JP5890253B2 - Thermally conductive thermosetting adhesive composition and thermally conductive thermosetting adhesive sheet - Google Patents
Thermally conductive thermosetting adhesive composition and thermally conductive thermosetting adhesive sheet Download PDFInfo
- Publication number
- JP5890253B2 JP5890253B2 JP2012125424A JP2012125424A JP5890253B2 JP 5890253 B2 JP5890253 B2 JP 5890253B2 JP 2012125424 A JP2012125424 A JP 2012125424A JP 2012125424 A JP2012125424 A JP 2012125424A JP 5890253 B2 JP5890253 B2 JP 5890253B2
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- JP
- Japan
- Prior art keywords
- adhesive
- thermally conductive
- thermosetting adhesive
- adhesive sheet
- epoxy resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000000853 adhesive Substances 0.000 title claims description 127
- 230000001070 adhesive effect Effects 0.000 title claims description 124
- 229920001187 thermosetting polymer Polymers 0.000 title claims description 21
- 239000000203 mixture Substances 0.000 title claims description 17
- 229920001721 polyimide Polymers 0.000 claims description 49
- 239000003822 epoxy resin Substances 0.000 claims description 45
- 229920000647 polyepoxide Polymers 0.000 claims description 45
- 239000009719 polyimide resin Substances 0.000 claims description 33
- 229920001296 polysiloxane Polymers 0.000 claims description 33
- 239000011231 conductive filler Substances 0.000 claims description 29
- 239000003795 chemical substances by application Substances 0.000 claims description 21
- 239000002245 particle Substances 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 14
- 239000000155 melt Substances 0.000 claims description 12
- -1 tetracarboxylic anhydride Chemical class 0.000 description 43
- 230000015556 catabolic process Effects 0.000 description 25
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 14
- 229920005989 resin Polymers 0.000 description 14
- 239000011347 resin Substances 0.000 description 14
- 239000004642 Polyimide Substances 0.000 description 13
- 238000000034 method Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 239000010408 film Substances 0.000 description 12
- 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 11
- 230000015572 biosynthetic process Effects 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 125000004432 carbon atom Chemical group C* 0.000 description 9
- 238000003475 lamination Methods 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 238000012545 processing Methods 0.000 description 9
- 239000000758 substrate Substances 0.000 description 9
- 239000004593 Epoxy Substances 0.000 description 8
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 7
- 239000011889 copper foil Substances 0.000 description 7
- 238000006731 degradation reaction Methods 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- 238000009413 insulation Methods 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 6
- 230000009477 glass transition Effects 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 6
- 229920003986 novolac Polymers 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 125000002947 alkylene group Chemical group 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 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 5
- 229920005575 poly(amic acid) Polymers 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 230000001681 protective effect Effects 0.000 description 5
- 239000013557 residual solvent Substances 0.000 description 5
- 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 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
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- 150000004985 diamines Chemical class 0.000 description 4
- 239000004205 dimethyl polysiloxane Substances 0.000 description 4
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 4
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- 239000000945 filler Substances 0.000 description 4
- 239000010419 fine particle Substances 0.000 description 4
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 4
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- 239000000047 product Substances 0.000 description 4
- 238000006798 ring closing metathesis reaction Methods 0.000 description 4
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 4
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 229910052582 BN Inorganic materials 0.000 description 3
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 239000004305 biphenyl Substances 0.000 description 3
- 235000010290 biphenyl Nutrition 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 3
- 229930003836 cresol Natural products 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 238000005187 foaming Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 238000010030 laminating Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000004381 surface treatment Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 2
- RCYNJDVUURMJOZ-UHFFFAOYSA-N 2-amino-5-[(4-amino-3-hydroxyphenyl)methyl]phenol Chemical compound C1=C(O)C(N)=CC=C1CC1=CC=C(N)C(O)=C1 RCYNJDVUURMJOZ-UHFFFAOYSA-N 0.000 description 2
- 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 2
- DKKYOQYISDAQER-UHFFFAOYSA-N 3-[3-(3-aminophenoxy)phenoxy]aniline Chemical compound NC1=CC=CC(OC=2C=C(OC=3C=C(N)C=CC=3)C=CC=2)=C1 DKKYOQYISDAQER-UHFFFAOYSA-N 0.000 description 2
- IZOMAKMJPXTDQO-UHFFFAOYSA-N 3-[[[(3-aminophenoxy)methyl-dimethylsilyl]oxy-dimethylsilyl]methoxy]aniline Chemical compound C=1C=CC(N)=CC=1OC[Si](C)(C)O[Si](C)(C)COC1=CC=CC(N)=C1 IZOMAKMJPXTDQO-UHFFFAOYSA-N 0.000 description 2
- AVCOFPOLGHKJQB-UHFFFAOYSA-N 4-(3,4-dicarboxyphenyl)sulfonylphthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1S(=O)(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 AVCOFPOLGHKJQB-UHFFFAOYSA-N 0.000 description 2
- 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 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 230000009102 absorption Effects 0.000 description 2
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- 150000008065 acid anhydrides Chemical class 0.000 description 2
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- 125000002723 alicyclic group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- ZLSMCQSGRWNEGX-UHFFFAOYSA-N bis(4-aminophenyl)methanone Chemical compound C1=CC(N)=CC=C1C(=O)C1=CC=C(N)C=C1 ZLSMCQSGRWNEGX-UHFFFAOYSA-N 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000007791 dehumidification Methods 0.000 description 2
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- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 2
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- 239000000835 fiber Substances 0.000 description 2
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
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- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
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- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 1
- RLXBOUUYEFOFSW-UHFFFAOYSA-N 2,5-diaminobenzene-1,4-diol Chemical compound NC1=CC(O)=C(N)C=C1O RLXBOUUYEFOFSW-UHFFFAOYSA-N 0.000 description 1
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- UDELTSIXRRZAID-UHFFFAOYSA-N 2-(4-aminophenoxy)-5-propylbenzoic acid Chemical compound C(=O)(O)C=1C=C(C=CC=1OC1=CC=C(C=C1)N)CCC UDELTSIXRRZAID-UHFFFAOYSA-N 0.000 description 1
- CIKCANOTXAHYEO-UHFFFAOYSA-N 2-(4-aminophenoxy)-5-propylphenol Chemical compound OC1=CC(CCC)=CC=C1OC1=CC=C(N)C=C1 CIKCANOTXAHYEO-UHFFFAOYSA-N 0.000 description 1
- AQJLUYXZEMDWLR-UHFFFAOYSA-N 2-amino-5-(4-amino-3-carboxybenzoyl)benzoic acid Chemical compound C1=C(C(O)=O)C(N)=CC=C1C(=O)C1=CC=C(N)C(C(O)=O)=C1 AQJLUYXZEMDWLR-UHFFFAOYSA-N 0.000 description 1
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- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
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- 238000004455 differential thermal analysis Methods 0.000 description 1
- WHGNXNCOTZPEEK-UHFFFAOYSA-N dimethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](C)(OC)CCCOCC1CO1 WHGNXNCOTZPEEK-UHFFFAOYSA-N 0.000 description 1
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- BXKDSDJJOVIHMX-UHFFFAOYSA-N edrophonium chloride Chemical compound [Cl-].CC[N+](C)(C)C1=CC=CC(O)=C1 BXKDSDJJOVIHMX-UHFFFAOYSA-N 0.000 description 1
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- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
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- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
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- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 1
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Images
Description
本発明は、主に金属ベース基板、金属コア基板、大電流基板などの有機系放熱基板、フレキシブルプリント基板（ＦＰＣ）の貼り合わせ、および各種モデュールの組み立て、電子機器と放熱部材の接着などに好適な熱伝導性と電気信頼性に優れた接着剤組成物及び接着剤シートに関するものである。 The present invention is suitable mainly for metal base substrates, metal core substrates, organic heat dissipation substrates such as high current substrates, bonding of flexible printed circuit boards (FPC), assembly of various modules, adhesion of electronic devices and heat dissipation members, etc. The present invention relates to an adhesive composition and an adhesive sheet excellent in thermal conductivity and electrical reliability.
近年、電子機器の高機能化、高密度実装化進み、電子機器の発熱量の増大、軽薄短小化による熱密度の増大がクローズアップされている。また照明や、液晶ＴＶのバックライトとしての発光ダイオード（以下、ＬＥＤという）が使用されている。更にスマートグリッドに代表されるエネルギー分野では、パワーデバイスの拡大が見込まれており、またＬＥＤ素子の実装や、パワーデバイスのパッケージにおいては金属基板を使用する事やチップに熱伝導性接着剤を介してヒートシンクを接着し、熱を効率よく放散し、素子の温度等の上昇を防ぎ、結果、安定した動作、超寿命化にする試みがなされている。電子機器の組み立て実装においては、多ピン化、小型化、高密度実装の開発が進められており、回路パターンのファイン化に対応する高い絶縁性が求められている。
このように、絶縁性が高く、熱伝導性の高い接着剤が求められている。
2. Description of the Related Art In recent years, electronic devices have advanced functions and high-density packaging, and the increase in heat generation due to the increase in heat generation of electronic devices and the reduction in lightness and thickness have been highlighted. In addition, light emitting diodes (hereinafter referred to as LEDs) are used as illumination and backlights of liquid crystal TVs. Furthermore, in the energy field represented by smart grids, the expansion of power devices is expected, and in the mounting of LED elements and in the packaging of power devices, the use of metal substrates and the use of thermally conductive adhesives on the chips. Attempts have been made to adhere heat sinks, dissipate heat efficiently, prevent the temperature of the elements from rising, and, as a result, achieve stable operation and long life. In assembly mounting of electronic devices, development of high pin count, miniaturization, and high-density mounting is underway, and high insulation properties corresponding to finer circuit patterns are required.
Thus, an adhesive having high insulation and high thermal conductivity is demanded.
従来、樹脂の熱伝導率を高める方法としてエポキシ樹脂、熱可塑性樹脂に熱伝導性の高い無機充填材を配合する方法が開示されている（例えば、特許文献１参照。）
しかしながら、これらには 熱可塑性樹脂としてアクリロニトリル−ブタジエン共重合体（ＮＢＲ）、アクリロニトリル−ブタジエンゴム−スチレン樹脂（ＡＢＳ）、ポリブタジエン、スチレン−ブタジエン−エチレン樹脂（ＳＥＢＳ）、炭素数１〜８の側鎖を有するアクリル酸および／またはメタクリル酸エステル樹脂（アクリルゴム）、ポリビニルブチラール、ポリアミド、ポリエステル、ポリイミド、ポリアミドイミド、ポリウレタン等の一般的な樹脂が例示されされるにとどまり、前述のような高い絶縁性に関する言及、また高温下で使用されることに対応した耐熱性に関して言及されていない。更には高温下で使用されるにも関わらず、絶縁性については常温での破壊に着目することがおおく、従来の熱伝導性の接着剤は耐熱性が不十分で、熱劣化を起こしやすく高温時の絶縁性などの低下が大きかった。また、熱伝導率をあげるために熱伝導性充填材の添加量が多くなり、フィルム化を行う際にまげると割れるなどの問題があった。
一方、熱伝導性接着剤は基材同士の接着に用いる為、その接触部位での濡れ性を十分確保することが必要であるが、熱伝導性を重視するあまりに、熱伝導充填材の含有量が多くなり、高温で積層しなければならないなどの組み立て上の問題が考慮されていないなどの問題も有していた。
Conventionally, as a method for increasing the thermal conductivity of a resin, a method of blending an inorganic filler with high thermal conductivity into an epoxy resin or a thermoplastic resin has been disclosed (for example, see Patent Document 1).
However, these include acrylonitrile-butadiene copolymer (NBR), acrylonitrile-butadiene rubber-styrene resin (ABS), polybutadiene, styrene-butadiene-ethylene resin (SEBS), and side chains having 1 to 8 carbon atoms as thermoplastic resins. Examples include acrylic resins and / or methacrylic acid ester resins (acrylic rubber), polyvinyl butyral, polyamides, polyesters, polyimides, polyamideimides, polyurethanes, and the like, which have high insulating properties as described above. No mention is made regarding the heat resistance corresponding to being used at high temperatures. In addition, although it is used at high temperatures, it is important to pay attention to breakdown at room temperature. Conventional heat conductive adhesives have insufficient heat resistance and are prone to thermal degradation. There was a significant decrease in insulation properties. In addition, the amount of the heat conductive filler added is increased in order to increase the thermal conductivity, and there has been a problem such as cracking when it is turned into a film.
On the other hand, since the heat conductive adhesive is used for bonding substrates, it is necessary to ensure sufficient wettability at the contact site, but too much heat conductivity is important, the content of heat conductive filler There were also problems such as the fact that assembly problems such as having to be laminated at a high temperature were not taken into account.
本発明は、以上のような問題点を鑑みてなされたものであり、その目的とする処は、優れた熱伝導性(熱伝導率として０．２ｗ／ｍ・以上)を有し、熱劣化性が小さく、高い絶縁性を有しながら、加工性に優れた熱伝導性熱硬化型接着剤組成物及び熱伝導性熱硬化型接着剤シートを提供することにある。 The present invention has been made in view of the problems as described above, and its intended treatment is excellent thermal conductivity (thermal conductivity of 0.2 w / m · or more) and thermal degradation. An object is to provide a heat conductive thermosetting adhesive composition and a heat conductive thermosetting adhesive sheet that are excellent in processability while having low properties and high insulation properties.
上記課題を解決するため、鋭意検討した結果、本発明の熱伝導性熱硬化型接着剤組成物は、ポリイミド樹脂、エポキシ樹脂、硬化剤及び熱伝導性充填材を含む熱伝導性熱硬化型接着剤組成物であって、前記エポキシ樹脂がシリコーン骨格を含有するか又は硬化剤がシリコーン骨格を含有し、加熱時の溶融粘度曲線において、最下限値が温度１３０〜２３０℃に有し、且つ最下限値の粘度が２００００ｐｏｉｓｅ以上であることを特徴とするものである。
また、本発明の熱伝導性熱硬化型接着剤シートは、ポリイミド樹脂、エポキシ樹脂、硬化剤及び熱伝導性充填材を含む熱伝導性熱硬化型接着剤シートであって、前記エポキシ樹脂がシリコーン骨格を含有するか又は硬化剤がシリコーン骨格を含有し、加熱時の溶融粘度曲線において、最下限値が温度１３０〜２３０℃に有し、且つ最下限値の粘度が２００００ｐｏｉｓｅ以上であることを特徴とする。
As a result of intensive studies to solve the above problems, the thermally conductive thermosetting adhesive composition of the present invention is a thermally conductive thermosetting adhesive including a polyimide resin, an epoxy resin, a curing agent, and a thermally conductive filler. The epoxy resin contains a silicone skeleton or the curing agent contains a silicone skeleton, and in the melt viscosity curve at the time of heating, the lowest limit is at a temperature of 130 to 230 ° C., and the highest The lower limit viscosity is 20000 poise or more.
The heat conductive thermosetting adhesive sheet of the present invention is a heat conductive thermosetting adhesive sheet including a polyimide resin, an epoxy resin, a curing agent and a heat conductive filler, and the epoxy resin is silicone. The skeleton is contained or the curing agent contains a silicone skeleton, and in the melt viscosity curve at the time of heating, the lowest limit has a temperature of 130 to 230 ° C., and the lowest viscosity has a viscosity of 20000 poise or more. And
本発明によれば、熱劣化性が小さく、高い絶縁性と熱伝導性を有し、比較的低温で加工できる熱伝導性熱硬化型接着剤組成物及び熱伝導性熱硬化型接着剤シートを提供することができる。 According to the present invention, there is provided a heat conductive thermosetting adhesive composition and a heat conductive thermosetting adhesive sheet that have low thermal degradation, high insulation and thermal conductivity, and can be processed at a relatively low temperature. Can be provided.
以下、本発明の実施の形態を詳しく説明する。
本発明の熱伝導性熱硬化型接着剤組成物（以下、単に接着剤ともいう）は、硬化する前は、加熱により溶融し、金属板に圧着できる。また熱による硬化後は加熱されても溶融することなく、高温で高い弾性率が得られる。本発明の接着剤はポリイミド樹脂を含有する。ポリイミド樹脂は接着剤に可撓性を付与することや、硬化前の接着剤の強度などを付与する為に必要である。可撓性を付与するには、ポリイミド樹脂のかわりに、アクリルニトリルブタジエンゴムやアクリルゴムなどの樹脂が使用できるが、これらは、熱分解温度が低いこと、高温に放置されると劣化しやすい傾向にある。更には絶縁破壊電圧や接着力の温度依存性が大きく、この点においてもポリイミド樹脂を使用する事で、そのような問題を回避できる。
ＬＥＤやパワーデバイス等の用途においては、高温での動作があり、耐熱性、特に熱劣化性の低い熱伝導性の接着剤が必要となり、接着剤の構成要素としてポリイミド樹脂は必須の成分である。
Hereinafter, embodiments of the present invention will be described in detail.
The heat conductive thermosetting adhesive composition of the present invention (hereinafter also simply referred to as an adhesive) can be melted by heating and pressure-bonded to a metal plate before being cured. Moreover, after hardening by heat, even if heated, it does not melt, and a high elastic modulus can be obtained at a high temperature. The adhesive of the present invention contains a polyimide resin. The polyimide resin is necessary for imparting flexibility to the adhesive and for imparting strength of the adhesive before curing. In order to give flexibility, resins such as acrylonitrile butadiene rubber and acrylic rubber can be used instead of polyimide resin, but these have low thermal decomposition temperatures and tend to deteriorate when left at high temperatures. It is in. Furthermore, the temperature dependence of the dielectric breakdown voltage and the adhesive force is large. In this respect as well, such a problem can be avoided by using the polyimide resin.
In applications such as LEDs and power devices, there is an operation at high temperature, and a heat conductive adhesive with low heat resistance, especially heat degradation, is required, and polyimide resin is an essential component as a component of the adhesive .
ポリイミド樹脂は主鎖中に酸イミド結合を有する重合体の総称であり、テトラカルボン酸無水物とジアミンの環化重縮合によって合成することができる。また、ポリイミド樹脂としては、可溶性若しくは可溶融性のものが好適である。
本発明におけるポリイミド樹脂は、少なくとも式（Ｉ）で示される構造単位を有し、式（ＩＩ）で示される構造単位及び式（ＩＩＩ）で示される構造単位が適宜、配列されるポリイミド樹脂である。
Polyimide resin is a general term for polymers having an acid imide bond in the main chain, and can be synthesized by cyclization polycondensation of tetracarboxylic anhydride and diamine. Moreover, as a polyimide resin, a soluble or meltable thing is suitable.
The polyimide resin in the present invention is a polyimide resin having at least a structural unit represented by the formula (I), in which the structural unit represented by the formula (II) and the structural unit represented by the formula (III) are appropriately arranged. .
一般的にポリイミド樹脂は剛直なものであり、接着剤としてある程度低温で加工する事を実現するには、Ｔｇや硬さを調整することが必要である。また熱伝導性を付与するには多量の熱伝導性充填材を添加する必要があり、接着剤は可撓性が低くなり、割れるなどの問題が発生する。そのような問題を改善する為に、ポリイミド樹脂中にシロキサン骨格を導入することが用いられる。シロキサン骨格の比率によりガラス転移温度（以下、Ｔｇという）や硬さ、更に延性がかわり、シロキサン骨格がおおいと低Ｔｇ、低弾性になるが、充填材が多量に添加されることで、弾性率は高くなる。また接着剤としては、エポキシ樹脂や硬化剤などの硬化成分により硬さなどの耐熱性、を補完することが可能である。またシロキサンの比率を下げるとより高温で高い弾性率が得られるものの、低温での加工が難しくなる。その場合には、エポキシ樹脂や硬化剤などの硬化成分にシロキサン骨格を導入する、もしくはシロキサン骨格のエポキシ樹脂、硬化剤を使用する事により、補完する事が出来る。Ｔｇとしては特に限定されるものではないが、Ｔｇとしては３５℃から１８０℃程度が望ましい。尚Ｔｇは示差熱分析により、吸熱がおこる温度を測定し、そのピークもしくはオンセット、オフセット温度から求める。 Generally, a polyimide resin is rigid, and it is necessary to adjust Tg and hardness in order to realize processing at a certain low temperature as an adhesive. Further, in order to impart thermal conductivity, it is necessary to add a large amount of thermally conductive filler, and the adhesive becomes less flexible and causes problems such as cracking. In order to improve such a problem, it is used to introduce a siloxane skeleton into the polyimide resin. Depending on the ratio of the siloxane skeleton, the glass transition temperature (hereinafter referred to as Tg), hardness, and ductility change. If the siloxane skeleton is thick, the Tg and low elasticity become low, but the elastic modulus is increased by adding a large amount of filler. Becomes higher. Moreover, as an adhesive agent, it is possible to supplement heat resistance, such as hardness, with hardening components, such as an epoxy resin and a hardening | curing agent. Further, when the ratio of siloxane is lowered, a high elastic modulus can be obtained at a higher temperature, but processing at a low temperature becomes difficult. In that case, it can be supplemented by introducing a siloxane skeleton into a curing component such as an epoxy resin or a curing agent, or using an epoxy resin or a curing agent having a siloxane skeleton. Tg is not particularly limited, but Tg is preferably about 35 to 180 ° C. Tg is obtained by measuring the temperature at which endotherm occurs by differential thermal analysis and calculating the Tg from the peak, onset, or offset temperature.
また硬さを調整する為に導入するシロキサン部位であるが、耐熱性等を考慮する必要があること、ならびに、接着性が必要であることから、含有量やシロキサン部位の重合度は制限され、ポリシロキサンの平均重合度は２〜３３（分子量としては、約２５０〜３０００）好ましくは平均重合度が４〜２４(分子量としては約４００〜２０００)のものが使用される。 Moreover, although it is the siloxane part introduced in order to adjust hardness, since it is necessary to consider heat resistance etc., and adhesiveness is required, content and the polymerization degree of a siloxane part are restricted, The average degree of polymerization of the polysiloxane is 2 to 33 (molecular weight is about 250 to 3000), preferably the average degree of polymerization is 4 to 24 (molecular weight is about 400 to 2000).
またポリイミド樹脂の分子量は溶融性を考慮し、約１５０００から７００００が望ましい。分子量はＧＰＣにて、テトラヒドロフラン（ＴＨＦ）を溶離液として用い測定でき、スチレン換算の平均分子量として得られる。その数平均分子量は、１５０００未満の場合は膜の靭性、延性が損なわれ、脆くなる。また７００００よりも大きい場合は溶剤溶解性が低下し、加工性が劣ることや、接着剤としての溶融性が低下し、加工温度が高くなり、実用に供しにくい。 The molecular weight of the polyimide resin is preferably about 15000 to 70000 in consideration of meltability. The molecular weight can be measured by GPC using tetrahydrofuran (THF) as an eluent, and obtained as an average molecular weight in terms of styrene. When the number average molecular weight is less than 15,000, the toughness and ductility of the film are impaired and the film becomes brittle. On the other hand, when it is larger than 70000, the solvent solubility is lowered, the workability is inferior, the meltability as an adhesive is lowered, the processing temperature is increased, and it is difficult to put it to practical use.
エポキシ基との反応性を付与することで、より耐熱性の高い接着剤が得られることから、官能基を有する反応性ポリイミドが、下記式（ＩＶ）で示されるテトラカルボン酸二無水物と、下記式（Ｖ）で示されるシロキサン化合物、下記式（ＶＩ）で示されるジアミン化合物および下記式（ＶＩＩ）で示されるエポキシ反応性基を有するジアミン化合物とを、有機溶剤中で重縮合させ、得られたポリアミック酸を閉環によりイミド化することによって得ることができる。
反応性を有することにより基板として使用される場合のＷ／Ｂ性などが向上する。また溶剤への膨潤性も抑制され、種々の使途に使用できる。反応する官能基としては、カルボキシル基、水酸基などが一般的には使用される。
By imparting reactivity with an epoxy group, an adhesive having higher heat resistance can be obtained, so that a reactive polyimide having a functional group is a tetracarboxylic dianhydride represented by the following formula (IV): A siloxane compound represented by the following formula (V), a diamine compound represented by the following formula (VI), and a diamine compound having an epoxy reactive group represented by the following formula (VII) are polycondensed in an organic solvent to obtain The obtained polyamic acid can be obtained by imidization by ring closure.
By having reactivity, the W / B property when used as a substrate is improved. Moreover, the swelling property to a solvent is also suppressed and it can be used for various uses. As the functional group that reacts, a carboxyl group, a hydroxyl group, or the like is generally used.
またポリイミド樹脂の接着剤中の樹脂分(接着剤から熱伝導性充填材を除いたもの)にしめる比率は３５〜６５質量％が望ましい。ポリイミド樹脂が３５質量％より少ないと、可撓性が不十分になり、６５質量％を越えると、高分子量量であるため、接着剤の溶融性が低下し、加工温度が高くなる。接着する基材との濡れが不十分になるなどの問題が発生しやすい。 The ratio of the resin component in the polyimide resin adhesive (excluding the heat conductive filler from the adhesive) is preferably 35 to 65% by mass. When the amount of the polyimide resin is less than 35% by mass, the flexibility becomes insufficient, and when it exceeds 65% by mass, since the molecular weight is high, the meltability of the adhesive is lowered and the processing temperature is increased. Problems such as insufficient wetting with the substrate to be bonded are likely to occur.
本発明に使用される式（Ｉ）で示されるポリイミド樹脂について説明する。下記式（ＩＶ）で示されるテトラカルボン酸二無水物と、下記式（Ｖ）で示されるシロキサン化合物、下記式（ＶＩ）で示されるジアミン化合物および、または下記式（ＶＩＩ）で示されるエポキシ反応性基を有するジアミン化合物とを、有機溶剤中で重縮合させ、得られたポリアミック酸を閉環によりイミド化することによって得ることができる。 The polyimide resin represented by the formula (I) used in the present invention will be described. Tetracarboxylic dianhydride represented by the following formula (IV), a siloxane compound represented by the following formula (V), a diamine compound represented by the following formula (VI), and an epoxy reaction represented by the following formula (VII) It can be obtained by polycondensing a diamine compound having a functional group in an organic solvent and imidating the resulting polyamic acid by ring closure.
前記式（ＩＶ）で示されるテトラカルボン酸二無水物としては、例えば、２，３，３’，４’−ビフェニルテトラカルボン酸二無水物、３，４，３’，４’−ビフェニルテトラカルボン酸二無水物、２，３，２’，３’−ビフェニルテトラカルボン酸二無水物、ビス（３，４−ジカルボキシフェニル）メタン二無水物、ビス（３，４−ジカルボキシフェニル）エーテル二無水物、ビス（３，４−ジカルボキシフェニル）スルホン二無水物、２，２−ビス（３，４−ジカルボキシフェニル）プロパン二無水物、３，４，３’，４’−ベンゾフェノンテトラカルボン酸二無水物、４’，４’−ビフタル酸二無水物等があげられる。 Examples of the tetracarboxylic dianhydride represented by the formula (IV) include 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, 3,4,3 ′, 4′-biphenyltetracarboxylic Acid dianhydride, 2,3,2 ′, 3′-biphenyltetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) ether Anhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 3,4,3 ′, 4′-benzophenonetetracarboxylic Examples thereof include acid dianhydride, 4 ′, 4′-biphthalic acid dianhydride, and the like.
前記式（Ｖ）で示される両末端にアミノ基を有するシロキサン化合物としては、１，３−ビス（３−アミノプロピル）−１，１，３，３−テトラメチルジシロキサン、α，ω−ビス（３−アミノプロピル）ポリジメチルシロキサン（例えば、アミノプロピル末端のジメチルシロキサンの４量体ないし８量体等）、１，３−ビス（３−アミノフェノキシメチル）−１，１，３，３−テトラメチルジシロキサン、α，ω−ビス（３−アミノフェノキシメチル）ポリジメチルシロキサン，１，３−ビス（２−（３−アミノフェノキシ）エチル）−１，１，３，３−テトラメチルジシロキサン、α，ω−ビス（２−（３−アミノフェノキシ）エチル）ポリジメチルシロキサン，１，３−ビス（３−（３−アミノフェノキシ）プロピル）−１，１，３，３−テトラメチルジシロキサン、α，ω−ビス（３−（３−アミノフェノキシ）プロピル）ポリジメチルシロキサン、等があげられる。上記のシロキサン化合物において、ポリシロキサンの場合は平均重合度が２〜３３（分子量としては、約２５０〜３０００）好ましくは平均重合度が４〜２４(分子量としては約４００〜２０００)のものが使用される。 Examples of the siloxane compound having amino groups at both ends represented by the formula (V) include 1,3-bis (3-aminopropyl) -1,1,3,3-tetramethyldisiloxane, α, ω-bis. (3-aminopropyl) polydimethylsiloxane (for example, tetramer to octamer of dimethylsiloxane having an aminopropyl terminal), 1,3-bis (3-aminophenoxymethyl) -1,1,3,3- Tetramethyldisiloxane, α, ω-bis (3-aminophenoxymethyl) polydimethylsiloxane, 1,3-bis (2- (3-aminophenoxy) ethyl) -1,1,3,3-tetramethyldisiloxane , Α, ω-bis (2- (3-aminophenoxy) ethyl) polydimethylsiloxane, 1,3-bis (3- (3-aminophenoxy) propyl) -1,1,3,3- Tetramethyl disiloxane, alpha, .omega.-bis (3- (3-aminophenoxy) propyl) polydimethyl siloxane, and the like. In the above siloxane compounds, in the case of polysiloxane, those having an average polymerization degree of 2 to 33 (molecular weight of about 250 to 3000), preferably an average polymerization degree of 4 to 24 (molecular weight of about 400 to 2000) are used. Is done.
前記式（ＶＩ）で示されるジアミン化合物としては、３，４’−ジアミノジフェニルエーテル、４，４’−ジアミノジフェニルエーテル、３，３’−ジメチル−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、４，４’−ジアミノベンゾフェノン、３，３’−ジメチル−４，４’−ジアミノベンゾフェノン、３，３’−ジアミノジフェニルメタン、３，３’−ジメトキシ−４，４’−ジアミノジフェニルメタン、２，２’−ビス（３−アミノフェニル）プロパン、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、ベンジジン、３，３’−ジメチルベンジジン、３，３’−ジメトキシベンジジン、３，３’−ジアミノビフェニル、１，３−ビス（３−アミノフェノキシ）ベンゼン、２，２−ビス［４−（４−アミノフェノキシ）フェニル］プロパン、２，２−ビス［３−メチル−４−（４−アミノフェノキシ）フェニル］プロパン、２，２−ビス［３−クロロ−４−（４−アミノフェノキシ）フェニル］プロパン、２，２−ビス［３，５−ジメチル−４−（４−アミノフェノキシ）フェニル］プロパン、１，１’−ビス［４−（４−アミノフェノキシ）フェニル］エタン、１，１’−ビス［３−クロロ−４−（４−アミノフェノキシ）フェニル］エタン、ビス［４−（４−アミノフェノキシ）フェニル］メタン、ビス［３−メチル−４−（４−アミノフェノキシ）フェニル］メタン、４，４’−［１，４−フェニレンビス（１−メチルエチリデン）］ビスアニリン、４，４’−［１，３−フェニレンビス（１−メチルエチリデン）］ビスアニリン、４，４’−［１，４−フェニレンビス（１−メチルエチリデン）］ビス（２，６−ジメチルビスアニリン）等があげられる。これらのジアミン化合物は２種以上を併用してもよい。 Examples of the diamine compound represented by the formula (VI) include 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminodiphenyl ether, and 3,3'-diamino. Diphenyl ether, 4,4′-diaminobenzophenone, 3,3′-dimethyl-4,4′-diaminobenzophenone, 3,3′-diaminodiphenylmethane, 3,3′-dimethoxy-4,4′-diaminodiphenylmethane, 2, 2′-bis (3-aminophenyl) propane, 4,4′-diaminodiphenylsulfone, 3,3′-diaminodiphenylsulfone, benzidine, 3,3′-dimethylbenzidine, 3,3′-dimethoxybenzidine, 3, 3′-diaminobiphenyl, 1,3-bis (3-aminophenoxy) Zen, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [3-methyl-4- (4-aminophenoxy) phenyl] propane, 2,2-bis [3- Chloro-4- (4-aminophenoxy) phenyl] propane, 2,2-bis [3,5-dimethyl-4- (4-aminophenoxy) phenyl] propane, 1,1′-bis [4- (4- Aminophenoxy) phenyl] ethane, 1,1′-bis [3-chloro-4- (4-aminophenoxy) phenyl] ethane, bis [4- (4-aminophenoxy) phenyl] methane, bis [3-methyl- 4- (4-aminophenoxy) phenyl] methane, 4,4 ′-[1,4-phenylenebis (1-methylethylidene)] bisaniline, 4,4 ′-[1,3-phenylenebis (1-methyl) Ruechiriden)] bisaniline, 4,4 '- [1,4-phenylene bis (1-methylethylidene)] bis (2,6-dimethyl-bis aniline) and the like. Two or more of these diamine compounds may be used in combination.
また、前記式（ＶＩＩ）で示されるエポキシ反応性基を有するジアミン化合物としては、２，５−ジヒドロキシ−ｐ−フェニレンジアミン、３，３’−ジヒドロキシ−４，４’−ジアミノジフェニルエーテル、４，３’−ジヒドロキシ−３，４’−ジアミノジフェニルエーテル、３，３’−ジヒドロキシ−４，４’−ジアミノベンゾフェノン、３，３’−ジヒドロキシ−４，４’−ジアミノジフェニルメタン、３，３’−ジヒドロキシ−４，４’−ジアミノジフェニルスルホン、４，４’−ジヒドロキシ−３，３’−ジアミノジフェニルスルホン、２，２’−ビス［３−ヒドロキシ−４−（４−アミノフェノキシ）フェニル］プロパン、ビス［３−ヒドロキシ−４−（４−アミノフェノキシ）フェニル］メタン、３，３’−ジカルボキシ−４，４’−ジアミノジフェニルエーテル、４，３’−ジカルボキシ−３，４’−ジアミノジフェニルエーテル、３，３’−ジカルボキシ−４，４’−ジアミノベンゾフェノン、３，３’−ジカルボキシ−４，４’−ジアミノジフェニルメタン、３，３’−ジカルボキシ−４，４’−ジアミノジフェニルスルホン、４，４’−ジカルボキシ−３，３’−ジアミノジフェニルスルホン、３，３’−ジカルボキシベンジジン、２，２’−ビス［３−カルボキシ−４−（４−アミノフェノキシ）フェニル］プロパン、ビス［３−カルボキシ−４−（４−アミノフェノキシ）フェニル］メタン等があげられる。これらのジアミン化合物は２種以上を併用してもよい。 Examples of the diamine compound having an epoxy reactive group represented by the formula (VII) include 2,5-dihydroxy-p-phenylenediamine, 3,3′-dihydroxy-4,4′-diaminodiphenyl ether, 4,3. '-Dihydroxy-3,4'-diaminodiphenyl ether, 3,3'-dihydroxy-4,4'-diaminobenzophenone, 3,3'-dihydroxy-4,4'-diaminodiphenylmethane, 3,3'-dihydroxy-4 , 4′-diaminodiphenylsulfone, 4,4′-dihydroxy-3,3′-diaminodiphenylsulfone, 2,2′-bis [3-hydroxy-4- (4-aminophenoxy) phenyl] propane, bis [3 -Hydroxy-4- (4-aminophenoxy) phenyl] methane, 3,3′-dicarboxy-4 4'-diaminodiphenyl ether, 4,3'-dicarboxy-3,4'-diaminodiphenyl ether, 3,3'-dicarboxy-4,4'-diaminobenzophenone, 3,3'-dicarboxy-4,4 ' -Diaminodiphenylmethane, 3,3'-dicarboxy-4,4'-diaminodiphenylsulfone, 4,4'-dicarboxy-3,3'-diaminodiphenylsulfone, 3,3'-dicarboxybenzidine, 2,2 Examples include '-bis [3-carboxy-4- (4-aminophenoxy) phenyl] propane, bis [3-carboxy-4- (4-aminophenoxy) phenyl] methane, and the like. Two or more of these diamine compounds may be used in combination.
本発明におけるポリイミド樹脂を得るためには、上記のテトラカルボン酸二無水物と、両末端にアミノ基を有するシロキサン化合物またはその他のジアミン化合物とを溶媒存在下で−２０〜１５０℃、好ましくは０〜６０℃の温度で数十分間ないし数日間反応させて、ポリアミック酸を生成させ、さらにイミド化することにより製造することができる。溶媒としては、例えば、Ｎ，Ｎ−ジメチルホルミアミド、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ，Ｎ−ジエチルアセトアミド、Ｎ−メチル−２−ピロリドン等のアミド系溶媒、ジメチルスルホキシド、ジメチルスルホン等の硫黄含有溶媒、フェノール、クレゾール、キシレノール等のフェノール系溶媒、アセトン、テトラヒドロフラン、ピリジン、テトラメチル尿素等をあげることができる。 In order to obtain the polyimide resin in the present invention, the above tetracarboxylic dianhydride and a siloxane compound or other diamine compound having an amino group at both ends are -20 to 150 ° C., preferably 0, in the presence of a solvent. It can be produced by reacting at a temperature of ˜60 ° C. for several tens of minutes to several days to produce a polyamic acid and further imidization. Examples of the solvent include amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, and N-methyl-2-pyrrolidone, and sulfur such as dimethylsulfoxide and dimethylsulfone. Examples of the solvent include phenol solvents such as phenol, cresol, and xylenol, acetone, tetrahydrofuran, pyridine, and tetramethylurea.
イミド化の方法としては加熱により脱水閉環させる方法及び脱水閉環触媒を用いて化学的に閉環させる方法がある。加熱により脱水閉環させる場合、反応温度は１５０〜４００℃、好ましくは１８０〜３５０℃あり、反応時間は数十分〜数日間、好ましくは２時間〜１２時間である。化学的に閉環させる場合の脱水閉環触媒としては、酢酸、プロピオン酸、酪酸、安息香酸等の酸無水物があり、閉環反応を促進させるピリジン等を併用することが好ましい。該触媒の使用量はジアミン総量の２００モル％以上、好ましくは３００〜１０００モル％である。 As the imidization method, there are a method of dehydrating and ring-closing by heating and a method of chemically ring-closing using a dehydrating and ring-closing catalyst. When dehydrating and ring-closing by heating, the reaction temperature is 150 to 400 ° C, preferably 180 to 350 ° C, and the reaction time is several tens of minutes to several days, preferably 2 to 12 hours. Examples of the dehydration ring closure catalyst in the case of chemical ring closure include acid anhydrides such as acetic acid, propionic acid, butyric acid, and benzoic acid, and it is preferable to use pyridine or the like that promotes the ring closure reaction. The amount of the catalyst used is 200 mol% or more, preferably 300 to 1000 mol% of the total amount of diamine.
本発明において使用するポリイミド樹脂において、上記式（Ｉ）で示される構造単位と上記式（ＩＩ）および式（ＩＩＩ）で示される構造単位は、５／９５〜５０／５０のモル比で配列されているのが好ましい。また、式（ＩＩ）で示される構造単位と式（ＩＩＩ）で示される構造単位との割合は、モル比で０：１００〜９９：１、好ましくは８０：２０〜９５：５、さらに好ましくは５０：５０〜９５：５の範囲である。 In the polyimide resin used in the present invention, the structural unit represented by the above formula (I) and the structural unit represented by the above formula (II) and formula (III) are arranged in a molar ratio of 5/95 to 50/50. It is preferable. The ratio of the structural unit represented by the formula (II) to the structural unit represented by the formula (III) is 0: 100 to 99: 1, preferably 80:20 to 95: 5, more preferably in molar ratio. It is in the range of 50:50 to 95: 5.
ポリイミド樹脂だけでは、加熱時に柔らかくなり、ＬＥＤの実装用の金属基板用接着剤等ではＬＥＤ素子のワイヤボンディング実装においてボンディング不良等の低下を招く可能性がある。シリコーンによる変性量が低い場合や、シロキサンを使用せずに比較的剛直なポリイミド樹脂を用いる場合には圧着時の温度が高くなりすぎる問題がある。これらを補完する為に、前者の課題に対してはエポキシ樹脂を併用することにより高温で柔らかくなることを抑制でき、また後者の課題に対してはポリイミド樹脂単独使用に比べて、低温で軟化して、圧着する温度の低温化が可能になり、実用に供することが出来る。 A polyimide resin alone softens when heated, and a metal substrate adhesive for LED mounting may lead to a reduction in bonding failure or the like in wire bonding mounting of LED elements. When the amount of modification by silicone is low, or when a relatively rigid polyimide resin is used without using siloxane, there is a problem that the temperature during pressure bonding becomes too high. To complement these, the former problem can be suppressed by using an epoxy resin together, and softening at a high temperature can be suppressed, and the latter problem can be softened at a lower temperature than using a polyimide resin alone. Thus, the temperature for pressure bonding can be lowered, and the pressure can be put to practical use.
エポキシ樹脂は、１分子中に２個以上のエポキシ基を有するもので、クレゾールノボラック型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、ビフェニル型骨格を含有する両末端やノボラック型エポキシ樹脂、ナフタレン骨格のエポキシ樹脂、トリフェニルメタン型のエポキシ、ビスフェノールＡ型、Ｆ型エポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂、線状脂肪族エポキシ樹脂、脂環式エポキシ樹脂、複素環式エポキシ樹脂、およびハロゲン化エポキシ樹脂等が挙げられる。
具体的には、多官能型エポキシ樹脂としては、トリフェニルメタン型エポキシ樹脂（例えば、日本化薬社製の商品名：ＥＰＰＮ５０２Ｈ）、ＪＥＲ社製の商品名：エピコート８２８、１００１、ナフタレン型エポキシ樹脂（例えば、ＤＩＣ社製の商品名：４０３２Ｄ、ＨＰ４７００）、クレゾールノボラック型エポキシ樹脂（日本化薬社製の商品名：ＥＯＣＮ１０２２）、プリンテック社製の多官能型エポキシ樹脂 商品名：ＶＧ３１０１などが挙げられる。
The epoxy resin has two or more epoxy groups in one molecule, and is a cresol novolak type epoxy resin, a phenol novolak type epoxy resin, a biphenyl type skeleton containing both ends, a novolak type epoxy resin, or a naphthalene skeleton epoxy resin. , Triphenylmethane type epoxy, bisphenol A type, F type epoxy resin, dicyclopentadiene type epoxy resin, linear aliphatic epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin, halogenated epoxy resin, etc. Can be mentioned.
Specifically, as the polyfunctional epoxy resin, a triphenylmethane type epoxy resin (for example, trade name: EPPN502H manufactured by Nippon Kayaku Co., Ltd.), a product name manufactured by JER: Epicoat 828, 1001, naphthalene type epoxy resin (For example, DIC Corporation trade name: 4032D, HP4700), cresol novolac type epoxy resin (Nippon Kayaku Co., Ltd. trade name: EOCN1022), Printtec's multifunctional epoxy resin trade name: VG3101, etc. It is done.
また両末端エポキシ樹脂としては、ビスフェノールＡ型のエポキシ樹脂、ビフェニル型エポキシ樹脂（例えばＪＥＲ社製 商品名：ＹＸ−４０００）、ジシクロペンタジエン型エポキシ樹脂（例えばＤＩＣ社製 商品名：ＨＰ７２００）などである。
耐熱性の高い多官能型エポキシと柔軟性や流動性を有する両末端や直鎖型のエポキシを併用することも好ましく使用できる。
またポリイミド樹脂にシリコーン骨格を含まない場合には、シリコーン骨格を有するエポキシ樹脂を使用する事で低温での構成、柔軟性のある接着剤が得られる。
シリコーン骨格のエポキシ樹脂としては、信越化学社製の商品名：Ｘ−２２−１６３Ａ、側鎖フェニルタイプのシロキサン骨格のエポキシ樹脂、脂環式エポキシ樹脂(信越化学社製 商品名：Ｘ−２２−２０４６等)などが使用できる。
またシリコーン骨格のエポキシ樹脂だけでは高温での硬さが得られない場合には、多官能型エポキシとの併用も出来る。
As both-end epoxy resins, bisphenol A type epoxy resins, biphenyl type epoxy resins (for example, product name: YX-4000 manufactured by JER), dicyclopentadiene type epoxy resins (for example, product name: HP7200 manufactured by DIC), etc. is there.
It is also possible to preferably use a polyfunctional epoxy having high heat resistance in combination with a terminal or linear epoxy having flexibility and fluidity.
Further, when the polyimide resin does not contain a silicone skeleton, the use of an epoxy resin having a silicone skeleton makes it possible to obtain a low-temperature adhesive and a flexible adhesive.
As epoxy resin of silicone skeleton, trade name: X-22-163A manufactured by Shin-Etsu Chemical Co., Ltd., epoxy resin of siloxane skeleton of phenyl chain type of side chain, alicyclic epoxy resin (trade name: X-22- manufactured by Shin-Etsu Chemical Co., Ltd.) 2046 etc.) can be used.
In addition, when hardness at high temperature cannot be obtained only with an epoxy resin having a silicone skeleton, it can be used in combination with a polyfunctional epoxy.
接着剤にはエポキシ基と架橋反応する硬化剤を含有する。エポキシ樹脂と硬化反応する硬化剤を含有することで硬化後の硬さ、耐熱性が向上する。硬化剤の例としては、３，３’，５，５’−テトラメチル−４，４’−ジアミノジフェニルメタンン、３，３’，５，５’−テトラエチル−４，４’−ジアミノジフェニルメタン、３，３’−ジメチル−５，５’−ジエチル−４，４’−ジアミノジフェニルメタン、３，３’−ジクロロ−４，４’−ジアミノジフェニルメタン、２，２’，３，３’−テトラクロロ−４，４’−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’−ジアミノベンゾフェノン、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スルホン、３，４’−ジアミノジフェニルスルホン、４，４’−ジアミノベンゾフェノン、３，４，４’−トリアミノジフェニルスルホン等の芳香族ポリアミン、ｐ−ｔ−ブチルフェノールやビスフェノールＡ骨格、パラフェニレン骨格、ビフェニル骨格等のノボラックフェノール樹脂、ビスフェノールＡなどのビスフェノール化合物等が使用できる。この中でも耐熱性に優れることからフェノール系の硬化剤が好ましい。また溶融性のコントロール等からこれらを単独または２種以上用いることが出来る。更には酸無水物なども使用できる。 The adhesive contains a curing agent that crosslinks with an epoxy group. By containing a curing agent that undergoes a curing reaction with the epoxy resin, the hardness and heat resistance after curing are improved. Examples of curing agents include 3,3 ′, 5,5′-tetramethyl-4,4′-diaminodiphenylmethane, 3,3 ′, 5,5′-tetraethyl-4,4′-diaminodiphenylmethane, 3 , 3'-dimethyl-5,5'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dichloro-4,4'-diaminodiphenylmethane, 2,2 ', 3,3'-tetrachloro-4 , 4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminobenzophenone, 3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone Aromatic polyamines such as 4,4′-diaminobenzophenone, 3,4,4′-triaminodiphenylsulfone, pt-butylphenol Nord, bisphenol A skeleton, paraphenylene skeleton, novolak phenolic resins such as biphenyl skeleton, bisphenol compounds such as bisphenol A can be used. Of these, phenolic curing agents are preferred because of their excellent heat resistance. These can be used alone or in combination of two or more for controlling the meltability. Furthermore, an acid anhydride or the like can also be used.
またポリイミド樹脂にシリコーン骨格を含まない場合には、特にシリコーン骨格の硬化剤を使用する事で、可撓性、低溶融粘度化などが可能になる。
シリコーン骨格の硬化剤としては、主鎖にジメチルシロキサン骨格を有し、側鎖や両末端にアミン、フェノール、カルボキシル基を有する変性シリコーンが使用できる。例えば信越化学の両末端アミンのＫＦ８０１０、ＫＦ８０１２、フェノール変性のＸ−２２−１８２１、両末端カルボキシル変性のＸ−２２−６２ｃ等が使用できる。
一方ポリアミドアミンなども可撓性を付与し、またエポキシ樹脂の硬化剤として使用されるが、本願発明においては、熱劣化等の点から好ましくは使用されない。
また、硬化速度をコントロールする目的等によりイミダゾール類、ジアミン類、トリフェニルホスフィン類の促進剤、触媒を使用する事もできる。
When the polyimide resin does not contain a silicone skeleton, flexibility and low melt viscosity can be achieved by using a silicone skeleton curing agent.
As the curing agent for the silicone skeleton, a modified silicone having a dimethylsiloxane skeleton in the main chain and having an amine, phenol, or carboxyl group in the side chain or both ends can be used. For example, Shin-Etsu Chemical's both terminal amines KF8010 and KF8012, phenol-modified X-22-1821, both-terminal carboxyl-modified X-22-62c, and the like can be used.
On the other hand, polyamidoamine or the like imparts flexibility and is used as a curing agent for epoxy resins, but is not preferably used in the present invention from the viewpoint of thermal degradation or the like.
Further, imidazoles, diamines, triphenylphosphine accelerators and catalysts may be used for the purpose of controlling the curing rate.
本発明の接着剤には熱伝導性充填材を含有することが必要である。
熱伝導性充填材としては、酸化珪素（シリカ）、酸化アルミ（アルミナ）、窒化珪素、窒化アルミ、窒化ホウ素、炭化珪素、酸化マグネシウム、水酸化マグネシウムなどの金属酸化物、金属水酸化物が使用できる。好ましくは絶縁性の観点から、酸化アルミ（アルミナ）、窒化珪素、窒化アルミ、窒化ホウ素である。
また、熱伝導性充填材としては、絶縁性が要求されず、耐熱性が必要であり、かつ熱伝導性が必要な場合には、ステンレス繊維、炭化珪素、銀、金などの金属微粒子、繊維などが適用できる。
The adhesive of the present invention needs to contain a heat conductive filler.
As the thermally conductive filler, silicon oxide (silica), aluminum oxide (alumina), silicon nitride, aluminum nitride, boron nitride, silicon carbide, magnesium oxide, magnesium hydroxide, and other metal oxides and metal hydroxides are used. it can. From the viewpoint of insulation, aluminum oxide (alumina), silicon nitride, aluminum nitride, and boron nitride are preferable.
In addition, as the heat conductive filler, insulation is not required, heat resistance is required, and when heat conductivity is required, metal fine particles such as stainless fiber, silicon carbide, silver, and gold, fibers Etc. are applicable.
熱伝導性充填材の添加量としては、接着剤中の体積比率は必要な熱伝導性の観点から、４０体積％以上が好ましい。また接着性の観点、また熱溶融性の観点から、７０体積％以下が好ましく、熱伝導性、耐絶縁破壊の両立が可能になる。
形状としては、破砕による不定形の微粒子、球状、板状、球状などが適用できるが、比表面積が大きいと充填量を高くすることが難しく、球状が望ましい。また細密充填の為に、粒径や形状の異なる複数の微粒子を使用する事で、より熱伝導性を高めることが可能になる。
たとえば、球状のアルミナ粒子において、平均粒径１０μｍと３μｍを併用し、大きい粒子系の無機充填材中に占める割合を５０％以上にする事で、より高い熱伝導率が得られる。また球状のアルミナ粒子とりんペン状の窒化ホウ素を併用することも出来る。
熱伝導性充填材同士の隙間に粒径の小さなもしくは、または形状の異なる充填材が充填される事により充填率が向上する事により熱伝導率は高くなる。
As the addition amount of the heat conductive filler, the volume ratio in the adhesive is preferably 40% by volume or more from the viewpoint of necessary heat conductivity. Further, from the viewpoint of adhesiveness and from the viewpoint of heat melting property, 70% by volume or less is preferable, and both heat conductivity and resistance to dielectric breakdown can be achieved.
As the shape, irregularly shaped fine particles obtained by crushing, spherical shape, plate shape, spherical shape and the like can be applied. However, when the specific surface area is large, it is difficult to increase the filling amount, and spherical shape is desirable. Further, by using a plurality of fine particles having different particle diameters and shapes for dense packing, it is possible to further improve the thermal conductivity.
For example, in the case of spherical alumina particles, an average particle size of 10 μm and 3 μm is used in combination, and the proportion of the large particle-based inorganic filler is 50% or more, so that higher thermal conductivity can be obtained. Spherical alumina particles and phosphorus pen-like boron nitride can also be used in combination.
By filling the gaps between the thermally conductive fillers with fillers having a small particle size or different shapes, the filling rate is improved and the thermal conductivity is increased.
また、本発明の接着剤をシート化して熱伝導性熱硬化型接着剤シート（以下、単に接着剤シートともいう）とした場合、熱伝導性充填材の最大粒径は、接着剤シートの厚さの１／２以下であることが好ましい。熱伝導性充填材は、絶縁破壊電圧が低く、また破壊は局部的に最弱点において発生する事から、接着剤シート中で、充填材の部位が厚さの半分以上を占めた時に絶縁破壊電圧の極端な低下を引き起こす場合がある。熱伝導性充填材の最大粒径が接着剤シートの厚さの１／２以下である場合では、微粒子間に絶縁樹脂が存在することで、個々の粒子が破壊をされても、有機樹脂によりブロックされることで、絶縁耐圧の極端な低下を引き起こさない。 Further, when the adhesive of the present invention is made into a sheet to form a heat conductive thermosetting adhesive sheet (hereinafter also simply referred to as an adhesive sheet), the maximum particle size of the heat conductive filler is the thickness of the adhesive sheet. It is preferable that it is 1/2 or less. Thermally conductive fillers have a low dielectric breakdown voltage, and the breakdown occurs locally at the weakest point. Therefore, the dielectric breakdown voltage when the filler part occupies more than half of the thickness in the adhesive sheet. May cause an extreme decrease in When the maximum particle size of the thermally conductive filler is ½ or less of the thickness of the adhesive sheet, the presence of the insulating resin between the fine particles allows the organic resin to break down even if the individual particles are destroyed. Blocking does not cause an extreme decrease in dielectric strength.
熱伝導性充填材は、シランカップリング剤で表面処理することが好ましい。表面処理を施すことで、熱伝導性充填材が接着剤中により均一に分散し、また樹脂と接着剤の界面の密着を向上することにより、接着剤としての強度が向上するなどの効果が得られる。また電子部品の実装における半田耐熱性の向上、樹脂の凝集破壊性の向上、しいては接着性の向上などが期待できる。 The thermally conductive filler is preferably surface treated with a silane coupling agent. By applying the surface treatment, the heat conductive filler is more evenly dispersed in the adhesive, and by improving the adhesion at the interface between the resin and the adhesive, the strength as an adhesive is improved. It is done. In addition, it can be expected to improve solder heat resistance, improve resin cohesiveness, and improve adhesiveness in mounting electronic components.
シラカップリング剤としてはエポキシシラン、アミノシラン、ビニルシラン、アクリルシラン等適宜使用できる。具体的にはビニルトリメトキシシラン、ビニルトリエトキシシラン、２−(３，４−エポキシシクロヘキシル)エチルトリメトキシシラン、３−グリシドキシプロピルメチルジメトキシシラン、３−グリシドキシプロピルトリメトキシシラン、３−グリシドキシプロピルメチルジエトキシシラン、３−グリシドキシプロピルトリエトキシシラン、Ｎ−２−（アミノエチル）−３−アミノプロピルメチルジメトキシシラン、Ｎ−２−（アミノエチル）−３−アミノプロピルトリメトキシシラン、Ｎ−２−（アミノエチル）−３−アミノプロピルトリエトキシシラン、３−アミノプロピルトリメトキシシラン、３−アミノプロピルトリエトキシシラン、３−トリエトキシシリル−Ｎ−（１，３−ジメチル-ブチリデン）プロピルアミン、Ｎ−フェニル−３−アミノプロピルトリメトキシシランなどである。 As the sila coupling agent, epoxy silane, amino silane, vinyl silane, acrylic silane and the like can be used as appropriate. Specifically, vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3 -Glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyl Trimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3- Dimethyl-butylidene) propylamine, N-phenyl 3-aminopropyltrimethoxysilane, and the like.
処理に使用する量は、熱伝導性充填材１００質量部に対して、０．２〜１質量部である。
また熱伝導性充填材に処理せずに、接着剤中に添加することも出来る。その場合は、熱伝導性充填材を含めた接着剤中の０．１５〜０．８質量％程度が望ましい。
本発明において平均粒径とは、粒度分布計で粒度分布を測定し、累積分布をパーセント（％）で表した時の５０％に相当する粒子径（メジアン径）をいう。粒子が球状でない場合には球相当体積を基準とした粒度分布を測定する。
The quantity used for a process is 0.2-1 mass part with respect to 100 mass parts of heat conductive fillers.
Moreover, it can also add to an adhesive agent, without processing to a heat conductive filler. In that case, about 0.15-0.8 mass% in the adhesive agent containing a heat conductive filler is desirable.
In the present invention, the average particle diameter means a particle diameter (median diameter) corresponding to 50% when the particle size distribution is measured with a particle size distribution meter and the cumulative distribution is expressed in percent (%). When the particles are not spherical, the particle size distribution based on the sphere equivalent volume is measured.
また接着剤中の樹脂成分とのぬれ性、接着性向上や特性向上の為に熱伝導性充填材に表面処理を施すことも有用である。
表面処理としては、酸化膜処理、上記カップリング処理、チタネート系カップリング処理等があげられる。例えば窒化アルミの場合にはプレッシャークッカー試験の条件（例えば１２１℃１００％ＲＨ２．１ａｔｍ）に暴露されると、アンモニアが発生する。アンモニアは半導体パッケージ等においては好まれない物質であり、例えばシリカによる表面被覆することで、アンモニアの発生を抑制することが出来る。
It is also useful to subject the thermally conductive filler to a surface treatment in order to improve the wettability with the resin component in the adhesive, the adhesiveness, and the characteristics.
Examples of the surface treatment include oxide film treatment, the above-described coupling treatment, titanate coupling treatment, and the like. For example, in the case of aluminum nitride, ammonia is generated when exposed to pressure cooker test conditions (for example, 121 ° C. and 100% RH 2.1 atm). Ammonia is an unfavorable substance in semiconductor packages and the like, and the generation of ammonia can be suppressed by, for example, surface coating with silica.
以上のように接着剤の樹脂分の組成としては、ポリイミド樹脂、エポキシ樹脂、硬化剤を含む接着剤成分のいずれかにシリコーン骨格を含有することが必要である。
シリコーン骨格を含有しないポリイミド樹脂と芳香族系のエポキシ樹脂や、ノボラックフェノールの組み合わせ、シリコーン骨格を含有しないポリイミド樹脂とシリコーン骨格を有するエポキシ樹脂と芳香族系のフェノールの組み合わせ、更にはシリコーン骨格を含有しないポリイミド樹脂とシリコーン骨格を有しないエポキシ樹脂とシリコーン骨格を含有するシリコーンジアミンの組み合わせ等が使用できる。
シリコーン骨格は溶融性を付与する点、また熱伝導性充填材を多量に添加する上において有効である。接着剤の溶融性は加工する上では重要な特性であり、特に熱伝導性充填材の比率が高くなると、みかけの溶融性が極端に高温化する為、例えば金属板への積層等においては高温での積層が必要となり、歪の問題などがある。また熱硬化時における吸湿水分の揮発、積層した界面での泡の巻き込みが原因となる発泡、更には積層による界面の濡れ性の点(結果的に濡れ性がわるいことによる界面での熱抵抗の発生)から、硬化前のＢステージの溶融粘度としては、加熱時の接着剤の溶融粘度曲線において、常温付近からの測定において、粘度が低下し、加温にしたがい、粘度が上昇するポイントが発生する。これは硬化反応が起きることによるものであり、接着剤の硬化挙動をはかる上で重要な情報となる。つまり、この下限の温度が極端に低い温度域にあることは、硬化速度が極めてはやいことを意味し、プレス機などによる積層加工が非常に難しくなることを意味する。
As described above, the composition of the resin component of the adhesive needs to contain a silicone skeleton in any of the adhesive components including a polyimide resin, an epoxy resin, and a curing agent.
Polyimide resin not containing a silicone skeleton and an aromatic epoxy resin, or a combination of novolac phenol, a polyimide resin not containing a silicone skeleton, a combination of an epoxy resin having a silicone skeleton and an aromatic phenol, and a silicone skeleton A combination of a polyimide resin that does not, an epoxy resin that does not have a silicone skeleton, and a silicone diamine that contains a silicone skeleton can be used.
The silicone skeleton is effective in imparting meltability and adding a large amount of a heat conductive filler. The meltability of the adhesive is an important characteristic for processing. Especially when the ratio of the thermally conductive filler is increased, the apparent meltability becomes extremely high. For example, in the lamination to a metal plate, the temperature is high. Therefore, there is a problem of distortion. In addition, the moisture caused by volatilization of moisture at the time of thermosetting, foaming due to entrainment of bubbles at the laminated interface, and the wettability of the interface due to lamination (as a result of the thermal resistance at the interface due to poor wettability) As for the melt viscosity of the B stage before curing, in the melt viscosity curve of the adhesive at the time of heating, in the measurement from around room temperature, the viscosity decreases and the point where the viscosity increases as the temperature is increased occurs. To do. This is due to the occurrence of a curing reaction and is important information for measuring the curing behavior of the adhesive. That is, the fact that the lower limit temperature is in an extremely low temperature range means that the curing rate is extremely fast, and that lamination processing by a press or the like becomes very difficult.
またこのポイントが高い温度域にあると、その温度域までは硬化が遅いこと及び、積層する加工温度が極めて高いことを意味することから、積層する過程で、樹脂分からの脱湿による発泡の問題等、積層時の被着体がひずむなどの問題を生じやすくする。また下限の粘度については、積層加工する際には被着体の凹凸への追従性の点ではよいが、粘度が低すぎると上記のように、吸湿分の脱湿に対して抗しきれずに泡になる可能性があることから最低粘度も重要な特性となる。そのような点から、図１に示す接着剤の溶融粘度曲線において、粘度の最下限値Ａが温度１２０〜２３０℃の範囲に存在し、且つ最下限値の粘度が２００００ｐｏｉｓｅ以上であることが望ましい。 Also, if this point is in a high temperature range, it means that the curing is slow up to that temperature range and the processing temperature to be laminated is extremely high, so the problem of foaming due to dehumidification from the resin component during the lamination process Such a problem that the adherend at the time of stacking is distorted easily occurs. As for the lower limit viscosity, it is good in terms of following the unevenness of the adherend when laminating, but if the viscosity is too low, as described above, it can not resist dehumidification of moisture absorption. Minimum viscosity is also an important property because it can become foam. From such a point, in the melt viscosity curve of the adhesive shown in FIG. 1, it is desirable that the minimum viscosity value A exists in the temperature range of 120 to 230 ° C., and the minimum viscosity value is 20000 poise or more. .
このような溶融粘度を得るには、前記記載のポリイミド樹脂、エポキシ樹脂、硬化剤の組成物が好適に用いられ、且つ促進剤、触媒による硬化速度の調整や接着剤を所定温度で長時間の熱処理（エージング）する事で反応状態をコントロールすることなどにより、適切な溶融粘度を得る事が出来る。溶融粘度の測定は英弘精機社製レオメータＲＳを用い、周波数１Ｈｚ、昇温速度１０℃／ｍｉｎにて測定して得られる。 In order to obtain such a melt viscosity, the polyimide resin, epoxy resin, and curing agent composition described above is preferably used, and the curing rate is adjusted with an accelerator and a catalyst, and the adhesive is used for a long time at a predetermined temperature. An appropriate melt viscosity can be obtained by controlling the reaction state by heat treatment (aging). The melt viscosity is measured by using a rheometer RS manufactured by Eiko Seiki Co., Ltd., at a frequency of 1 Hz and a heating rate of 10 ° C./min.
本発明の接着剤は、シート化して接着剤シートとすることができる。接着剤シートの厚さは１０〜２００μｍ、好ましくは３０〜１００μｍである。熱伝導の点では被着体の表面の凹凸を吸収できる厚さであれば、なるべく薄いほうが好ましいが、一方で、銅箔などの粗面を有する場合には、その凹凸により接着剤の実効厚さが薄くなり、絶縁破壊特性の低下などもあり、上記厚さが望ましい。また厚さが薄い場合には、それに適した熱伝導性充填材の選択が必要になる。必要とする接着剤シートが厚い場合には、複数の接着剤シートを積層して得てもよく、また一度に形成してもかまわない。一度に形成する場合には残留溶剤が多くなる傾向にあり、積層した後接着剤硬化処理時の泡の発生などの可能性があり、残留溶剤としては、１００ｐｐｍ以下が望ましく、更に望ましくは５０ｐｐｍ以下である。
特に金属同士の接着に用いる場合には、揮発する残留溶剤が逃げることが出来ずに、発泡する可能性がある。接着剤シートとしての可撓性を得る為に残留溶剤を意図的に数％等残留させる場合があるが残留溶剤を保持することは難しく、好ましくは上記方法は採られない。
The adhesive of the present invention can be made into a sheet by forming a sheet. The thickness of the adhesive sheet is 10 to 200 μm, preferably 30 to 100 μm. In terms of heat conduction, the thickness is preferably as thin as possible as long as it can absorb the unevenness of the surface of the adherend. On the other hand, if it has a rough surface such as copper foil, the effective thickness of the adhesive due to the unevenness. The above thickness is desirable because the thickness is reduced and the dielectric breakdown characteristics are degraded. When the thickness is small, it is necessary to select a heat conductive filler suitable for the thickness. When the required adhesive sheet is thick, it may be obtained by laminating a plurality of adhesive sheets, or may be formed at a time. In the case of forming at one time, the residual solvent tends to increase, and there is a possibility of generation of bubbles during the adhesive curing process after lamination. The residual solvent is preferably 100 ppm or less, more preferably 50 ppm or less. It is.
In particular, when used for bonding metals, the residual solvent that volatilizes cannot escape and foaming may occur. In order to obtain flexibility as an adhesive sheet, there are cases where the residual solvent is intentionally left by several percent, but it is difficult to retain the residual solvent, and the above method is preferably not employed.
接着剤シートの両面もしくは片面には保護フィルムが積層されていていもよい。接着剤の両面に保護フィルムが積層された状態の場合には保護フィルムの剥離力は、両面の保護フィルムで異なることが好ましい。保護フィルムの剥離力は、フィルム除去の際に、接着剤の特性を損なわない程度であれば、特段の値に限定されない。
また、接着剤シートは、少なくとも片面にプラスチックフィルムまたは金属層を有していてもよい。
A protective film may be laminated on both sides or one side of the adhesive sheet. When the protective film is laminated on both sides of the adhesive, the peel strength of the protective film is preferably different between the protective films on both sides. The peeling force of the protective film is not limited to a special value as long as it does not impair the properties of the adhesive during film removal.
The adhesive sheet may have a plastic film or a metal layer on at least one side.
以下本発明に係る実施例及び比較例について説明する。
以下のようにして合成例１〜合成例５にもとづくポリイミド樹脂を作製した。
（合成例１）(シリコーン骨格有り)
撹拌機を備えたフラスコに、２，２−ビス［４−（４−アミノフェノキシ）フェニル］プロパン１７．８ｇ（４３ミリモル）、３，３’−ジカルボキシ−４，４’−ジアミノジフェニルメタン２．３ｇ（９ミリモル）、１，３−ビス（３−アミノフェノキシメチル）−１，１，３，３−テトラメチルジシロキサン１８．３ｇ（４８ミリモル）、３，４，３’，４’−ベンゾフェノンテトラカルボン酸二無水物３２．２２ｇ（１００ミリモル）およびＮ−メチル−２−ピロリドン（ＮＭＰ）３００ｍｌを氷温下導入し、１時間撹拌を続けた。次いで、得られた溶液を窒素雰囲気下、室温で３時間反応させてポリアミック酸を合成した。得られたポリアミック酸溶液に、トルエン５０ｍｌおよびｐ−トルエンスルホン酸１．０ｇを加え、１６０℃に加熱した。トルエンと共沸してきた水を分離しながら３時間イミド化反応を行った。トルエンを留去し、得られたポリイミドワニスをメタノール中に注ぎ、得られた沈殿を分離し、粉砕、洗浄、乾燥させる工程を経ることにより、ポリイミド６２．５ｇ（収率９３％）を得た。このポリイミドについて、赤外吸収スペトルを測定したところ、１７１８および１７８３ｃｍ-1に、典型的なイミドの吸収が認められた。また、その数平均分子量、ガラス転移温度を測定した。それらの結果を表１に示す。
Examples and comparative examples according to the present invention will be described below.
Polyimide resins based on Synthesis Examples 1 to 5 were prepared as follows.
(Synthesis Example 1) (with silicone skeleton)
To a flask equipped with a stirrer, 17.8 g (43 mmol) of 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 3,3′-dicarboxy-4,4′-diaminodiphenylmethane2. 3 g (9 mmol), 1,3-bis (3-aminophenoxymethyl) -1,1,3,3-tetramethyldisiloxane 18.3 g (48 mmol), 3,4,3 ′, 4′-benzophenone Tetracarboxylic dianhydride 32.22 g (100 mmol) and N-methyl-2-pyrrolidone (NMP) 300 ml were introduced under ice temperature, and stirring was continued for 1 hour. Next, the resulting solution was reacted at room temperature for 3 hours under a nitrogen atmosphere to synthesize polyamic acid. To the obtained polyamic acid solution, 50 ml of toluene and 1.0 g of p-toluenesulfonic acid were added and heated to 160 ° C. An imidization reaction was performed for 3 hours while separating water azeotroped with toluene. Toluene was distilled off, and the resulting polyimide varnish was poured into methanol, and the resulting precipitate was separated, pulverized, washed, and dried to obtain 62.5 g of polyimide (yield 93%). . When the infrared absorption spectrum of this polyimide was measured, typical imide absorptions were observed at 1718 and 1783 cm @ -1. Moreover, the number average molecular weight and glass transition temperature were measured. The results are shown in Table 1.
（合成例２）(シリコーン骨格有り)
２，２−ビス［４−（４−アミノフェノキシ）フェニル］プロパン３２．０ｇ（７８ミリモル）、アミノプロピル末端ジメチルシロキサン８量体１７．０ｇ（２２ミリモル）、ビス（３，４−ジカルボキシフェニル）スルホン二無水物３５．８ｇ（１００ミリモル）およびＮ−メチル−２−ピロリドン３００ｍｌを用いて、合成例１と同様の方法でポリイミド７８．７ｇ（収率９７％）を得た。このポリイミドについて、その数平均分子量、ガラス転移温度を測定した。それらの結果を表１に示す。
(Synthesis Example 2) (with silicone skeleton)
2,2-bis [4- (4-aminophenoxy) phenyl] propane 32.0 g (78 mmol), aminopropyl-terminated dimethylsiloxane octamer 17.0 g (22 mmol), bis (3,4-dicarboxyphenyl) ) 78.7 g (yield 97%) of polyimide was obtained in the same manner as in Synthesis Example 1 using 35.8 g (100 mmol) of sulfone dianhydride and 300 ml of N-methyl-2-pyrrolidone. The number average molecular weight and glass transition temperature of this polyimide were measured. The results are shown in Table 1.
（合成例３）(シリコーン骨格有り)
２，２−ビス［４−（４−アミノフェノキシ）フェニル］プロパン３０．４ｇ（７４ミリモル）、３，３’−ジカルボキシ−４，４’−ジアミノジフェニルメタン１．１ｇ（４ミリモル）、アミノプロピル末端ジメチルシロキサン８量体１６．９ｇ（２２ミリモル）、ビス（３，４−ジカルボキシフェニル）スルホン二無水物３５．８３ｇ（１００ミリモル）およびＮ−メチル−２−ピロリドン３００ｍｌを用いて、合成例１と同様の方法で反応性ポリイミド７５．０ｇ（収率９３％）を得た。このポリイミドについて、その数平均分子量、ガラス転移温度を測定した。それらの結果を表１に示す。
(Synthesis example 3) (with silicone skeleton)
3,0.4 g (74 mmol) of 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 1.1 g (4 mmol) of 3,3′-dicarboxy-4,4′-diaminodiphenylmethane, aminopropyl Synthesis example using 16.9 g (22 mmol) of terminal dimethylsiloxane octamer, 35.83 g (100 mmol) of bis (3,4-dicarboxyphenyl) sulfone dianhydride and 300 ml of N-methyl-2-pyrrolidone In the same manner as in Example 1, 75.0 g (yield 93%) of reactive polyimide was obtained. The number average molecular weight and glass transition temperature of this polyimide were measured. The results are shown in Table 1.
（合成例４）(シリコーン骨格有り)
１，３−ビス（３−アミノフェノキシ）ベンゼン２３．６ｇ（８１ミリモル）、３，３’−ジヒドロキシ−４，４’−ジアミノジフェニルメタン２．１ｇ（９ミリモル）、アミノプロピル末端ジメチルシロキサン８量体８．１ｇ（１０ミリモル）、ビス（３，４−ジカルボキシフェニル）エーテル二無水物２０．０ｇ（１００ミリモル）およびＮ−メチル−２−ピロリドン３００ｍｌを用いて、合成例１と同様の方法でポリイミド４５．６ｇ（収率９１％）を得た。このポリイミドについその数平均分子量、ガラス転移温度を測定した。それらの結果を表１に示す。
(Synthesis Example 4) (with silicone skeleton)
1,3-bis (3-aminophenoxy) benzene 23.6 g (81 mmol), 3,3′-dihydroxy-4,4′-diaminodiphenylmethane 2.1 g (9 mmol), aminopropyl-terminated dimethylsiloxane octamer In the same manner as in Synthesis Example 1, 8.1 g (10 mmol), 20.0 g (100 mmol) of bis (3,4-dicarboxyphenyl) ether dianhydride and 300 ml of N-methyl-2-pyrrolidone were used. 45.6 g (yield 91%) of polyimide was obtained. The number average molecular weight and glass transition temperature of this polyimide were measured. The results are shown in Table 1.
（合成例５）(シリコーン骨格なし)
４,４’-メチレンビス（２,６-ジエチルアニリン３．２g(１０ミリモル)、１,３-ビス(３-アミノフェノキシ)ベンゼン１１．７ｇ(４０ミリモル)、４,４’-オキシジフタル酸無水物１５．５ｇ(５０ミリモル)およびＮ−メチル−２−ピロリドン３００ｍｌを用いて、合成例１と同様の方法でポリイミド７８．７ｇ（収率９７％）を得た。このポリイミドについて、その数平均分子量、ガラス転移温度を測定した。それらの結果を表１に示す。
(Synthesis Example 5) (No silicone skeleton)
4,4′-methylenebis (2,6-diethylaniline 3.2 g (10 mmol), 1,3-bis (3-aminophenoxy) benzene 11.7 g (40 mmol), 4,4′-oxydiphthalic anhydride Using 15.5 g (50 mmol) and 300 ml of N-methyl-2-pyrrolidone, 78.7 g (yield 97%) of polyimide was obtained in the same manner as in Synthesis Example 1. About this polyimide, its number average molecular weight The glass transition temperature was measured and the results are shown in Table 1.
次に下記表２及び表３の配合表に基づいて、ポリイミド樹脂、エポキシ樹脂、硬化剤、熱伝導性充填材等を混合して、ビーズミルにより充填材を分散し、実施例２、３の本発明の接着剤組成物、参考例の接着剤組成物及び比較例１〜８の比較用の接着剤組成物を調製した。表２及び表３の配合表における単位は質量部である。
そして、上記接着剤組成物を剥離処理されたポリエステルフィルムに塗布し、乾燥後の厚さが表２及び表３の厚さになるように塗布し、１００℃で１０分間程度乾燥し、本発明の接着剤シート、参考例の接着剤シート及び比較用の接着剤シートを作製した。
上記接着剤シートの溶融粘度曲線における最下限値、該最下限値の粘度について表２及び表３に記した。溶融粘度は、接着剤シートを１ｍｍ厚さまで加熱により積層し、英弘精機社製レオメータＲＳを用い、周波数１Ｈｚ、昇温速度１０℃／ｍｉｎにて測定し、粘度が最小になる温度とそのときの粘度を測定した。
Then, based on the recipe in the following Table 2 and Table 3, polyimide resin, epoxy resin, curing agent, a mixture of thermally conductive filler or the like and dispersing the filler material by a bead mill, the embodiment 2 and 3 The adhesive composition of the invention, the adhesive composition of the reference example, and the comparative adhesive composition of Comparative Examples 1 to 8 were prepared. The units in the recipes in Tables 2 and 3 are parts by mass.
And the said adhesive composition is apply | coated to the polyester film by which the peeling process was carried out, it applied so that the thickness after drying might become the thickness of Table 2 and Table 3, and it dried for about 10 minutes at 100 degreeC, and this invention Adhesive sheet , a reference example adhesive sheet, and a comparative adhesive sheet.
Tables 2 and 3 show the lower limit value and the viscosity of the lower limit value in the melt viscosity curve of the adhesive sheet. The melt viscosity is measured by laminating an adhesive sheet by heating to a thickness of 1 mm, using a rheometer RS manufactured by Eihiro Seiki Co., Ltd., at a frequency of 1 Hz and a temperature increase rate of 10 ° C./min. The viscosity was measured.
次に、上記実施例２、３の本発明の接着剤シート、参考例の接着剤シート及び比較例１〜８の比較用の接着剤シートを用いて次の評価を行った。 Next, the following evaluation was performed using the adhesive sheet of the present invention of Examples 2 and 3 , the adhesive sheet of the reference example, and the comparative adhesive sheet of Comparative Examples 1 to 8.
［絶縁破壊試験］
実施例２、３の接着剤シート、参考例の接着剤シート及び比較例１〜８の接着剤シートに対して硬化処理(常温から１７５℃まで３時間、１７５℃で１時間)を行い評価用の接着剤シートとした。次に該評価用の接着剤シートを温度２５℃、湿度６０％ＲＨの環境条件下に２４時間放置した後、昇圧速度 １ｋＶ／ｓｅｃにて直流電圧を印加し、破壊するまで電圧（破壊電圧）を加えた。絶縁破壊強度として、破壊電圧を厚さで除し、１ｍｍあたりの絶縁破壊電圧（ｋＶ／ｍｍ）を求め、この結果を表４及び表５に記した。
同様に各評価用の接着剤シートの１５０℃での破壊電圧を測定し、その結果を表４及び表５に記した。
次の数式により絶縁破壊電圧の保持率を算出してその結果を表４及び表５に記した。この保持率は５０％以上が実用上使用できるものである。
絶縁破壊電圧の保持率＝（１５０℃における絶縁破壊電圧）／(２５℃における絶縁破壊電圧)×１００［％］
[Dielectric breakdown test]
The adhesive sheets of Examples 2 and 3, the adhesive sheets of Reference Examples and the adhesive sheets of Comparative Examples 1 to 8 were subjected to curing treatment (from room temperature to 175 ° C. for 3 hours and 175 ° C. for 1 hour) for evaluation. This was an adhesive sheet. Next, the adhesive sheet for evaluation was allowed to stand for 24 hours under an environmental condition of a temperature of 25 ° C. and a humidity of 60% RH, and then a DC voltage was applied at a boosting rate of 1 kV / sec until the voltage was broken (breakdown voltage). Was added. As the breakdown strength, the breakdown voltage was divided by the thickness to determine the breakdown voltage (kV / mm) per 1 mm. The results are shown in Tables 4 and 5.
Similarly, the breakdown voltage at 150 ° C. of each adhesive sheet for evaluation was measured, and the results are shown in Tables 4 and 5.
The retention rate of the dielectric breakdown voltage was calculated by the following formula, and the results are shown in Tables 4 and 5. As for this retention rate, 50% or more can be used practically.
Dielectric breakdown voltage retention ratio = (dielectric breakdown voltage at 150 ° C.) / (Dielectric breakdown voltage at 25 ° C.) × 100 [%]
［熱劣化試験］
実施例２、３の接着剤シート、参考例の接着剤シート及び比較例１〜８の接着剤シートを各々ポリイミドフィルム(東レデュポン社製 商品名：カプトン２００ＥＮ ５０μｍ)に1４０℃ １ｍ／ｍｉｎでロールラミネーションにより積層し、次に三井鉱業社製 電解銅箔ＳＱ-ＶＬＰ １２μｍを１６０℃ １ｍ／ｍｉｎにてロールラミネーションし、硬化処理(常温から１７５℃まで３時間、１７５℃で１時間)を行った。次にこの積層体を５ｍｍ幅のパターンに形成して帯状物を得た。
次に、上記帯状物を温度２５℃、湿度６０％ＲＨの環境条件下に２４時間放置した後、初期接着力を測定し、その結果を表４及び表５に記した。初期接着力は、万能引張試験器（テンシロン社製）を用いて、銅箔を接着剤シートに対して角度が９０°になるように剥離する方法で、その時の引張力を測定したものである。接着力は１ｃｍ幅あたりに換算する。
次に上記帯状物を温度１５０℃環境条件下に５００時間放置した後、上記初期接着力と同様な測定方法で接着力を測定し、その結果を表４及び表５に記した。
次の数式により接着力の保持率を算出してその結果を表４及び表５に記した。この保持率は５０％以上が実用上使用できるものである。
接着力の保持率＝（１５０℃放置後の接着力）／(初期接着力)×１００［％］
ここでポリイミドフィルムを使用する目的は、酸化劣化の観点から酸素透過性を有する基材としてポリイミドフィルムを選択し、接着剤の劣化特性を明確にするためである。
[Thermal degradation test]
The adhesive sheets of Examples 2 and 3, the adhesive sheets of Reference Examples and the adhesive sheets of Comparative Examples 1 to 8 were each rolled onto a polyimide film (trade name: Kapton 200EN 50 μm manufactured by Toray DuPont) at 140 ° C. at 1 m / min. Lamination was followed by roll lamination of electrolytic copper foil SQ-VLP 12 μm manufactured by Mitsui Mining Co., Ltd. at 160 ° C. and 1 m / min, followed by curing treatment (from room temperature to 175 ° C. for 3 hours and 175 ° C. for 1 hour). . Next, this laminated body was formed into a pattern having a width of 5 mm to obtain a belt-like product.
Next, the strip was left under environmental conditions of a temperature of 25 ° C. and a humidity of 60% RH for 24 hours, and then the initial adhesive strength was measured. The results are shown in Tables 4 and 5. The initial adhesive strength is a method in which the tensile strength at that time is measured by a method in which the copper foil is peeled off at an angle of 90 ° with respect to the adhesive sheet using a universal tensile tester (manufactured by Tensilon). . The adhesive force is converted per 1 cm width.
Next, the strip was allowed to stand for 500 hours at 150 ° C. and then the adhesive strength was measured by the same measurement method as the initial adhesive strength. The results are shown in Tables 4 and 5.
The retention rate of the adhesive force was calculated by the following formula, and the results are shown in Tables 4 and 5. As for this retention rate, 50% or more can be used practically.
Adhesive strength retention rate = (adhesive strength after standing at 150 ° C.) / (Initial adhesive strength) × 100 [%]
The purpose of using the polyimide film here is to select the polyimide film as a base material having oxygen permeability from the viewpoint of oxidative deterioration, and to clarify the deterioration characteristics of the adhesive.
［熱伝導率測定］
実施例２、３の接着剤シート、参考例の接着剤シート及び比較例１〜８の接着剤シートを１ｍｍ厚さまで加熱により積層し、硬化処理(常温から１７５℃まで３時間、１７５℃で１時間)を行った。
次にアルバック理工株式会社製の熱定数測定装置により熱拡散率を測定した。アルキメデス法により接着剤の密度を測定し、ＤＳＣ法により比熱を測定し、これらから熱伝導率を算出し、その結果を表４及び表５に記した。
通常の有機樹脂が０．１から０．２２ｗ／ｍ・ｋであり、熱伝導率としては０．６ｗ／ｍ・ｋ以上であれば、熱伝導性の絶縁接着剤といえる。
[Thermal conductivity measurement]
The adhesive sheets of Examples 2 and 3, the adhesive sheets of Reference Examples and the adhesive sheets of Comparative Examples 1 to 8 were laminated by heating to a thickness of 1 mm and cured (from room temperature to 175 ° C. for 3 hours at 175 ° C. for 1 hour. Time).
Next, the thermal diffusivity was measured with a thermal constant measuring device manufactured by ULVAC-RIKO. The density of the adhesive was measured by the Archimedes method, the specific heat was measured by the DSC method, the thermal conductivity was calculated from these, and the results are shown in Tables 4 and 5.
If the normal organic resin is 0.1 to 0.22 w / m · k and the thermal conductivity is 0.6 w / m · k or more, it can be said to be a thermally conductive insulating adhesive.
［フィルム性評価］
実施例２、３の接着剤シート、参考例の接着剤シート及び比較例１〜８の接着剤シートを１ｍｍ厚さまで加熱により積層した。積層時の加熱による接着剤シートの硬化度への影響はない。この硬化処理していない積層された接着シートの端を固定した後、該接着シートを９０度折り曲げた。折り曲げした際に接着剤に亀裂が生じなければ○、亀裂が生じたものを×とした。その結果を表４及び表５に記した。
[Film evaluation]
The adhesive sheets of Examples 2 and 3, the adhesive sheets of Reference Examples, and the adhesive sheets of Comparative Examples 1 to 8 were laminated to a thickness of 1 mm by heating. There is no effect on the degree of cure of the adhesive sheet by heating during lamination. After fixing the ends of the laminated adhesive sheets that were not cured, the adhesive sheets were bent 90 degrees. When the adhesive was not cracked when bent, it was rated as “◯”, and the cracked material was marked as “X”. The results are shown in Tables 4 and 5.
［加工性評価］
北側精機の成形プレス ＫＶＨＣ−ＰＲＥＳＳを用いて、銅箔とアルミ板の間に硬化処理していない実施例２、３の接着剤シート、参考例の接着剤シート及び比較例１〜８の接着剤シートを各々挿入し、真空下で圧着し、２５℃から２００℃まで３℃／ｍｉｎで昇温後、２００℃３０ｍｉｎ保持し、プレスした。
プレス後、泡の発生、銅箔への埋まり込みを目視により確認した。泡が生じないで銅箔に埋まり込んだものを○、泡が生じるか、もしくは銅箔に埋まり込まないものは×とした。その結果を表４及び表５に記した。
[Processability evaluation]
Using the molding press KVHC-PRESS of Kita Seiki, the adhesive sheets of Examples 2 and 3 that were not cured between the copper foil and the aluminum plate, the adhesive sheets of the reference examples, and the adhesive sheets of Comparative Examples 1 to 8 Each was inserted, pressure-bonded under vacuum, heated from 25 ° C. to 200 ° C. at 3 ° C./min, held at 200 ° C. for 30 min, and pressed.
After pressing, the generation of bubbles and the embedding in the copper foil were confirmed visually. Those in which bubbles were not embedded and embedded in the copper foil were marked with ◯, and those in which bubbles were generated or not embedded in the copper foil were marked with ×. The results are shown in Tables 4 and 5.
表から明らかのように、本発明により得られた接着剤シートは熱伝導率が高く、比較用の接着シートと比較し、脆さ等が改善されフィルム性評価が良好であり、絶縁破壊の温度依存性が小さく、また高温に放置した際の熱劣化が小さく、また積層加工時の泡などの問題もすくなく、且つ従来より比較的薄い膜厚の熱伝導性の接着剤シートが得られる。 As is clear from the table, the adhesive sheet obtained by the present invention has a high thermal conductivity, the brittleness is improved and the film property evaluation is good compared to the comparative adhesive sheet, and the dielectric breakdown temperature. The dependence is small, the thermal degradation when left at high temperature is small, and there are few problems such as bubbles at the time of lamination processing, and a heat conductive adhesive sheet having a relatively thin film thickness can be obtained.
Ａ 最下限値 A Lower limit
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| JP6487829B2 (en) * | 2015-11-20 | 2019-03-20 | 株式会社巴川製紙所 | Thermally conductive thermosetting adhesive composition and thermally conductive thermosetting adhesive sheet |
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| JP3063935B2 (en) * | 1992-05-12 | 2000-07-12 | 宇部興産株式会社 | Polyimide siloxane composition having adhesiveness, heat resistance and curl resistance |
| JP5293496B2 (en) * | 2000-11-28 | 2013-09-18 | 日立化成株式会社 | Adhesive composition, adhesive film, and semiconductor device |
| WO2008143253A1 (en) * | 2007-05-21 | 2008-11-27 | Hitachi Chemical Company, Ltd. | Adhesive composition and adhesive film using the same |
| JP2009084563A (en) * | 2007-09-13 | 2009-04-23 | Hitachi Chem Co Ltd | Adhesive composition, film adhesive, adhesion sheet, and semiconductor device |
| JP5180684B2 (en) * | 2008-06-02 | 2013-04-10 | 新日鉄住金化学株式会社 | Coverlay film |
| JP2011195674A (en) * | 2010-03-18 | 2011-10-06 | Sekisui Chem Co Ltd | Self-adhesive sheet and method for producing laminate |
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