thermal conductivity. However, in order to maintain the adhesive strength with the metal layer, thermal conduction is performed between the metal layer and the metal layer. A polyimide resin layer that does not contain a conductive filler is interposed as an adhesive layer. For this reason, there is a concern that the thermal conductivity is lowered depending on the thickness of the adhesive layer, and there remains room for improvement in that respect. Moreover, since the resin layer containing a heat conductive filler also has the adhesive force with a metal layer essentially that the thing shown by patent document 4 is sufficient, in order to ensure this, it is necessary to provide an adhesive layer. It was necessary.
なお、熱伝導性フィラーを配合した熱伝導性ポリイミド樹脂層の接着性を改善するため、熱伝導性ポリイミド樹脂層を主に熱可塑性樹脂によって形成することも考えられる。しかし、熱可塑性樹脂を主体とする場合、その熱膨張係数が大きいという特性から回路基板用途に求められる寸法安定性が得られなくなる可能性がある。また、熱可塑性樹脂は一般的に耐熱性も低いため、単に熱可塑性樹脂を適用するだけでは十分な耐熱性を確保することができず、高温環境で使用される放熱基板の主樹脂層としての適用には、技術常識に照らして不向きと考えられるため、これまで検討がされていなかった。 In addition, in order to improve the adhesiveness of the heat conductive polyimide resin layer which mix | blended the heat conductive filler, it is also considered that a heat conductive polyimide resin layer is mainly formed with a thermoplastic resin. However, when a thermoplastic resin is mainly used, there is a possibility that the dimensional stability required for circuit board use cannot be obtained due to the characteristic that the coefficient of thermal expansion is large. In addition, since thermoplastic resins generally have low heat resistance, it is not possible to ensure sufficient heat resistance simply by applying a thermoplastic resin, and as a main resin layer of a heat dissipation board used in a high temperature environment. The application was considered unsuitable in the light of technical common sense, and has not been studied so far.
そこで、接着層を必要とせずに、金属層と絶縁層との間の実用的接着強度を有し、かつ絶縁層の熱伝導性に優れた金属張積層体及び熱伝導性ポリイミドフィルムの提供が望まれていた。 Accordingly, there is provided a metal-clad laminate and a thermally conductive polyimide film that have a practical adhesive strength between the metal layer and the insulating layer without requiring an adhesive layer, and that have excellent thermal conductivity of the insulating layer. It was desired.
本発明は、熱伝導特性に優れ、接着層を設けなくても金属層と絶縁層との実用的接着強度を有し、更に耐熱性も良好な金属張積層体及び熱伝導性ポリイミドフィルムを提供することを目的とする。 The present invention provides a metal-clad laminate and a heat-conducting polyimide film that have excellent heat conduction characteristics, have a practical adhesion strength between a metal layer and an insulating layer without providing an adhesive layer, and also have good heat resistance. The purpose is to do.
本発明者等は、上記課題を解決するために検討を重ねた結果、金属張積層体のポリイミド樹脂層の少なくとも１層又は熱伝導性ポリイミドフィルムを構成するポリイミド樹脂層の少なくとも１層を、高熱伝導性フィラーを含有するとともに、金属層に対して高い接着性を示す特定のポリイミド樹脂により形成することで上記課題を解決し得ることを見出し、本発明を完成するに至った。 As a result of repeated investigations to solve the above problems, the present inventors have determined that at least one layer of the polyimide resin layer of the metal-clad laminate or at least one layer of the polyimide resin layer constituting the thermally conductive polyimide film is highly heated. It has been found that the above-mentioned problems can be solved by forming with a specific polyimide resin containing a conductive filler and exhibiting high adhesion to the metal layer, and the present invention has been completed.
すなわち、本発明の金属張積層体は、単層又は複数層から構成されるポリイミド樹脂層（Ｉ）と、
前記ポリイミド樹脂層（Ｉ）の片面又は両面に設けられた金属層と、
を備えた金属張積層体であって、
前記ポリイミド樹脂層（Ｉ）は、その全体の厚みの７０％以上の厚みを有するポリイミド樹脂層（ｉ）を有しており、かつ、前記ポリイミド樹脂層（Ｉ）全体のガラス転移温度が３００℃以上であり、
前記ポリイミド樹脂層（ｉ）が、下記一般式（１）で表される構造単位を６０モル％以上含有するポリイミド樹脂によって構成されるとともに、熱伝導性フィラーを４０〜８０ｖｏｌ％の範囲内で含有するものであることを特徴とする［一般式（１）中、Ａｒ1は芳香環を１個以上有する４価の有機基である。］。
That is, the metal-clad laminate of the present invention includes a polyimide resin layer (I) composed of a single layer or a plurality of layers,
A metal layer provided on one or both sides of the polyimide resin layer (I);
A metal-clad laminate comprising:
The polyimide resin layer (I) has a polyimide resin layer (i) having a thickness of 70% or more of the total thickness, and the glass transition temperature of the entire polyimide resin layer (I) is 300 ° C. That's it,
While the said polyimide resin layer (i) is comprised with the polyimide resin which contains 60 mol% or more of structural units represented by following General formula (1), it contains a heat conductive filler in the range of 40-80 vol%. [In general formula (1), Ar 1 is a tetravalent organic group having one or more aromatic rings. ].
また、本発明の熱伝導性ポリイミドフィルムは、単層又は複数層から構成される熱伝導性ポリイミドフィルムであって、
前記熱伝導性ポリイミドフィルムの全体の厚みの７０％以上の厚みを有するポリイミド樹脂層（ｉ）を有しており、かつ、前記熱伝導性ポリイミドフィルム全体のガラス転移温度が３００℃以上であり、
前記ポリイミド樹脂層（ｉ）が、下記一般式（１）で表される構造単位を６０モル％以上含有するポリイミド樹脂によって構成されるとともに、熱伝導性フィラーを４０〜８０ｖｏｌ％の範囲内で含有するものであることを特徴とする［一般式（１）中、Ａｒ1は芳香環を１個以上有する４価の有機基である。］。
The thermally conductive polyimide film of the present invention is a thermally conductive polyimide film composed of a single layer or a plurality of layers,
It has a polyimide resin layer (i) having a thickness of 70% or more of the total thickness of the thermally conductive polyimide film, and the glass transition temperature of the entire thermally conductive polyimide film is 300 ° C. or higher,
While the said polyimide resin layer (i) is comprised with the polyimide resin which contains 60 mol% or more of structural units represented by following General formula (1), it contains a heat conductive filler in the range of 40-80 vol%. [In general formula (1), Ar 1 is a tetravalent organic group having one or more aromatic rings. ].
本発明の好ましい実施の態様を次に示す。
１） ポリイミド樹脂層（ｉ）の少なくとも一方の面が金属層と直接接している上記の金属張積層体。
２） 片面又は両面に金属層と直接張り合わされる粘着性貼着面を備えている上記の熱伝導性ポリイミドフィルム。
３） 熱伝導性フィラーがシリカ、アルミナ、窒化アルミニウム、窒化ホウ素、窒化ケイ素及びマグネシアから選ばれる少なくとも１種類以上のフィラーであり、平均粒子径が０．０１〜２５μｍの範囲にある上記の金属張積層体又は上記の熱伝導性ポリイミドフィルム。
４） ポリイミド樹脂層（Ｉ）の熱伝導率が１．０Ｗ／ｍＫ以上であり、ポリイミド樹脂層（Ｉ）と金属層とのピール強度が０．５ｋＮ／ｍ以上である上記の金属張積層体。
５） 熱伝導率が１．０Ｗ／ｍＫ以上である上記の熱伝導性ポリイミドフィルム。
A preferred embodiment of the present invention will be described below.
1) The above metal-clad laminate in which at least one surface of the polyimide resin layer (i) is in direct contact with the metal layer.
2) Said heat conductive polyimide film provided with the adhesive sticking surface bonded directly to a metal layer on one or both surfaces.
3) The above metal-clad, wherein the thermally conductive filler is at least one filler selected from silica, alumina, aluminum nitride, boron nitride, silicon nitride and magnesia, and has an average particle diameter in the range of 0.01 to 25 μm. A laminate or the above-mentioned thermally conductive polyimide film.
4) The above metal-clad laminate in which the thermal conductivity of the polyimide resin layer (I) is 1.0 W / mK or more and the peel strength between the polyimide resin layer (I) and the metal layer is 0.5 kN / m or more. .
5) Said heat conductive polyimide film whose heat conductivity is 1.0 W / mK or more.
本発明の金属張積層体及び熱伝導性ポリイミドフィルムは、上記一般式（１）で表される構造単位を６０モル％以上含有するポリイミド樹脂によって構成されるとともに熱伝導性フィラーを４０〜８０ｖｏｌ％の範囲内で含有するポリイミド樹脂層（ｉ）が、ポリイミド樹脂層（Ｉ）又は熱伝導性ポリイミドフィルムの全体の厚みの７０％以上の厚みで存在し、かつ、ポリイミド樹脂層（Ｉ）又は熱伝導性ポリイミドフィルムの全体のガラス転移温度が３００℃以上であるため、熱伝導性と金属層への接着性に優れているとともに、十分な耐熱性を有する。従って、本発明の金属張積層体及び熱伝導性ポリイミドフィルムは、良好な放熱性が求められる電子機器、照明機器などの基板材料として好適に用いることができる。 The metal-clad laminate and the heat conductive polyimide film of the present invention are composed of a polyimide resin containing 60 mol% or more of the structural unit represented by the general formula (1) and have a heat conductive filler of 40 to 80 vol%. The polyimide resin layer (i) contained within the range of is present in a thickness of 70% or more of the total thickness of the polyimide resin layer (I) or the heat conductive polyimide film, and the polyimide resin layer (I) or heat Since the entire glass transition temperature of the conductive polyimide film is 300 ° C. or higher, the conductive polyimide film has excellent heat conductivity and adhesion to the metal layer, and has sufficient heat resistance. Therefore, the metal-clad laminate and the heat conductive polyimide film of the present invention can be suitably used as a substrate material for electronic devices and lighting devices that require good heat dissipation.
以下、本発明の実施の形態について詳細に説明する。まず、本発明の第１の実施の形態として、金属張積層体について説明し、次に、本発明の第２の実施の形態として熱伝導性ポリイミドフィルムについて説明する。 Hereinafter, embodiments of the present invention will be described in detail. First, a metal-clad laminate will be described as a first embodiment of the present invention, and then a thermally conductive polyimide film will be described as a second embodiment of the present invention.
［第１の実施の形態］
金属張積層体：
本実施の形態の金属張積層体は、単層又は複数層からなるポリイミド樹脂層（Ｉ）と、このポリイミド樹脂層（Ｉ）の片面又は両面に設けられた金属層と、を備えている。以下、ポリイミド樹脂層（Ｉ）、金属層、金属張積層体の積層構造、金属張積層体の製造例及び金属張積層体の物性（ピール強度）の順に説明する。
[First Embodiment]
Metal-clad laminate:
The metal-clad laminate of the present embodiment includes a polyimide resin layer (I) composed of a single layer or a plurality of layers, and a metal layer provided on one side or both sides of the polyimide resin layer (I). Hereinafter, the polyimide resin layer (I), the metal layer, the laminated structure of the metal-clad laminate, the production example of the metal-clad laminate, and the physical properties (peel strength) of the metal-clad laminate will be described in this order.
［ポリイミド樹脂層（Ｉ）］
ポリイミド樹脂層（Ｉ）は、単一の層のみからなるものであっても、複数層からなるものであってもよいが、少なくとも、上記一般式（１）で表される構造単位を６０モル％以上含有するポリイミド樹脂によって構成され、かつ熱伝導性フィラーを４０〜８０ｖｏｌ％の範囲内で含有するポリイミド樹脂層（ｉ）を有している。
[Polyimide resin layer (I)]
The polyimide resin layer (I) may be composed of a single layer or a plurality of layers, but at least 60 mol of the structural unit represented by the general formula (1) is used. The polyimide resin layer (i) is composed of a polyimide resin containing at least% and contains a thermally conductive filler in the range of 40 to 80 vol%.
＜ポリイミド樹脂層（ｉ）＞
（構成樹脂）
ポリイミド樹脂層（ｉ）を構成するポリイミド樹脂は、一般式（１）で表される構造単位を６０モル％以上含有することが必要であり、８０モル％以上含有することが好ましい。一般式（１）で表される構造単位の含有量が６０モル％未満であると、耐熱性、引裂き伝播抵抗及び金属層への接着性が低下する。
<Polyimide resin layer (i)>
(Constituent resin)
The polyimide resin constituting the polyimide resin layer (i) needs to contain 60 mol% or more of the structural unit represented by the general formula (1), and preferably contains 80 mol% or more. When the content of the structural unit represented by the general formula (1) is less than 60 mol%, heat resistance, tear propagation resistance and adhesion to the metal layer are lowered.
一般式（１）中、Ａｒ1は芳香環を１個以上有する４価の有機基である。Ａｒ1は、ポリイミド原料である芳香族テトラカルボン酸の残基と見ることができるので、芳香族テトラカルボン酸の具体例を示すことにより、Ａｒ1が理解される。 In general formula (1), Ar 1 is a tetravalent organic group having one or more aromatic rings. Since Ar 1 can be regarded as a residue of an aromatic tetracarboxylic acid that is a polyimide raw material, Ar 1 is understood by showing a specific example of an aromatic tetracarboxylic acid.
芳香族テトラカルボン酸の具体例としては、ピロメリット酸二無水物(PMDA)、3,3',4,4'-ベンゾフェノンテトラカルボン酸二無水物、2,2',3,3'-ベンゾフェノンテトラカルボン酸二無水物、2,3,3',4'-ベンゾフェノンテトラカルボン酸二無水物、ナフタレン-2,3,6,7-テトラカルボン酸二無水物(NTCDA)、ナフタレン-1,2,5,6-テトラカルボン酸二無水物、ナフタレン-1,2,4,5-テトラカルボン酸二無水物、ナフタレン-1,4,5,8-テトラカルボン酸二無水物、ナフタレン-1,2,6,7-テトラカルボン酸二無水物、4,8-ジメチル-1,2,3,5,6,7-ヘキサヒドロナフタレン-1,2,5,6-テトラカルボン酸二無水物、4,8-ジメチル-1,2,3,5,6,7-ヘキサヒドロナフタレン-2,3,6,7-テトラカルボン酸二無水物、2,6-ジクロロナフタレン-1,4,5,8-テトラカルボン酸二無水物、2,7-ジクロロナフタレン-1,4,5,8-テトラカルボン酸二無水物、2,3,6,7-テトラクロロナフタレン-1,4,5,8-テトラカルボン酸二無水物、1,4,5,8-テトラクロロナフタレン-2,3,6,7-テトラカルボン酸二無水物、3,3',4,4'-ビフェニルテトラカルボン酸二無水物(BPDA)、2,2',3,3'-ビフェニルテトラカルボン酸二無水物、2,3,3',4'-ビフェニルテトラカルボン酸二無水物、3,3'',4,4''-p-テルフェニルテトラカルボン酸二無水物、2,2'',3,3''-p-テルフェニルテトラカルボン酸二無水物、2,3,3'',4''-p-テルフェニルテトラカルボン酸二無水物、2,2-ビス(2,3-ジカルボキシフェニル)-プロパン二無水物、2,2-ビス(3,4-ジカルボキシフェニル)-プロパン二無水物、ビス(2,3-ジカルボキシフェニル)エーテル二無水物、ビス(2,3-ジカルボキシフェニル)メタン二無水物、ビス(3.4-ジカルボキシフェニル)メタン二無水物、ビス(2,3-ジカルボキシフェニル)スルホン二無水物、ビス(3,4-ジカルボキシフェニル)スルホン二無水物、1,1-ビス(2,3-ジカルボキシフェニル)エタン二無水物、1,1-ビス(3,4-ジカルボキシフェニル)エタン二無水物、ペリレン-2,3,8,9-テトラカルボン酸二無水物、ペリレン-3,4,9,10-テトラカルボン酸二無水物、ペリレン-4,5,10,11-テトラカルボン酸二無水物、ペリレン-5,6,11,12-テトラカルボン酸二無水物、フェナンスレン-1,2,7,8-テトラカルボン酸二無水物、フェナンスレン-1, 2,6,7-テトラカルボン酸二無水物、フェナンスレン-1,2,9,10-テトラカルボン酸二無水物、シクロペンタン-1,2,3,4-テトラカルボン酸二無水物、ピラジン-2,3,5,6-テトラカルボン酸二無水物、ピロリジン-2,3,4,5-テトラカルボン酸二無水物、チオフェン-2,3,4,5-テトラカルボン酸二無水物、4,4'-オキシジフタル酸二無水物などが挙げられる。これらの中でも、ポリイミド樹脂に耐熱性、寸法安定性を付与する観点から、ピロメリット酸二無水物（ＰＭＤＡ）が好ましく、これを全酸無水物成分に対して６０モル％以上、特には８０モル％以上の割合で用いることが好ましい。 Specific examples of aromatic tetracarboxylic acids include pyromellitic dianhydride (PMDA), 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride, 2,2', 3,3'-benzophenone Tetracarboxylic dianhydride, 2,3,3 ', 4'-benzophenonetetracarboxylic dianhydride, naphthalene-2,3,6,7-tetracarboxylic dianhydride (NTCDA), naphthalene-1,2 , 5,6-tetracarboxylic dianhydride, naphthalene-1,2,4,5-tetracarboxylic dianhydride, naphthalene-1,4,5,8-tetracarboxylic dianhydride, naphthalene-1, 2,6,7-tetracarboxylic dianhydride, 4,8-dimethyl-1,2,3,5,6,7-hexahydronaphthalene-1,2,5,6-tetracarboxylic dianhydride, 4,8-dimethyl-1,2,3,5,6,7-hexahydronaphthalene-2,3,6,7-tetracarboxylic dianhydride, 2,6-dichloronaphthalene-1,4,5, 8-tetracarboxylic dianhydride, 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic acid Anhydride, 2,3,6,7-tetrachloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 1,4,5,8-tetrachloronaphthalene-2,3,6,7- Tetracarboxylic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride (BPDA), 2,2', 3,3'-biphenyltetracarboxylic dianhydride, 2,3, 3 ', 4'-biphenyltetracarboxylic dianhydride, 3,3``, 4,4' '-p-terphenyltetracarboxylic dianhydride, 2,2``, 3,3' '-p -Terphenyltetracarboxylic dianhydride, 2,3,3``, 4 ''-p-terphenyltetracarboxylic dianhydride, 2,2-bis (2,3-dicarboxyphenyl) -propane Anhydride, 2,2-bis (3,4-dicarboxyphenyl) -propane dianhydride, bis (2,3-dicarboxyphenyl) ether dianhydride, bis (2,3-dicarboxyphenyl) methane Anhydride, bis (3.4-dicarboxyphenyl) methane dianhydride, bis (2,3-dicarboxyphenyl) sulfur Dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-di Carboxyphenyl) ethane dianhydride, perylene-2,3,8,9-tetracarboxylic dianhydride, perylene-3,4,9,10-tetracarboxylic dianhydride, perylene-4,5,10, 11-tetracarboxylic dianhydride, perylene-5,6,11,12-tetracarboxylic dianhydride, phenanthrene-1,2,7,8-tetracarboxylic dianhydride, phenanthrene-1, 2,6 , 7-tetracarboxylic dianhydride, phenanthrene-1,2,9,10-tetracarboxylic dianhydride, cyclopentane-1,2,3,4-tetracarboxylic dianhydride, pyrazine-2,3 , 5,6-tetracarboxylic dianhydride, pyrrolidine-2,3,4,5-tetracarboxylic dianhydride, thiophene-2,3,4,5-tetracarboxylic dianhydride, 4,4 ' -Oxydiphthalic dianhydride . Among these, pyromellitic dianhydride (PMDA) is preferable from the viewpoint of imparting heat resistance and dimensional stability to the polyimide resin, and this is 60 mol% or more, particularly 80 mol, based on the total acid anhydride component. It is preferable to use it in the ratio of% or more.
また、一般式（１）で表される構造単位の原料となるジアミンとしては、２,２-ビス［４−（４-アミノフェノキシ）フェニル］プロパン（ＢＡＰＰ）を用いることができる。ジアミンとしてＢＡＰＰを用いることで、ポリイミド樹脂層（ｉ）に優れた接着性を付与することができる。また、全ジアミン成分に対して６０モル％以上のＢＡＰＰと、全酸無水物成分に対して６０モル％以上のピロメリット酸二無水物（ＰＭＤＡ）とを組み合わせて用いることによって、ポリイミド樹脂層（ｉ）、さらには、これを含むポリイミド樹脂層（Ｉ）のガラス転移温度Ｔｇを高くすることが可能であり、耐熱性を向上させることができる。 In addition, 2,2-bis [4- (4-aminophenoxy) phenyl] propane (BAPP) can be used as a diamine which is a raw material for the structural unit represented by the general formula (1). By using BAPP as the diamine, excellent adhesiveness can be imparted to the polyimide resin layer (i). Further, by using a combination of 60 mol% or more of BAPP with respect to the total diamine component and 60 mol% or more of pyromellitic dianhydride (PMDA) with respect to the total acid anhydride component, a polyimide resin layer ( i) Furthermore, it is possible to increase the glass transition temperature Tg of the polyimide resin layer (I) containing this, and to improve the heat resistance.
ポリイミド樹脂層（ｉ）中に含まれる、一般式（１）で表される構造単位以外の構造単位としては、ポリイミド原料である芳香族テトラカルボン酸の残基と芳香族ジアミンの残基とに分けて説明すると、芳香族テトラカルボン酸の残基としては、上記Ａｒ1で説明したものと同様な芳香族テトラカルボン酸の残基を挙げることができる。 As structural units other than the structural unit represented by the general formula (1) contained in the polyimide resin layer (i), there are aromatic tetracarboxylic acid residues and aromatic diamine residues which are polyimide raw materials. If it demonstrates separately, the residue of aromatic tetracarboxylic acid similar to what was demonstrated by said Ar < 1 > can be mentioned as a residue of aromatic tetracarboxylic acid.
芳香族ジアミンの残基としては、次に示すような芳香族ジアミンの残基を挙げることができる。すなわち、4,6-ジメチル-ｍ-フェニレンジアミン、2,5-ジメチル-p-フェニレジアミン、2,4-ジアミノメシチレン、4,4'-メチレンジ-o-トルイジン、4,4'-メチレンジ-2,6-キシリジン、4,4'-メチレン-2,6-ジエチルアニリン、2,4-トルエンジアミン、ｍ-フェニレンジアミン、p-フェニレンジアミン、4,4'-ジアミノジフェニルプロパン、3,3'-ジアミノジフェニルプロパン、4,4'-ジアミノジフェニルエタン、3,3'-ジアミノジフェニルエタン、4,4'-ジアミノジフェニルメタン、3,3'-ジアミノジフェニルメタン、4,4'-ジアミノジフェニルスルフィド、3,3'-ジアミノジフェニルスルフィド、4,4'-ジアミノジフェニルスルホン、3,3'-ジアミノジフェニルスルホン、4,4'-ジアミノジフェニルエーテル、3,3-ジアミノジフェニルエーテル、1,3-ビス（3-アミノフェノキシ）ベンゼン、1,3-ビス（4-アミノフェノキシ）ベンゼン、1,4-ビス（4-アミノフェノキシ）ベンゼン、ベンジジン、3,3'-ジアミノビフェニル、3,3'-ジメチル-4,4'-ジアミノビフェニル、3,3'-ジメトキシベンジジン、4,4'-ジアミノ-p-テルフェニル、3,3'-ジアミノ-p-テルフェニル、ビス(p-アミノシクロヘキシル)メタン、ビス(p-β-アミノ-t-ブチルフェニル)エーテル、ビス(p-β-メチル-δ-アミノペンチル)ベンゼン、p-ビス(2-メチル-4-アミノペンチル)ベンゼン、p-ビス(1,1-ジメチル-5-アミノペンチル)ベンゼン、1,5-ジアミノナフタレン、2,6-ジアミノナフタレン、2,4-ビス(β-アミノ-t-ブチル)トルエン、2,4-ジアミノトルエン、ｍ-キシレン-2,5-ジアミン、p-キシレン-2,5-ジアミン、ｍ-キシリレンジアミン、p-キシリレンジアミン、2,6-ジアミノピリジン、2,5-ジアミノピリジン、2,5-ジアミノ-1,3,4-オキサジアゾール、ピペラジン、2,2'-ジメチル-4,4'-ジアミノビフェニル、3,7-ジアミノジベンゾフラン、1,5-ジアミノフルオレン、ジベンゾ-p-ジオキシン-2,7-ジアミン、4,4'-ジアミノベンジルなどが挙げられる。 Examples of the aromatic diamine residue include the following aromatic diamine residues. Namely, 4,6-dimethyl-m-phenylenediamine, 2,5-dimethyl-p-phenylediamine, 2,4-diaminomesitylene, 4,4'-methylenedi-o-toluidine, 4,4'-methylenedi- 2,6-xylidine, 4,4'-methylene-2,6-diethylaniline, 2,4-toluenediamine, m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenylpropane, 3,3 ' -Diaminodiphenylpropane, 4,4'-diaminodiphenylethane, 3,3'-diaminodiphenylethane, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide, 3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl ether, 3,3-diaminodiphenyl ether, 1,3-bis (3-aminophenoxy ) Benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, benzidine, 3,3'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3 ' -Dimethoxybenzidine, 4,4'-diamino-p-terphenyl, 3,3'-diamino-p-terphenyl, bis (p-aminocyclohexyl) methane, bis (p-β-amino-t-butylphenyl) Ether, bis (p-β-methyl-δ-aminopentyl) benzene, p-bis (2-methyl-4-aminopentyl) benzene, p-bis (1,1-dimethyl-5-aminopentyl) benzene, 1 , 5-diaminonaphthalene, 2,6-diaminonaphthalene, 2,4-bis (β-amino-t-butyl) toluene, 2,4-diaminotoluene, m-xylene-2,5-diamine, p-xylene- 2,5-diamine, m-xylylenediamine, p-xylylenediamine, 2,6-diaminopyridine, 2,5-diaminopyridine, 2,5-diamino-1,3,4 -Oxadiazole, piperazine, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,7-diaminodibenzofuran, 1,5-diaminofluorene, dibenzo-p-dioxin-2,7-diamine, 4, 4'-diaminobenzyl and the like can be mentioned.
ポリイミド樹脂層（ｉ）を構成するポリイミド樹脂を合成する場合、ジアミン、酸無水物はそれぞれ１種のみを使用してもよく、２種以上を併用することもできる。 When synthesize | combining the polyimide resin which comprises a polyimide resin layer (i), only 1 type may be used for a diamine and an acid anhydride, respectively, and 2 or more types can also be used together.
本発明では、ポリイミド樹脂層（ｉ）に熱伝導性フィラーを含有するため、ポリイミド樹脂の優れた耐熱性や寸法安定性を維持しながら、その機械的強度を保持させる必要がある。そのような観点から、上記他のジアミンとしては、一般式（１）で表わされる構造単位を与えるジアミンより剛直な構造を有する芳香族ジアミンが適する。有利には、ジアミン成分に、例えば1,4-フェニレンジアミン、2,2'-ジメチル-4,4'-ジアミノビフェニル、2,7-ジアミノフルオレン、3,7-ジアミノジベンゾフラン、3,8-ジアミノジベンゾピラノンから選択される少なくとも１種のジアミンを他のジアミンとして併用することがよい。他のジアミンの使用割合は０〜４０モル％の範囲内が好ましく、０〜２０モル％の範囲内が好ましい。 In the present invention, since the polyimide resin layer (i) contains a thermally conductive filler, it is necessary to maintain the mechanical strength while maintaining the excellent heat resistance and dimensional stability of the polyimide resin. From such a viewpoint, as the other diamine, an aromatic diamine having a structure more rigid than the diamine that gives the structural unit represented by the general formula (1) is suitable. Advantageously, the diamine component is, for example, 1,4-phenylenediamine, 2,2′-dimethyl-4,4′-diaminobiphenyl, 2,7-diaminofluorene, 3,7-diaminodibenzofuran, 3,8-diamino. At least one diamine selected from dibenzopyranone may be used in combination as another diamine. The use ratio of the other diamine is preferably in the range of 0 to 40 mol%, and preferably in the range of 0 to 20 mol%.
（熱伝導フィラー）
ポリイミド樹脂層（ｉ）中の熱伝導性フィラーの含有割合は、４０〜８０ｖｏｌ％の範囲内であることが必要であり、４５〜７０ｖｏｌ％の範囲内が好ましい。熱伝導性フィラーの含有割合が４０ｖｏｌ％に満たないと、回路基板等の電子部品とした際の放熱特性が十分でなく、８０ｖｏｌ％を超えると耐折性や耐屈曲性の低下が顕著となり、また、ポリイミド樹脂層の強度も低下する。熱伝導性フィラーとしては、高熱伝導性のフィラーが好ましく、具体的には、例えばアルミニウム、銅、ニッケル、シリカ、ダイヤモンド、アルミナ、マグネシア、ベリリア、窒化ホウ素、窒化アルミニウム、窒化ケイ素、炭化ケイ素等が挙げられる。これらの中でも、シリカ、アルミナ、窒化アルミニウム、窒化ホウ素、窒化ケイ素及びマグネシアから選ばれる少なくとも１種類のフィラーが好ましい。ポリイミド樹脂層は絶縁層として作用するので、その観点からはポリイミド樹脂層に配合されるフィラーは絶縁性であるものが適する。フィラー形状は、特に制限されるものではなく、例えば板状（燐片状を含む）、球状、針状、棒状のいずれでも良い。また、熱伝導性フィラーの含有量を高め、熱伝導性などの特性とのバランスを考慮すると異なる形状（例えば、板状と球状、板状と針状など）のフィラーを併用することも好ましい。
(Thermal conductive filler)
The content ratio of the heat conductive filler in the polyimide resin layer (i) needs to be in the range of 40 to 80 vol%, and preferably in the range of 45 to 70 vol%. When the content ratio of the heat conductive filler is less than 40 vol%, the heat dissipation characteristics when the electronic parts such as the circuit board are used are not sufficient, and when it exceeds 80 vol%, the bending resistance and the bending resistance decrease significantly. In addition, the strength of the polyimide resin layer also decreases. As the thermally conductive filler, a highly thermally conductive filler is preferable, and specifically, for example, aluminum, copper, nickel, silica, diamond, alumina, magnesia, beryllia, boron nitride, aluminum nitride, silicon nitride, silicon carbide, etc. Can be mentioned. Among these, at least one filler selected from silica, alumina, aluminum nitride, boron nitride, silicon nitride, and magnesia is preferable. Since the polyimide resin layer acts as an insulating layer, the filler blended in the polyimide resin layer is suitable from that viewpoint. The filler shape is not particularly limited, and may be, for example, a plate shape (including a flake shape), a spherical shape, a needle shape, or a rod shape. It is also preferable to use fillers having different shapes (for example, plate-shaped and spherical, plate-shaped and needle-shaped) in consideration of increasing the content of the heat-conductive filler and considering the balance with characteristics such as heat conductivity.
熱伝導性フィラーの粒子サイズは、ポリイミド樹脂層（ｉ）の厚み方向にフィラーを均一に分散させて熱伝導性を向上させる観点から、例えば、平均粒子径が０．０１〜２５μｍの範囲内にあることが好ましく、１〜８μｍの範囲内にあることがより好ましい。熱伝導性フィラーの平均粒子径が０．０１μｍに満たないと、個々のフィラー内部での熱伝導が小さくなり、結果としてポリイミド樹脂層（ｉ）の熱伝導率が向上しないばかりでなく、粒子同士が凝集を起こしやすくなり、均一に分散させることが困難となる恐れがある。一方、２５μｍを超えると、ポリイミド樹脂層（ｉ）への充填率が低下し、かつフィラー界面においてポリイミド樹脂層（ｉ）が脆くなる傾向にある。 The particle size of the thermally conductive filler is, for example, in the range of an average particle diameter of 0.01 to 25 μm from the viewpoint of improving the thermal conductivity by uniformly dispersing the filler in the thickness direction of the polyimide resin layer (i). It is preferable that it exists, and it is more preferable that it exists in the range of 1-8 micrometers. If the average particle size of the thermally conductive filler is less than 0.01 μm, the thermal conductivity inside each filler is reduced, and as a result, the thermal conductivity of the polyimide resin layer (i) is not improved, and the particles Tends to agglomerate and may be difficult to disperse uniformly. On the other hand, when it exceeds 25 μm, the filling rate of the polyimide resin layer (i) is lowered, and the polyimide resin layer (i) tends to be brittle at the filler interface.
なお、熱伝導フィラーとして、板状フィラーを用いる場合、本発明では、その粒子サイズは平均長径ＤLで表される。板状フィラーを用いる場合、平均長径ＤLの好ましい範囲は、例えば０．１〜１５μｍの範囲内であり、特に好ましくは０．５〜１０μｍの範囲内である。板状フィラーとしては窒化ホウ素が好ましく使用される。平均長径ＤLが０．１μｍに満たないと、熱伝導率が低く、熱膨張係数が大きくなり、形状を板状とすることの効果が小さくなってしまう。一方、平均長径ＤLが１５μｍを超えると製膜時に配向させることが困難となる。ここで、平均長径ＤLとは板状フィラーの長手直径の平均値を意味する。平均径はメディアン径を意味し、モード径は上記範囲内で１つのピークであることがよく、これは球状フィラーについても同様である。 Incidentally, as the heat conduction filler, when using a plate-like filler, in the present invention, the particle size is expressed by an average long diameter D L. When using the plate-like filler, the preferred range of the average long diameter D L is, for example, in the range of 0.1-15, particularly preferably in the range of 0.5 to 10 [mu] m. As the plate filler, boron nitride is preferably used. If the average major axis D L is less than 0.1 μm, the thermal conductivity is low, the thermal expansion coefficient is increased, and the effect of making the shape plate-like is reduced. On the other hand, when the average major axis D L exceeds 15 μm, it becomes difficult to align during film formation. Here, the average major axis D L means the average value of the longitudinal diameters of the plate-like fillers. The average diameter means the median diameter, and the mode diameter is preferably one peak within the above range, and this is the same for the spherical filler.
＜ポリイミド樹脂層（ｉｉ）＞
ポリイミド樹脂層（Ｉ）中には、任意の層として、ポリイミド樹脂層（ｉ）以外のポリイミド樹脂層（ｉｉ）を含むことができる。この場合、ポリイミド樹脂層（ｉｉ）は、１層に限らず、２層以上であってもよい。ポリイミド樹脂層（ｉｉ）を構成するポリイミド樹脂は、ポリイミド樹脂層（Ｉ）の熱伝導率をはじめとする物性を損なわない限り、特に限定されるものではなく、例えば、一般式（１）で表される構造単位以外の構造単位のポリイミド樹脂について例示した上記芳香族テトラカルボン酸及び芳香族ジアミンを原料にして製造できる。
<Polyimide resin layer (ii)>
In polyimide resin layer (I), polyimide resin layers (ii) other than polyimide resin layer (i) can be included as arbitrary layers. In this case, the polyimide resin layer (ii) is not limited to one layer, and may be two or more layers. The polyimide resin constituting the polyimide resin layer (ii) is not particularly limited as long as the physical properties such as the thermal conductivity of the polyimide resin layer (I) are not impaired. For example, the polyimide resin layer (ii) is represented by the general formula (1). The aromatic tetracarboxylic acid and aromatic diamine exemplified for the polyimide resin having a structural unit other than the structural unit to be produced can be used as raw materials.
＜ポリイミド樹脂層の厚み＞
ポリイミド樹脂層（Ｉ）の全体厚みに対するポリイミド樹脂層（ｉ）の厚みは７０％以上であることが必要であり、８０〜１００％の範囲内が好ましい。ポリイミド樹脂層（Ｉ）の高熱伝導率化の観点からは１００％（つまり、ポリイミド樹脂層（Ｉ）の全体がポリイミド樹脂層（ｉ）により構成されていること）が好ましい。ポリイミド樹脂層（ｉ）の厚みが７０％未満であると、放熱性が十分でないばかりでなく、例えば、回路基板として使用する場合に寸法安定性が十分でなく、耐熱性も低いものとなる。また、ポリイミド樹脂層（Ｉ）の全体の厚みは、例えば１０〜５０μｍの範囲内が好ましく、１５〜４０μｍの範囲内がより好ましい。ポリイミド樹脂層（Ｉ）の厚みが１０μｍに満たないと、脆く破れ易くなり、一方で５０μｍを超えると耐折性や耐屈曲性が低下する傾向にある。
<Thickness of polyimide resin layer>
The thickness of the polyimide resin layer (i) with respect to the total thickness of the polyimide resin layer (I) needs to be 70% or more, and preferably in the range of 80 to 100%. From the viewpoint of increasing the thermal conductivity of the polyimide resin layer (I), 100% (that is, the entire polyimide resin layer (I) is constituted by the polyimide resin layer (i)) is preferable. When the thickness of the polyimide resin layer (i) is less than 70%, not only the heat dissipation is not sufficient, but also, for example, when used as a circuit board, the dimensional stability is not sufficient and the heat resistance is low. The total thickness of the polyimide resin layer (I) is preferably in the range of 10 to 50 μm, for example, and more preferably in the range of 15 to 40 μm. If the thickness of the polyimide resin layer (I) is less than 10 μm, it is brittle and easily broken, while if it exceeds 50 μm, the folding resistance and the bending resistance tend to be lowered.
＜ポリイミド樹脂層（Ｉ）の物性＞
次に、ポリイミド樹脂層（Ｉ）の物性について、ガラス転移温度、熱伝導率及び引裂き伝播抵抗を挙げて説明する。
<Physical properties of polyimide resin layer (I)>
Next, physical properties of the polyimide resin layer (I) will be described with reference to glass transition temperature, thermal conductivity, and tear propagation resistance.
（ガラス転移温度）
ポリイミド樹脂層（Ｉ）は、その全体のガラス転移温度（Ｔｇ）が３００℃以上であることが好ましく、Ｔｇが３１０〜３５０℃の範囲内にあることがより好ましい。ポリイミド樹脂層（Ｉ）の全体のＴｇが３００℃以上であることにより、金属張積層体に十分な耐熱性を付与できる。このように高いＴｇは、ポリイミド樹脂層（ｉ）を構成するポリイミド樹脂に、一般式（１）で表される構造単位を６０モル％以上含有させるとともに、ポリイミド樹脂層（ｉ）の厚みを、ポリイミド樹脂層（Ｉ）の全体厚みの７０％以上とすることによって実現できる。
(Glass-transition temperature)
The polyimide resin layer (I) preferably has an overall glass transition temperature (Tg) of 300 ° C. or higher, and more preferably has a Tg in the range of 310 to 350 ° C. When the total Tg of the polyimide resin layer (I) is 300 ° C. or more, sufficient heat resistance can be imparted to the metal-clad laminate. In this way, the high Tg causes the polyimide resin constituting the polyimide resin layer (i) to contain 60 mol% or more of the structural unit represented by the general formula (1), and the thickness of the polyimide resin layer (i), This can be realized by setting it to 70% or more of the total thickness of the polyimide resin layer (I).
（熱伝導率）
ポリイミド樹脂層（Ｉ）は、その全体の熱伝導率が１．０Ｗ／ｍＫ以上であることが好ましく、１．２〜３．０Ｗ／ｍＫ以上であることがより好ましい。ポリイミド樹脂層（Ｉ）の全体の熱伝導率が１．０Ｗ／ｍＫ以上であることにより、金属張積層体の放熱特性が優れたものとなり、高温環境で使用される回路基板等への適用が可能になる。このように優れた熱伝導率は、ポリイミド樹脂層（ｉ）への熱伝導性フィラーの添加量を４０ｖｏｌ％以上にするとともに、ポリイミド樹脂層（ｉ）の厚みを、ポリイミド樹脂層（Ｉ）の全体厚みの７０％以上とすることによって実現できる。ポリイミド樹脂層（ｉ）への熱伝導性フィラーの添加量が４０ｖｏｌ％未満である場合、及び／又は、ポリイミド樹脂層（ｉ）の厚みがポリイミド樹脂層（Ｉ）の全体厚みの７０％未満である場合には、熱伝導率が１．０Ｗ／ｍＫ未満となり放熱特性が低下する。本実施の形態の金属張積層体では、特に、ポリイミド樹脂層（Ｉ）の厚みに占めるポリイミド樹脂層（ｉ）の厚みの割合を１００％とし、接着層を介在させないことによって、高い熱伝導率を得ることができる。なお、本明細書において、特に断りがない限り、熱伝導率は、層の厚み方向の熱伝導率（λｚＴＣ）を意味する。
(Thermal conductivity)
The overall thermal conductivity of the polyimide resin layer (I) is preferably 1.0 W / mK or more, and more preferably 1.2 to 3.0 W / mK or more. When the overall thermal conductivity of the polyimide resin layer (I) is 1.0 W / mK or more, the heat dissipation characteristics of the metal-clad laminate are excellent, and it can be applied to circuit boards used in high-temperature environments. It becomes possible. Thus excellent thermal conductivity makes the addition amount of the thermal conductive filler to the polyimide resin layer (i) 40 vol% or more, and the polyimide resin layer (i) has a thickness of the polyimide resin layer (I). This can be realized by setting it to 70% or more of the total thickness. When the amount of the thermally conductive filler added to the polyimide resin layer (i) is less than 40 vol%, and / or the thickness of the polyimide resin layer (i) is less than 70% of the total thickness of the polyimide resin layer (I). In some cases, the thermal conductivity is less than 1.0 W / mK and the heat dissipation characteristics are degraded. In the metal-clad laminate of the present embodiment, in particular, the ratio of the thickness of the polyimide resin layer (i) to the thickness of the polyimide resin layer (I) is 100%, and the adhesive layer is not interposed, thereby providing high thermal conductivity. Can be obtained. In the present specification, unless otherwise specified, the thermal conductivity means the thermal conductivity in the thickness direction of the layer (λzTC).
（引裂き伝播抵抗）
ポリイミド樹脂層（Ｉ）は、引裂き伝播抵抗が０．７〜１．０ｋＮ／ｍの範囲内にあることが好ましい。ポリイミド樹脂層（Ｉ）の引裂き伝播抵抗が０．７ｋＮ／ｍに満たないと回路基板にする際の加工時に樹脂が裂けたり、割れを生じる恐れがある。ポリイミド樹脂層（Ｉ）の引裂き伝播抵抗が１．０ｋＮ／ｍを超えるとポリイミド樹脂層（Ｉ）の熱膨張係数が大きくなり、寸法安定性が悪化する傾向にある。ポリイミド樹脂層（Ｉ）の引裂き伝播抵抗を０．７〜１．０ｋＮ／ｍの範囲内にするためには、ポリイミド樹脂層（ｉ）における熱伝導性フィラーの種類や含有量を上記した適正範囲するとともに、一般式（１）で表される構造単位を６０モル％以上含有させることがよい。
(Tear propagation resistance)
The polyimide resin layer (I) preferably has a tear propagation resistance in the range of 0.7 to 1.0 kN / m. If the tear propagation resistance of the polyimide resin layer (I) is less than 0.7 kN / m, the resin may be torn or cracked during processing when forming a circuit board. If the tear propagation resistance of the polyimide resin layer (I) exceeds 1.0 kN / m, the thermal expansion coefficient of the polyimide resin layer (I) increases and the dimensional stability tends to deteriorate. In order to set the tear propagation resistance of the polyimide resin layer (I) within the range of 0.7 to 1.0 kN / m, the appropriate range of the type and content of the thermally conductive filler in the polyimide resin layer (i) is described above. In addition, it is preferable to contain 60 mol% or more of the structural unit represented by the general formula (1).
なお、ポリイミド樹脂層（Ｉ）、（ｉ）、（ｉｉ）中には、上記物性を損なわない限りにおいて、例えば加工助剤、抗酸化剤、光安定剤、難燃剤、帯電防止剤、界面活性剤、分散剤、沈降防止剤、熱安定剤、紫外線吸収剤、熱伝導性以外の有機もしくは無機フィラーなどの任意成分を含むことができる。また、ポリイミド樹脂層（Ｉ）は、ポリイミド樹脂層（ｉ）以外のポリイミド樹脂層（ｉｉ）に、熱伝導性フィラーを含有していてもよい。 In addition, in the polyimide resin layers (I), (i), (ii), for example, processing aids, antioxidants, light stabilizers, flame retardants, antistatic agents, surface active agents, as long as the above physical properties are not impaired. An optional component such as an organic or inorganic filler other than an agent, a dispersant, an anti-settling agent, a heat stabilizer, an ultraviolet absorber, and thermal conductivity can be contained. Moreover, the polyimide resin layer (I) may contain a thermally conductive filler in the polyimide resin layer (ii) other than the polyimide resin layer (i).
［金属層］
本実施の形態の金属張積層体において導体層となる金属層としては、例えば銅、アルミニウム、鉄、銀、パラジウム、ニッケル、クロム、モリブデン、タングステン、亜鉛及びそれらの合金等の導電性金属箔を挙げることができ、これらの中でも銅箔又は銅を９０％以上含む合金銅箔が好ましく用いられる。金属層の好ましい厚み範囲は、金属張積層体の用途によって異なり、例えば金属層が放熱基板のベース基板となる場合には、１００μｍ〜３ｍｍの範囲内が好ましい。また、フレキシブル回路基板として用いる場合には、例えば５〜７５μｍの範囲内が好ましく、８〜３５μｍの範囲内がより好ましい。
[Metal layer]
Examples of the metal layer to be a conductor layer in the metal-clad laminate of the present embodiment include conductive metal foils such as copper, aluminum, iron, silver, palladium, nickel, chromium, molybdenum, tungsten, zinc, and alloys thereof. Among these, a copper foil or an alloy copper foil containing 90% or more of copper is preferably used. The preferable thickness range of the metal layer varies depending on the use of the metal-clad laminate. For example, when the metal layer is the base substrate of the heat dissipation substrate, the thickness is preferably in the range of 100 μm to 3 mm. Moreover, when using as a flexible circuit board, the inside of the range of 5-75 micrometers is preferable, for example, and the inside of the range of 8-35 micrometers is more preferable.
［金属張積層体の積層構造］
本実施の形態の金属張積層体は、単層又は複数層からなるポリイミド樹脂層（Ｉ）と、このポリイミド樹脂層（Ｉ）の片面又は両面に設けられた金属層と、を備え、ポリイミド樹脂層（ｉ）の厚みをポリイミド樹脂層（Ｉ）の全体厚みの７０％以上とするものである。金属張積層体を構成するポリイミド樹脂層（Ｉ）中には、２層以上のポリイミド樹脂層（ｉ）を設けてもよい。ただし、層を増やすことは工程数の増加につながるため、ポリイミド樹脂層（Ｉ）中に、１層のポリイミド樹脂層（ｉ）を設けることが好ましい。この場合、ポリイミド樹脂層（Ｉ）の全体をポリイミド樹脂層（ｉ）により形成することがより好ましい。すなわち、金属張積層体は、ポリイミド樹脂層（Ｉ）としてのポリイミド樹脂層（ｉ）の片面又は両面に金属層を設けた積層構造であることによって、最も優れた熱伝導性が得られる。
[Laminated structure of metal-clad laminate]
The metal-clad laminate of this embodiment includes a polyimide resin layer (I) composed of a single layer or a plurality of layers, and a metal layer provided on one or both sides of the polyimide resin layer (I), and a polyimide resin. The thickness of the layer (i) is 70% or more of the total thickness of the polyimide resin layer (I). Two or more polyimide resin layers (i) may be provided in the polyimide resin layer (I) constituting the metal-clad laminate. However, since increasing the number of layers leads to an increase in the number of steps, it is preferable to provide one polyimide resin layer (i) in the polyimide resin layer (I). In this case, it is more preferable to form the entire polyimide resin layer (I) with the polyimide resin layer (i). That is, the metal-clad laminate has a laminated structure in which a metal layer is provided on one or both sides of the polyimide resin layer (i) as the polyimide resin layer (I), whereby the most excellent thermal conductivity is obtained.
また、ポリイミド樹脂層（Ｉ）中のポリイミド樹脂層（ｉ）の少なくとも一方の面が金属層と直接接するように金属層を配することが好ましい。ポリイミド樹脂層（Ｉ）の両面に金属層を設ける場合は、ポリイミド樹脂層（ｉ）の両側に直接金属層を配してもよく、また、ポリイミド樹脂層（ｉ）の片側に金属層を配し、もう片側に別のポリイミド樹脂層（ｉｉ）を設けてもよい。 In addition, the metal layer is preferably arranged so that at least one surface of the polyimide resin layer (i) in the polyimide resin layer (I) is in direct contact with the metal layer. When providing metal layers on both sides of the polyimide resin layer (I), the metal layers may be arranged directly on both sides of the polyimide resin layer (i), or the metal layers are arranged on one side of the polyimide resin layer (i). Then, another polyimide resin layer (ii) may be provided on the other side.
［金属張積層体の製造例］
上記ポリイミド樹脂層（ｉ）は、ポリイミド樹脂の前駆体であるポリアミド酸溶液を、適当な支持体上に直接塗布し、乾燥及び硬化させることによって形成することができる。この場合、ポリイミド樹脂層（ｉ）の上に、さらに同様の方法で、ポリイミド樹脂層（ｉｉ）を積層形成してもよい。ここで、支持体として放熱基板や回路基板の導体層となる上記した銅箔等の金属箔を用いれば、金属層と、少なくともポリイミド樹脂層（ｉ）を有するポリイミド樹脂層（Ｉ）と、を備えた金属張積層体とすることができる。
[Production example of metal-clad laminate]
The said polyimide resin layer (i) can be formed by apply | coating the polyamic acid solution which is a precursor of a polyimide resin directly on a suitable support body, and making it dry and harden | cure. In this case, the polyimide resin layer (ii) may be laminated on the polyimide resin layer (i) by the same method. Here, if a metal foil such as the above-mentioned copper foil which becomes a conductor layer of a heat dissipation board or a circuit board is used as a support, a metal layer and a polyimide resin layer (I) having at least a polyimide resin layer (i), It can be set as the provided metal-clad laminate.
支持体へのポリアミド酸溶液の塗布は、公知の方法で行うことができ、例えば、バーコード方式、グラビアコート方式、ロールコート方式、ダイコート方式等から適宜選択して採用することができる。 Application of the polyamic acid solution to the support can be performed by a known method. For example, a barcode method, a gravure coating method, a roll coating method, a die coating method, or the like can be selected as appropriate.
本発明をよりわかりやすく説明するために、ポリイミド樹脂層（Ｉ）の片面に金属層を有する金属張積層体の製造例を示す。ここでは、ポリイミド樹脂層（Ｉ）が、１層のポリイミド樹脂層（ｉ）のみにより構成される場合を例に挙げて説明する。まず、金属張積層体の金属層を構成する銅箔などの金属箔を準備する。この金属箔上に熱伝導性フィラー入りのポリイミド樹脂層（ｉ）を形成するためのポリアミド酸溶液を塗布し、例えば１４０℃以下の温度で乾燥し一定量の溶媒を除去する。その後、更に高温で熱処理してポリアミド酸をイミド化し、ポリイミド樹脂層（Ｉ）の片面に金属層を有する金属張積層体とする。ここで、イミド化のための熱処理は、例えば１３０〜３６０℃の範囲内の加熱温度で、段階的に１５〜６０分程度の時間をかけて行うことが好ましい。 In order to explain the present invention more clearly, an example of producing a metal-clad laminate having a metal layer on one side of the polyimide resin layer (I) is shown. Here, the case where the polyimide resin layer (I) is composed of only one polyimide resin layer (i) will be described as an example. First, a metal foil such as a copper foil constituting the metal layer of the metal-clad laminate is prepared. A polyamic acid solution for forming a polyimide resin layer (i) containing a heat conductive filler is applied on the metal foil, and dried at a temperature of, for example, 140 ° C. or less to remove a certain amount of solvent. Thereafter, the polyamic acid is imidized by heat treatment at a higher temperature to obtain a metal-clad laminate having a metal layer on one side of the polyimide resin layer (I). Here, the heat treatment for imidization is preferably performed at a heating temperature within a range of 130 to 360 ° C., for example, in a time step of about 15 to 60 minutes.
また、上記熱伝導性フィラーを含有するポリアミド酸溶液の調製は、例えば、予め重合して得られた溶媒を含むポリアミド酸溶液に熱伝導性フィラーを一定量添加し、攪拌装置などで分散させることで調製する方法や、溶媒中に熱伝導性フィラーを分散させながらジアミンと酸無水物を添加して重合を行い調製する方法が挙げられる。ここで、ポリアミド酸は、芳香族ジアミン成分と芳香族テトラカルボン酸二無水物成分とを実質的に等モル使用し、溶媒中で重合する公知の方法によって製造することができる。すなわち、例えば窒素気流下でＮ,Ｎ−ジメチルアセトアミドなどの溶媒に上記芳香族ジアミン成分を溶解させた後、芳香族テトラカルボン酸二無水物を加えて、室温で３時間程度反応させることによりポリアミド酸が得られる。ポリイミド樹脂層（ｉ）を形成する目的に適したポリアミド酸の好ましい重合度は、その粘度範囲で表したとき、例えば溶液粘度が５〜２，０００Ｐの範囲内であることが好ましく、２００〜３００Ｐの範囲内がより好ましい。上記粘度範囲であれば、熱伝導性フィラーを配合しても均一な分散状態に保つことができる。溶液粘度の測定は、恒温水槽付のコーンプレート式粘度計によって行うことができる。なお、上記溶媒には、Ｎ,Ｎ−ジメチルアセトアミドの他、ｎ-メチルピロリジノン、２-ブタノン、ジグライム、キシレン等が挙げられ、これらを１種若しくは２種以上併用して使用することもできる。 In addition, the preparation of the polyamic acid solution containing the above heat conductive filler is, for example, adding a certain amount of the heat conductive filler to the polyamic acid solution containing a solvent obtained by polymerization in advance, and dispersing with a stirrer or the like. And a method in which a diamine and an acid anhydride are added and polymerization is performed while dispersing a thermally conductive filler in a solvent. Here, the polyamic acid can be produced by a known method in which an aromatic diamine component and an aromatic tetracarboxylic dianhydride component are used in substantially equimolar amounts and polymerized in a solvent. That is, for example, after the aromatic diamine component is dissolved in a solvent such as N, N-dimethylacetamide under a nitrogen stream, an aromatic tetracarboxylic dianhydride is added and reacted at room temperature for about 3 hours. An acid is obtained. The preferred degree of polymerization of the polyamic acid suitable for the purpose of forming the polyimide resin layer (i), when expressed in the viscosity range, for example, the solution viscosity is preferably in the range of 5 to 2,000 P, 200 to 300 P The range of is more preferable. If it is the said viscosity range, even if it mix | blends a heat conductive filler, it can maintain a uniform dispersion state. The solution viscosity can be measured with a cone plate viscometer with a thermostatic water bath. Examples of the solvent include N, N-dimethylacetamide, n-methylpyrrolidinone, 2-butanone, diglyme, xylene and the like, and these may be used alone or in combination of two or more.
［金属張積層体の物性（ピール強度）］
本実施の形態の金属張積層体において、ポリイミド樹脂層（Ｉ）と金属層とのピール強度は、例えば０．５ｋＮ／ｍ以上であることが好ましく、０．７〜１．８ｋＮ／ｍの範囲内であることがより好ましい。このような高いピール強度は、ポリイミド樹脂層（ｉ）中に含まれる一般式（１）で表される構造単位の比率によって制御できる。ポリイミド樹脂層（ｉ）中に含まれる一般式（１）で表される構造単位が６０モル％未満であると金属層とのピール強度が０．５ｋＮ／ｍ未満となって金属層との密着力が不足する。また、ポリイミド樹脂層（ｉ）が破れやすくなるため、うまく加工できないなどの諸問題が発生しやすくなる。
[Physical properties of metal-clad laminate (peel strength)]
In the metal-clad laminate of the present embodiment, the peel strength between the polyimide resin layer (I) and the metal layer is preferably 0.5 kN / m or more, for example, in the range of 0.7 to 1.8 kN / m. More preferably, it is within. Such high peel strength can be controlled by the ratio of the structural unit represented by the general formula (1) contained in the polyimide resin layer (i). When the structural unit represented by the general formula (1) contained in the polyimide resin layer (i) is less than 60 mol%, the peel strength with the metal layer is less than 0.5 kN / m and the metal layer is in close contact with the metal layer. Lack of power. Moreover, since the polyimide resin layer (i) is easily broken, various problems such as inability to process it easily occur.
以上のように、本実施の形態の金属張積層体では、熱伝導性フィラーの種類や含有量を適正範囲にし、また、使用するポリイミド原料を選択するとともに、ポリイミド樹脂層（Ｉ）におけるポリイミド樹脂層（ｉ）の厚み比率を適正な範囲に設定している。これによって、接着層を介在させなくても金属層とポリイミド樹脂層（Ｉ）との実用的接着強度を有しており、ポリイミド樹脂層（Ｉ）全体のガラス転移温度が３００℃以上で十分な耐熱性を有し、かつ熱伝導性に優れた金属張積層体が得られる。したがって、本実施の形態の金属張積層体は、例えば放熱基板や回路基板等の用途で使用するために適したものである。 As described above, in the metal-clad laminate of the present embodiment, the type and content of the thermally conductive filler are within an appropriate range, the polyimide raw material to be used is selected, and the polyimide resin in the polyimide resin layer (I) The thickness ratio of the layer (i) is set to an appropriate range. This has practical adhesive strength between the metal layer and the polyimide resin layer (I) without interposing an adhesive layer, and the glass transition temperature of the entire polyimide resin layer (I) is sufficient at 300 ° C. or more. A metal-clad laminate having heat resistance and excellent thermal conductivity is obtained. Therefore, the metal-clad laminate of the present embodiment is suitable for use in applications such as a heat dissipation board and a circuit board.
［第２の実施の形態］
熱伝導性ポリイミドフィルム：
本実施の形態の熱伝導性ポリイミドフィルムは、単層又は複数層から構成され、熱伝導性ポリイミドフィルムの全体の厚みの７０％以上の厚みを有するポリイミド樹脂層（ｉ）を有しており、かつ、熱伝導性ポリイミドフィルム全体のガラス転移温度が３００℃以上である。ここで、ポリイミド樹脂層（ｉ）は、第１の実施の形態におけるポリイミド樹脂層（ｉ）と同様の構成である。すなわち、本実施の形態のポリイミド樹脂層（ｉ）は、上記一般式（１）で表される構造単位を６０モル％以上（好ましくは８０モル％以上）含有するポリイミド樹脂によって構成されるとともに、熱伝導性フィラーを４０〜８０ｖｏｌ％（好ましくは４５〜７０ｖｏｌ％）の範囲内で含有するものである。本実施の形態のポリイミド樹脂層（ｉ）を構成する樹脂や熱伝導性フィラーは、第１の実施の形態で説明したものを使用できる。
[Second Embodiment]
Thermally conductive polyimide film:
The thermally conductive polyimide film of the present embodiment is composed of a single layer or a plurality of layers, and has a polyimide resin layer (i) having a thickness of 70% or more of the total thickness of the thermally conductive polyimide film, And the glass transition temperature of the whole heat conductive polyimide film is 300 degreeC or more. Here, the polyimide resin layer (i) has the same configuration as the polyimide resin layer (i) in the first embodiment. That is, the polyimide resin layer (i) of the present embodiment is composed of a polyimide resin containing 60 mol% or more (preferably 80 mol% or more) of the structural unit represented by the general formula (1), A heat conductive filler is contained in the range of 40-80 vol% (preferably 45-70 vol%). As the resin and the heat conductive filler constituting the polyimide resin layer (i) of the present embodiment, those described in the first embodiment can be used.
また、本実施の形態の熱伝導性ポリイミドフィルムは、その全体がポリイミド樹脂層（ｉ）によって構成されていてもよいし、ポリイミド樹脂層（ｉ）以外に、第１の実施の形態と同様のポリイミド樹脂層（ｉｉ）を備えていてもよい。 Moreover, the heat conductive polyimide film of this Embodiment may be comprised with the polyimide resin layer (i) as a whole, and is the same as that of 1st Embodiment other than a polyimide resin layer (i). A polyimide resin layer (ii) may be provided.
また、本実施の形態の熱伝導性ポリイミドフィルムは、その全体の熱伝導率が１．０Ｗ／ｍＫ以上であることが好ましく、１．２〜３．０Ｗ／ｍＫ以上であることがより好ましい。さらに、熱伝導性ポリイミドフィルムは、引裂き伝播抵抗が４〜３０ｍＮの範囲内にあることが好ましい。このように、本実施の形態の熱伝導性ポリイミドフィルムは、金属層と張り合わされていない点を除き、上記第１の実施の形態で説明したポリイミド樹脂層（Ｉ）と同様の構造及び物性を有している。そして、熱伝導性ポリイミドフィルムは、第１の実施の形態の金属張積層体におけるポリイミド樹脂層（Ｉ）と同様にして製造できる。 Moreover, it is preferable that the whole heat conductivity of the heat conductive polyimide film of this Embodiment is 1.0 W / mK or more, and it is more preferable that it is 1.2-3.0 W / mK or more. Furthermore, the heat conductive polyimide film preferably has a tear propagation resistance in the range of 4 to 30 mN. Thus, the thermally conductive polyimide film of this embodiment has the same structure and physical properties as the polyimide resin layer (I) described in the first embodiment, except that it is not bonded to the metal layer. Have. And a heat conductive polyimide film can be manufactured similarly to the polyimide resin layer (I) in the metal-clad laminated body of 1st Embodiment.
本実施の形態の熱伝導性ポリイミドフィルムは、金属層に対して実用的接着強度を有しており、ガラス転移温度が３００℃以上で十分な耐熱性を有し、かつ熱伝導性に優れている。この熱伝導性ポリイミドフィルムは、接着層を介在させなくても、金属層と張り合わせることができる。つまり、熱伝導性ポリイミドフィルムは、その片面又は両面に、接着層を必要とせずに金属層と直接張り合わせることが可能な粘着性貼着面を備えている。したがって、本実施の形態の熱伝導性ポリイミドフィルムは、例えば放熱基板や回路基板等の用途で金属層に積層して使用するために適したフィルムである。 The thermally conductive polyimide film of this embodiment has a practical adhesive strength to the metal layer, has a sufficient heat resistance at a glass transition temperature of 300 ° C. or higher, and is excellent in thermal conductivity. Yes. This heat conductive polyimide film can be bonded to the metal layer without an adhesive layer. That is, the heat conductive polyimide film is provided with an adhesive sticking surface that can be directly bonded to the metal layer without requiring an adhesive layer on one side or both sides thereof. Therefore, the thermally conductive polyimide film of the present embodiment is a film suitable for being used by being laminated on a metal layer for applications such as a heat dissipation board and a circuit board.
本実施の形態の熱伝導性ポリイミドフィルムの他の構成及び効果は、第１の実施の形態の金属張積層体におけるポリイミド樹脂層（Ｉ）と同様であるため説明を省略する。 Since the other structure and effect of the heat conductive polyimide film of this Embodiment are the same as that of the polyimide resin layer (I) in the metal-clad laminated body of 1st Embodiment, description is abbreviate | omitted.
以下、実施例に基づいて本発明の内容を具体的に説明するが、本発明はこれらの実施例の範囲に限定されるものではない。 EXAMPLES Hereinafter, although the content of this invention is demonstrated concretely based on an Example, this invention is not limited to the range of these Examples.
本実施例に用いた略号は以下の化合物を示す。
ｍ−ＴＢ：２,２’−ジメチル−４,４’−ジアミノビフェニル
ＴＰＥ−Ｒ：１,３−ビス(４−アミノフェノキシ)ベンゼン
ＢＡＰＰ：２,２-ビス［４−（４-アミノフェノキシ）フェニル］プロパン
ＰＭＤＡ：ピロメリット酸二無水物
ＢＰＤＡ：３,３’４,４’−ビフェニルテトラカルボン酸
ＤＳＤＡ：３,３’４,４’−ジフェニルスルホンテトラカルボン酸二無水物
ＤＭＡｃ：Ｎ,Ｎ−ジメチルアセトアミド
The abbreviations used in the examples represent the following compounds.
m-TB: 2,2′-dimethyl-4,4′-diaminobiphenyl TPE-R: 1,3-bis (4-aminophenoxy) benzene BAPP: 2,2-bis [4- (4-aminophenoxy) Phenyl] propane PMDA: pyromellitic dianhydride BPDA: 3,3′4,4′-biphenyltetracarboxylic acid DSDA: 3,3′4,4′-diphenylsulfone tetracarboxylic dianhydride DMAc: N, N -Dimethylacetamide
また、実施例において評価した各特性については、下記評価方法に従った。 Moreover, the following evaluation method was followed about each characteristic evaluated in the Example.
[粘度の測定]
ポリアミド酸溶液の粘度は、恒温水槽付のコーンプレート式粘度計（トキメック社製）にて、２５℃で測定した。
[Measurement of viscosity]
The viscosity of the polyamic acid solution was measured at 25 ° C. with a cone plate viscometer (manufactured by Tokimec Co., Ltd.) equipped with a constant temperature water bath.
［銅箔引剥し強度（ピール強度）］
積層体の銅箔層を幅１．０ｍｍ、長さ１８０ｍｍの長矩形にパターンエッチングし、そのパターンが中央になるように、幅２０ｍｍ、長さ２００ｍｍに試験片を切り抜き、ＩＰＣ−ＴＭ−６５０．２．４．１９（東洋精機製）により１８０°引剥し試験を行った。
[Copper foil peel strength (peel strength)]
The copper foil layer of the laminate was pattern-etched into a long rectangle having a width of 1.0 mm and a length of 180 mm, and a test piece was cut out to a width of 20 mm and a length of 200 mm so that the pattern was in the center, and IPC-TM-650. A 180 ° peeling test was performed according to 2.4.19 (manufactured by Toyo Seiki).
［厚み方向熱伝導率（λzＴＣ）］
ポリイミドフィルムを３０ｍｍ×３０ｍｍのサイズに切り出し、周期加熱法による厚み方向の熱拡散率（アルバック理工製ＦＴＣ−１装置）、ＤＳＣによる比熱、水中置換法による密度をそれぞれ測定し、これらの結果をもとに熱伝導率（Ｗ／ｍ・Ｋ）を算出した。
[Thickness direction thermal conductivity (λzTC)]
The polyimide film was cut into a size of 30 mm × 30 mm, and the thermal diffusivity in the thickness direction by the periodic heating method (FTC-1 device manufactured by ULVAC-RIKO), the specific heat by DSC, and the density by the underwater substitution method were measured, respectively. And thermal conductivity (W / m · K) was calculated.
［熱膨張係数（ＣＴＥ）］
３ｍｍ×１５ｍｍのサイズのポリイミドフィルムを、熱機械分析(ＴＭＡ)装置（セイコーインスツル社製）にて５gの荷重を加えながら一定の昇温速度（２０℃/ｍｉｎ）で３０℃から２６０℃の温度範囲で引張り試験を行い、温度に対するポリイミドフィルムの伸び量から熱膨張係数（ｐｐｍ／Ｋ）を測定した。
[Coefficient of thermal expansion (CTE)]
A polyimide film having a size of 3 mm × 15 mm is heated from 30 ° C. to 260 ° C. at a constant heating rate (20 ° C./min) while applying a 5 g load with a thermomechanical analysis (TMA) apparatus (manufactured by Seiko Instruments Inc.). A tensile test was performed in the temperature range, and the coefficient of thermal expansion (ppm / K) was measured from the amount of elongation of the polyimide film with respect to temperature.
［ガラス転移温度(Ｔｇ)］
ポリイミドフィルム（１０ｍｍ×２２．６ｍｍ）を動的熱器械分析装置（ティー・エイ・インスツルメント社製）にて２０℃から５００℃まで５℃／分で昇温させたときの動的粘弾性を測定し、ガラス転移温度（tanδ極大値：℃）を求めた。
[Glass transition temperature (Tg)]
Dynamic viscoelasticity when a polyimide film (10 mm × 22.6 mm) is heated from 20 ° C. to 500 ° C. at a rate of 5 ° C./min with a dynamic thermoanalyzer (manufactured by TA Instruments). Was measured, and the glass transition temperature (tan δ maximum value: ° C.) was determined.
［引裂き伝播抵抗（伝播抵抗）］
６３．５ｍｍ×５０ｍｍのポリイミドフィルムを試験片とし、試験片に長さ１２．７ｍｍの切り込みを入れ、東洋精機製の軽荷重引裂き試験機を用い測定した。
[Tear propagation resistance (propagation resistance)]
A 63.5 mm × 50 mm polyimide film was used as a test piece, a 12.7 mm length cut was made in the test piece, and measurement was performed using a light load tear tester manufactured by Toyo Seiki.
合成例１
ポリアミド酸Ａを合成するため、攪拌装置を備えた５００ｍlセパラブルフラスコ中の２５５ｇのＤＭＡｃに、２８．９ｇのＢＡＰＰを窒素気流下で攪拌しながら加えて溶解させた後、攪拌を維持したまま、１．０７ｇのＢＰＤＡと１５．０３ｇのＰＭＤＡを加えた。その後、室温で３．５時間攪拌を続けて重合反応を行い、ポリイミド前駆体となるポリアミド酸Ａの粘稠な溶液を得た。
Synthesis example 1
In order to synthesize polyamic acid A, 28.9 g of BAPP was added to 255 g of DMAc in a 500 ml separable flask equipped with a stirrer while stirring under a nitrogen stream, and the stirring was maintained. 1.07 g BPDA and 15.03 g PMDA were added. Thereafter, the polymerization reaction was continued for 3.5 hours at room temperature to obtain a viscous solution of polyamic acid A serving as a polyimide precursor.
合成例２
ポリアミド酸Ｂを合成するため、攪拌装置を備えた５００ｍlセパラブルフラスコ中の２５５ｇのＤＭＡｃに、１９．１１ｇのｍ−ＴＢと２．９２ｇのＴＰＥ−Ｒを窒素気流下で攪拌しながら加えて溶解させた後、攪拌を維持したまま、５．７９ｇのＢＰＤＡと１７．１７ｇのＰＭＤＡを加えた。その後、室温で３．５時間攪拌を続けて重合反応を行い、ポリイミド前駆体となるポリアミド酸Ｂの粘稠な溶液を得た。
Synthesis example 2
In order to synthesize polyamic acid B, 19.11 g of m-TB and 2.92 g of TPE-R were added to 255 g of DMAc in a 500 ml separable flask equipped with a stirrer while stirring under a nitrogen stream and dissolved. After that, 5.79 g BPDA and 17.17 g PMDA were added while maintaining stirring. Thereafter, the polymerization reaction was continued for 3.5 hours at room temperature to obtain a viscous solution of polyamic acid B as a polyimide precursor.
合成例３
ポリアミド酸Ｃを合成するため、攪拌装置を備えた５００ｍlセパラブルフラスコ中の２５５ｇのＤＭＡｃに、２２．２５ｇのＴＰＥ−Ｒを窒素気流下で攪拌しながら加えて溶解させた後、攪拌を維持したまま、１６．１８ｇのＤＳＤＡと６．５７ｇのＰＭＤＡを加えた。その後、室温で３．５時間攪拌を続けて重合反応を行い、ポリイミド前駆体となるポリアミド酸Ｃの粘稠な溶液を得た。
Synthesis example 3
In order to synthesize the polyamic acid C, 22.25 g of TPE-R was added to 255 g of DMAc in a 500 ml separable flask equipped with a stirrer while stirring under a nitrogen stream, and the stirring was maintained. As it was, 16.18 g DSDA and 6.57 g PMDA were added. Thereafter, the polymerization reaction was continued for 3.5 hours at room temperature to obtain a viscous solution of polyamic acid C as a polyimide precursor.
上記各合成例によって得られたポリアミド酸の粘度とこれらポリアミド酸から得られたポリイミド樹脂のガラス転移温度（Ｔｇ）を表１に示す。 Table 1 shows the viscosity of the polyamic acid obtained in each of the above synthesis examples and the glass transition temperature (Tg) of the polyimide resin obtained from the polyamic acid.
実施例１
合成例１にて得られたポリアミド酸Ａの溶液に平均粒子径１．１μｍの球状窒化アルミニウムフィラーを添加し、均一になるまで遠心攪拌機で混合し、熱伝導性フィラーを５０ｖｏｌ％含有するポリアミド酸溶液イとした。次に、厚み１８μｍの銅箔（圧延銅箔、Ｒｚ＝０．７μｍ）上に、ポリアミド酸溶液イを硬化後の厚みが２５μｍとなるように塗布し、１２０℃で加熱乾燥し溶剤を除去した。その後、１３０〜３６０℃の温度範囲で、段階的に３０分かけて昇温加熱して、金属張積層体Ｍ１を作製した。なお、このときの銅箔上のポリイミド樹脂層の厚みは２５μｍであった。金属張積層体Ｍ１におけるポリイミド樹脂層の特性を評価するために銅箔をエッチング除去してポリイミドフィルムｍ１を作製し、ＣＴＥ、熱伝導率、引裂き伝播抵抗をそれぞれ評価した。また、金属張積層体Ｍ１のポリイミド樹脂層と銅箔とのピール強度を評価した。結果を表２に示す。
Example 1
A spherical aluminum nitride filler having an average particle diameter of 1.1 μm is added to the polyamic acid A solution obtained in Synthesis Example 1, and mixed with a centrifugal stirrer until uniform, and the polyamic acid containing 50 vol% of the heat conductive filler. Solution a was used. Next, the polyamic acid solution (a) was applied onto a 18 μm thick copper foil (rolled copper foil, Rz = 0.7 μm) so that the thickness after curing was 25 μm, and the solvent was removed by heating at 120 ° C. . Thereafter, the metal-clad laminate M1 was manufactured by heating in a temperature range of 130 to 360 ° C. over 30 minutes stepwise. At this time, the thickness of the polyimide resin layer on the copper foil was 25 μm. In order to evaluate the characteristics of the polyimide resin layer in the metal-clad laminate M1, the copper foil was removed by etching to produce a polyimide film m1, and the CTE, thermal conductivity, and tear propagation resistance were evaluated. Moreover, the peel strength of the polyimide resin layer of the metal-clad laminate M1 and the copper foil was evaluated. The results are shown in Table 2.
実施例２
合成例１にて得られたポリアミド酸樹脂Ａに平均粒径１．１μｍの球状窒化アルミニウムフィラーと平均長径２．２μｍの板状窒化ホウ素フィラーを添加し、均一になるまで遠心攪拌機で混合し、熱伝導性フィラーを５５ｖｏｌ％（球状窒化アルミニウムフィラー：板状窒化ホウ素フィラー＝９：１）含有するポリアミド酸溶液ロとした。その後は実施例１と同様にして、金属張積層体Ｍ２を作製した。なお、このときの銅箔上のポリイミド樹脂層の厚みは２５μｍであった。金属張積層体におけるポリイミド樹脂層の特性を評価するために銅箔をエッチング除去してポリイミドフィルムｍ２を作製し、ＣＴＥ、熱伝導率、引裂き伝播抵抗をそれぞれ評価した。また、金属張積層体のポリイミド樹脂層と銅箔とのピール強度を評価した。結果を表２に示す。
Example 2
A spherical aluminum nitride filler having an average particle diameter of 1.1 μm and a plate-like boron nitride filler having an average major diameter of 2.2 μm are added to the polyamic acid resin A obtained in Synthesis Example 1, and mixed with a centrifugal stirrer until uniform, A polyamic acid solution containing 55 vol% of a thermally conductive filler (spherical aluminum nitride filler: plate-like boron nitride filler = 9: 1) was used. Thereafter, in the same manner as in Example 1, a metal-clad laminate M2 was produced. At this time, the thickness of the polyimide resin layer on the copper foil was 25 μm. In order to evaluate the characteristics of the polyimide resin layer in the metal-clad laminate, the copper foil was removed by etching to produce a polyimide film m2, and the CTE, thermal conductivity, and tear propagation resistance were evaluated. Further, the peel strength between the polyimide resin layer of the metal-clad laminate and the copper foil was evaluated. The results are shown in Table 2.
実施例３
合成例１にて得られたポリアミド酸樹脂Ａの溶液に平均粒径１．１μｍの球状窒化アルミニウムフィラーを添加し、均一になるまで遠心攪拌機で混合し、熱伝導性フィラーを５０ｖｏｌ％含有するポリアミド酸溶液ハとした。また、合成例１にて得られたポリアミド酸樹脂Ａに平均粒径１．１μｍの球状窒化アルミニウムフィラーを添加し、均一になるまで遠心攪拌機で混合し、熱伝導性フィラーを２０ｖｏｌ％含有するポリアミド酸溶液ニとした。次に、厚み１８μｍの銅箔（圧延銅箔、Ｒｚ＝０．７μｍ）上に、ポリアミド酸樹脂ハの溶液を硬化後の厚みが２０μｍとなるように塗布し、１２０〜１４０℃で加熱乾燥し溶剤を除去した。次に、その上にポリアミド酸樹脂ニの溶液を硬化後の厚みが５μｍとなるように塗布し、１２０℃で加熱乾燥し溶剤を除去した。その後、１３０〜３６０℃の温度範囲で、段階的に３０分かけて昇温加熱して、銅箔上に２層のポリイミド樹脂層からなる金属張積層体Ｍ３を作製した。なお、銅箔上のポリイミド樹脂層の厚みは、銅箔側から塗布されたポリアミド酸溶液ハ／ニの順に２０μｍ／５μｍであった。金属張積層体におけるポリイミド樹脂層の特性を評価するために銅箔をエッチング除去してポリイミドフィルムｍ３を作製し、ＣＴＥ、熱伝導率、引裂き伝播抵抗をそれぞれ評価した。また、金属張積層体のポリイミド樹脂層と銅箔とのピール強度を評価した。結果を表２に示す。
Example 3
A polyamide containing 50 vol% of heat conductive filler is added to the solution of polyamic acid resin A obtained in Synthesis Example 1 and a spherical aluminum nitride filler having an average particle size of 1.1 μm is mixed with a centrifugal stirrer until uniform. Acid solution C was used. Further, a polyamide containing 20 vol% of heat conductive filler is added to the polyamic acid resin A obtained in Synthesis Example 1 by adding a spherical aluminum nitride filler having an average particle diameter of 1.1 μm and mixing with a centrifugal stirrer until uniform. An acid solution was used. Next, the polyamic acid resin solution is applied onto a copper foil having a thickness of 18 μm (rolled copper foil, Rz = 0.7 μm) so that the thickness after curing is 20 μm, followed by heating and drying at 120 to 140 ° C. The solvent was removed. Next, a solution of the polyamic acid resin d was applied thereon so that the thickness after curing was 5 μm, and dried by heating at 120 ° C. to remove the solvent. Then, it heated up in steps over 30 minutes in the temperature range of 130-360 degreeC, and produced the metal-clad laminated body M3 which consists of two polyimide resin layers on copper foil. The thickness of the polyimide resin layer on the copper foil was 20 μm / 5 μm in the order of the polyamic acid solution applied from the copper foil side. In order to evaluate the characteristics of the polyimide resin layer in the metal-clad laminate, the copper foil was removed by etching to prepare a polyimide film m3, and CTE, thermal conductivity, and tear propagation resistance were evaluated. Further, the peel strength between the polyimide resin layer of the metal-clad laminate and the copper foil was evaluated. The results are shown in Table 2.
実施例４
実施例３と全く同様にして、銅箔上に２層のポリイミド樹脂層からなる金属張積層体Ｍ３を作製した。次に、金属張積層体の樹脂面に厚み１８μmの銅箔（圧延銅箔、Ｒｚ＝０．７μｍ）をバッチプレスにて温度３８５℃で積層し、両面金属張積層体Ｍ３’を作製した。両面金属張積層体におけるポリイミド樹脂層の特性を評価するために銅箔をエッチング除去してポリイミドフィルムｍ３’を作製し、ＣＴＥ、熱伝導率、引裂き伝播抵抗をそれぞれ評価した。また、両面金属張積層体のポリイミド樹脂層と銅箔とのピール強度をそれぞれ評価した。結果を表２に示す。
Example 4
In exactly the same manner as in Example 3, a metal-clad laminate M3 composed of two polyimide resin layers on a copper foil was produced. Next, a copper foil (rolled copper foil, Rz = 0.7 μm) having a thickness of 18 μm was laminated on the resin surface of the metal-clad laminate by a batch press at a temperature of 385 ° C. to produce a double-sided metal-clad laminate M3 ′. In order to evaluate the characteristics of the polyimide resin layer in the double-sided metal-clad laminate, the copper foil was removed by etching to prepare a polyimide film m3 ′, and CTE, thermal conductivity, and tear propagation resistance were evaluated. Moreover, the peel strength of the polyimide resin layer and copper foil of a double-sided metal-clad laminate was evaluated. The results are shown in Table 2.
実施例５
合成例１にて得られたポリアミド酸樹脂Ａに平均粒径１．５μｍの球状アルミナフィラーを添加し、均一になるまで遠心攪拌機で混合し、熱伝導性フィラーを５０ｖｏｌ％含有するポリアミド酸溶液ホとした。その後は実施例１と同様にして、金属張積層体Ｍ４を作製した。なお、このときの銅箔上のポリイミド樹脂層の厚みは２５μｍであった。金属張積層体におけるポリイミド樹脂層の特性を評価するために銅箔をエッチング除去してポリイミドフィルムｍ４を作製し、ＣＴＥ、熱伝導率、引裂き伝播抵抗をそれぞれ評価した。また、金属張積層体のポリイミド樹脂層と銅箔とのピール強度を評価した。結果を表２に示す。
Example 5
A polyamic acid resin A obtained in Synthesis Example 1 is added with a spherical alumina filler having an average particle diameter of 1.5 μm, mixed with a centrifugal stirrer until uniform, and a polyamic acid solution containing 50 vol% of heat conductive filler. It was. Thereafter, in the same manner as in Example 1, a metal-clad laminate M4 was produced. At this time, the thickness of the polyimide resin layer on the copper foil was 25 μm. In order to evaluate the characteristics of the polyimide resin layer in the metal-clad laminate, the copper foil was removed by etching to prepare a polyimide film m4, and CTE, thermal conductivity, and tear propagation resistance were evaluated. Further, the peel strength between the polyimide resin layer of the metal-clad laminate and the copper foil was evaluated. The results are shown in Table 2.
実施例６
合成例１にて得られたポリアミド酸樹脂Ａに平均粒径１．５μｍの球状アルミナフィラーと平均長径２．２μｍの板状窒化ホウ素フィラーを添加し、均一になるまで遠心攪拌機で混合し、熱伝導性フィラーを５５ｖｏｌ％（球状アルミナフィラー：板状窒化ホウ素フィラー＝９：１）含有するポリアミド酸溶液ヘとした。その後は実施例１と同様にして、金属張積層体Ｍ５を作製した。なお、このときの銅箔上のポリイミド樹脂層の厚みは２５μｍであった。金属張積層体におけるポリイミド樹脂層の特性を評価するために銅箔をエッチング除去してポリイミドフィルムｍ５を作製し、ＣＴＥ、熱伝導率、引裂き伝播抵抗、をそれぞれ評価した。また、金属張積層体のポリイミド樹脂層と銅箔とのピール強度を評価した。結果を表２に示す。
Example 6
A spherical alumina filler with an average particle diameter of 1.5 μm and a plate-like boron nitride filler with an average major diameter of 2.2 μm are added to the polyamic acid resin A obtained in Synthesis Example 1, and mixed with a centrifugal stirrer until uniform. A polyamic acid solution containing 55 vol% of conductive filler (spherical alumina filler: plate-like boron nitride filler = 9: 1) was used. Thereafter, in the same manner as in Example 1, a metal-clad laminate M5 was produced. At this time, the thickness of the polyimide resin layer on the copper foil was 25 μm. In order to evaluate the characteristics of the polyimide resin layer in the metal-clad laminate, the copper foil was removed by etching to produce a polyimide film m5, and CTE, thermal conductivity, and tear propagation resistance were evaluated. Further, the peel strength between the polyimide resin layer of the metal-clad laminate and the copper foil was evaluated. The results are shown in Table 2.
比較例１
合成例１にて得られたポリアミド酸樹脂Ａに平均粒径１．１μｍの球状窒化アルミニウムフィラーを添加し、均一になるまで遠心攪拌機で混合し、熱伝導性フィラーを３０ｖｏｌ％含有するポリアミド酸溶液トとした。その後は実施例１と同様にして、金属張積層体Ｍ６を作製した。なお、このときの銅箔上のポリイミド樹脂層の厚みは２５μｍであった。金属張積層体におけるポリイミド樹脂層の特性を評価するために銅箔をエッチング除去してポリイミドフィルムｍ６を作製し、ＣＴＥ、熱伝導率、引裂き伝播抵抗をそれぞれ評価した。また、金属張積層体のポリイミド樹脂層と銅箔とのピール強度を評価した。結果を表２に示す。
Comparative Example 1
A polyamic acid solution containing 30 vol% of thermally conductive filler is added to the polyamic acid resin A obtained in Synthesis Example 1 by adding a spherical aluminum nitride filler having an average particle size of 1.1 μm and mixing with a centrifugal stirrer until uniform. And Thereafter, in the same manner as in Example 1, a metal-clad laminate M6 was produced. At this time, the thickness of the polyimide resin layer on the copper foil was 25 μm. In order to evaluate the characteristics of the polyimide resin layer in the metal-clad laminate, the copper foil was removed by etching to produce a polyimide film m6, and the CTE, thermal conductivity, and tear propagation resistance were evaluated. Further, the peel strength between the polyimide resin layer of the metal-clad laminate and the copper foil was evaluated. The results are shown in Table 2.
比較例２
合成例１にて得られたポリアミド酸樹脂Ａに平均粒径１．１μｍの球状窒化アルミニウムフィラーを添加し、均一になるまで遠心攪拌機で混合し、熱伝導性フィラーを９０ｖｏｌ％含有するポリアミド酸溶液チとした。その後は実施例１と同様にして、金属張積層体Ｍ７を作製した。なお、このときの銅箔上のポリイミド樹脂層の厚みは２５μｍであった。ところが、金属張積層体におけるポリイミド樹脂層の特性を評価するために銅箔をエッチング除去してポリイミドフィルムｍ７を作製したところ、フィルムが脆いため、ＣＴＥ、熱伝導率、引裂き伝播抵抗の測定を実施することはできなかった。
Comparative Example 2
A polyamic acid solution containing 90 vol% of thermally conductive filler is added to the polyamic acid resin A obtained in Synthesis Example 1 by adding a spherical aluminum nitride filler having an average particle size of 1.1 μm and mixing with a centrifugal stirrer until uniform. I made it. Thereafter, in the same manner as in Example 1, a metal-clad laminate M7 was produced. At this time, the thickness of the polyimide resin layer on the copper foil was 25 μm. However, in order to evaluate the characteristics of the polyimide resin layer in the metal-clad laminate, the copper foil was removed by etching to produce a polyimide film m7. Since the film was brittle, CTE, thermal conductivity, and tear propagation resistance were measured. I couldn't.
比較例３
合成例２にて得られたポリアミド酸樹脂Ｂに平均粒径１．１μｍの球状窒化アルミニウムフィラーを添加し、均一になるまで遠心攪拌機で混合し、熱伝導性フィラーを５０ｖｏｌ％含有するポリアミド酸溶液リとした。その後は実施例１と同様にして、金属張積層体Ｍ８を作製した。なお、このときの銅箔上のポリイミド樹脂層の厚みは２５μｍであった。金属張積層体におけるポリイミド樹脂層の特性を評価するために銅箔をエッチング除去してポリイミドフィルムｍ８を作製し、ＣＴＥ、熱伝導率、引裂き伝播抵抗をそれぞれ評価した。また、金属張積層体のポリイミド樹脂層と銅箔とのピール強度を評価した。結果を表２に示す。
Comparative Example 3
A polyamic acid solution containing 50 vol% of thermally conductive filler is added to the polyamic acid resin B obtained in Synthesis Example 2 by adding a spherical aluminum nitride filler having an average particle size of 1.1 μm and mixing with a centrifugal stirrer until uniform. I was relieved. Thereafter, in the same manner as in Example 1, a metal-clad laminate M8 was produced. At this time, the thickness of the polyimide resin layer on the copper foil was 25 μm. In order to evaluate the characteristics of the polyimide resin layer in the metal-clad laminate, the copper foil was removed by etching to prepare a polyimide film m8, and the CTE, thermal conductivity, and tear propagation resistance were evaluated. Further, the peel strength between the polyimide resin layer of the metal-clad laminate and the copper foil was evaluated. The results are shown in Table 2.
比較例４
合成例３にて得られたポリアミド酸樹脂Ｃに平均粒径１．１μｍの球状窒化アルミニウムフィラーを添加し、均一になるまで遠心攪拌機で混合し、熱伝導性フィラーを５０ｖｏｌ％含有するポリアミド酸溶液ヌとした。その後は実施例１と同様にして、金属張積層体Ｍ９を作製した。なお、このときの銅箔上のポリイミド樹脂層の厚みは２５μｍであった。金属張積層体におけるポリイミド樹脂層の特性を評価するために銅箔をエッチング除去してポリイミドフィルムｍ９を作製し、ＣＴＥ、熱伝導率、引裂き伝播抵抗をそれぞれ評価した。また、金属張積層体のポリイミド樹脂層と銅箔とのピール強度を評価した。結果を表２に示す。
Comparative Example 4
A polyamic acid solution containing 50 vol% of heat conductive filler is added to the polyamic acid resin C obtained in Synthesis Example 3 by adding a spherical aluminum nitride filler having an average particle diameter of 1.1 μm and mixing with a centrifugal stirrer until uniform. I was Thereafter, a metal-clad laminate M9 was produced in the same manner as in Example 1. At this time, the thickness of the polyimide resin layer on the copper foil was 25 μm. In order to evaluate the characteristics of the polyimide resin layer in the metal-clad laminate, the copper foil was removed by etching to prepare a polyimide film m9, and the CTE, thermal conductivity, and tear propagation resistance were evaluated. Further, the peel strength between the polyimide resin layer of the metal-clad laminate and the copper foil was evaluated. The results are shown in Table 2.
（実施例・比較例の評価）
表２に示す結果から、実施例１〜６の金属張積層体は、いずれも、厚み方向熱伝導率（λｚＴＣ）が１．０(Ｗ/ｍＫ)以上、ガラス転移温度（Ｔｇ）が３００℃以上、引裂き伝播抵抗が０．７（ｋＮ／ｍ）以上１．０ｋＮ／ｍの範囲内で、かつピール強度が０．５ｋＮ／ｍ以上であった。従って、実施例１〜６の金属張積層体は、ポリイミド樹脂層の熱伝導性に優れ、しかも、耐熱性、機械強度及び金属層に対する接着性も良好で、これらの特性をバランスよく備えていた。これは、実施例１〜６の金属張積層体が、上記一般式（１）で表される構造単位を６０モル％以上含有し、熱伝導性フィラーを４０〜８０ｖｏｌ％の範囲内で含有するポリイミド樹脂層を、ポリイミド樹脂層全体の厚みの７０％以上の厚みで備えていたためである。
(Evaluation of Examples and Comparative Examples)
From the results shown in Table 2, all of the metal-clad laminates of Examples 1 to 6 have a thickness direction thermal conductivity (λzTC) of 1.0 (W / mK) or more and a glass transition temperature (Tg) of 300 ° C. As described above, the tear propagation resistance was within the range of 0.7 (kN / m) to 1.0 kN / m, and the peel strength was 0.5 kN / m or more. Therefore, the metal-clad laminates of Examples 1 to 6 were excellent in the thermal conductivity of the polyimide resin layer, and also had good heat resistance, mechanical strength, and adhesion to the metal layer, and had these characteristics in a well-balanced manner. . This is because the metal-clad laminates of Examples 1 to 6 contain 60 mol% or more of the structural unit represented by the above general formula (1) and contain the thermally conductive filler in the range of 40 to 80 vol%. This is because the polyimide resin layer is provided with a thickness of 70% or more of the total thickness of the polyimide resin layer.
それに対して、熱伝導性フィラーの配合量が４０ｖｏｌ％を下回る比較例１では、引裂き伝播抵抗は大きいものの、厚み方向熱伝導率が十分でなく、また熱膨張係数が大きいことから、回路基板に求められる寸法安定性に劣ることが懸念された。また、熱伝導性フィラーの配合量が８０ｖｏｌ％を超える比較例２では、ポリイミド樹脂層が著しく脆弱で諸特性の評価が不能であり、実用性を欠くものであった。さらに、一般式（１）で表される構造単位を含まないポリイミド樹脂を使用した比較例３、４では、熱伝導性は優れていたが、比較例３は引裂伝播抵抗及びピール強度が劣っており、比較例４は耐熱性及び引裂伝播抵抗の点で満足のいく特性が得られなかった。 On the other hand, in Comparative Example 1 in which the blending amount of the heat conductive filler is less than 40 vol%, although the tear propagation resistance is large, the thermal conductivity in the thickness direction is not sufficient, and the thermal expansion coefficient is large. There was concern that the required dimensional stability was inferior. Moreover, in the comparative example 2 with the compounding quantity of a heat conductive filler exceeding 80 vol%, a polyimide resin layer was remarkably weak and evaluation of various characteristics was impossible, and lacked practicality. Furthermore, in Comparative Examples 3 and 4 using the polyimide resin not containing the structural unit represented by the general formula (1), the thermal conductivity was excellent, but Comparative Example 3 was inferior in tear propagation resistance and peel strength. In Comparative Example 4, satisfactory characteristics were not obtained in terms of heat resistance and tear propagation resistance.
本発明によれば、熱伝導性に優れ、十分な耐熱性と金属層への接着性を有する金属張積層体及び熱伝導性ポリイミドフィルムを提供することができる。本発明の金属張積層体及び熱伝導性ポリイミドフィルムは、良好な放熱性を示し、金属層との接着性にも優れることから、これらの特性が求められる携帯電話や、ノートパソコンなどの小型電子機器、ＬＥＤ照明機器などにおける放熱基板や回路基板等の用途に好適に用いることができる。 According to the present invention, it is possible to provide a metal-clad laminate and a thermally conductive polyimide film that are excellent in thermal conductivity and have sufficient heat resistance and adhesion to a metal layer. Since the metal-clad laminate and the heat conductive polyimide film of the present invention exhibit good heat dissipation and excellent adhesion to the metal layer, small electronic devices such as mobile phones and notebook computers that require these characteristics. It can be suitably used for applications such as heat dissipation boards and circuit boards in devices and LED lighting devices.
以上、本発明の実施の形態を例示の目的で詳細に説明したが、本発明は上記実施の形態に制約されることはない。 As mentioned above, although embodiment of this invention was described in detail for the purpose of illustration, this invention is not restrict | limited to the said embodiment.
Claims (10)
前記ポリイミド樹脂層（Ｉ）の片面又は両面に設けられた金属層と、
を備えた金属張積層体であって、
前記ポリイミド樹脂層（Ｉ）は、その全体の厚みの７０％以上の厚みを有するポリイミド樹脂層（ｉ）を有しており、かつ、前記ポリイミド樹脂層（Ｉ）全体のガラス転移温度が３００℃以上であり、
前記ポリイミド樹脂層（ｉ）が、下記一般式（１）で表される構造単位を６０モル％以上含有するポリイミド樹脂によって構成されるとともに、熱伝導性フィラーを４０〜８０ｖｏｌ％の範囲内で含有するものであり、
前記ポリイミド樹脂層（ｉ）の少なくとも一方の面が前記金属層と直接接していることを特徴とする金属張積層体。
A metal layer provided on one or both sides of the polyimide resin layer (I);
A metal-clad laminate comprising:
The polyimide resin layer (I) has a polyimide resin layer (i) having a thickness of 70% or more of the total thickness, and the glass transition temperature of the entire polyimide resin layer (I) is 300 ° C. That's it,
While the said polyimide resin layer (i) is comprised with the polyimide resin which contains 60 mol% or more of structural units represented by following General formula (1), it contains a heat conductive filler in the range of 40-80 vol%. Is what
A metal-clad laminate, wherein at least one surface of the polyimide resin layer (i) is in direct contact with the metal layer.
前記熱伝導性ポリイミドフィルムの全体の厚みの７０％以上の厚みを有するポリイミド樹脂層（ｉ）を有しており、かつ、前記熱伝導性ポリイミドフィルム全体のガラス転移温度が３００℃以上であり、
前記ポリイミド樹脂層（ｉ）が、下記一般式（１）で表される構造単位を６０モル％以上含有するポリイミド樹脂によって構成されるとともに、熱伝導性フィラーを４０〜８０ｖｏｌ％の範囲内で含有するものであり、
片面又は両面に金属層と直接張り合わされる粘着性貼着面を備えていることを特徴とする熱伝導性ポリイミドフィルム。
It has a polyimide resin layer (i) having a thickness of 70% or more of the total thickness of the thermally conductive polyimide film, and the glass transition temperature of the entire thermally conductive polyimide film is 300 ° C. or higher,
While the said polyimide resin layer (i) is comprised with the polyimide resin which contains 60 mol% or more of structural units represented by following General formula (1), it contains a heat conductive filler in the range of 40-80 vol%. der which is,
A thermally conductive polyimide film comprising an adhesive sticking surface directly bonded to a metal layer on one side or both sides .
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| WO2020017543A1 (en) | 2018-07-18 | 2020-01-23 | 三菱マテリアル株式会社 | Metal base substrate |
| WO2020017550A1 (en) | 2018-07-18 | 2020-01-23 | 三菱マテリアル株式会社 | Metal base substrate |
| WO2021200895A1 (en) | 2020-03-31 | 2021-10-07 | 三菱マテリアル株式会社 | Metal base substrate, electronic component mounting substrate |
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| TWI455822B (en) * | 2008-09-08 | 2014-10-11 | Nippon Steel & Sumikin Chem Co | High thermal conductivity polyimide film, high thermal conductivity metal-clad laminate and method for producing same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2020017543A1 (en) | 2018-07-18 | 2020-01-23 | 三菱マテリアル株式会社 | Metal base substrate |
| WO2020017550A1 (en) | 2018-07-18 | 2020-01-23 | 三菱マテリアル株式会社 | Metal base substrate |
| KR20210031457A (en) | 2018-07-18 | 2021-03-19 | 미쓰비시 마테리알 가부시키가이샤 | Metal base substrate |
| KR20210031458A (en) | 2018-07-18 | 2021-03-19 | 미쓰비시 마테리알 가부시키가이샤 | Metal base substrate |
| WO2021200895A1 (en) | 2020-03-31 | 2021-10-07 | 三菱マテリアル株式会社 | Metal base substrate, electronic component mounting substrate |
| KR20220159996A (en) | 2020-03-31 | 2022-12-05 | 미쓰비시 마테리알 가부시키가이샤 | Metal base board, electronic component mounting board |
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