JP6517034B2 - Resin composition, film, substrate, semiconductor device, adhesive for thermal transfer roll, and office equipment - Google Patents
Resin composition, film, substrate, semiconductor device, adhesive for thermal transfer roll, and office equipment Download PDFInfo
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- JP6517034B2 JP6517034B2 JP2015024846A JP2015024846A JP6517034B2 JP 6517034 B2 JP6517034 B2 JP 6517034B2 JP 2015024846 A JP2015024846 A JP 2015024846A JP 2015024846 A JP2015024846 A JP 2015024846A JP 6517034 B2 JP6517034 B2 JP 6517034B2
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- 239000011342 resin composition Substances 0.000 title claims description 49
- 239000000853 adhesive Substances 0.000 title claims description 35
- 230000001070 adhesive effect Effects 0.000 title claims description 34
- 239000000758 substrate Substances 0.000 title claims description 16
- 239000004065 semiconductor Substances 0.000 title claims description 7
- 239000010408 film Substances 0.000 title 1
- 239000007788 liquid Substances 0.000 claims description 25
- 239000003822 epoxy resin Substances 0.000 claims description 21
- 229920000647 polyepoxide Polymers 0.000 claims description 21
- 150000003949 imides Chemical class 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 7
- 125000004018 acid anhydride group Chemical group 0.000 claims description 6
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 6
- 239000004593 Epoxy Substances 0.000 claims description 5
- 239000000463 material Substances 0.000 claims 2
- 239000011248 coating agent Substances 0.000 description 16
- 238000000576 coating method Methods 0.000 description 16
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 11
- 239000002966 varnish Substances 0.000 description 11
- -1 imide siloxane Chemical class 0.000 description 10
- 238000011156 evaluation Methods 0.000 description 9
- 239000000126 substance Substances 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 229920001721 polyimide Polymers 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 6
- 239000002585 base Substances 0.000 description 5
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 5
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 description 5
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 150000008065 acid anhydrides Chemical class 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 235000010290 biphenyl Nutrition 0.000 description 3
- 239000004305 biphenyl Substances 0.000 description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 3
- 150000002430 hydrocarbons Chemical group 0.000 description 3
- 229920003986 novolac Polymers 0.000 description 3
- 239000004843 novolac epoxy resin Substances 0.000 description 3
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 2
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 2
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-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
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 239000004842 bisphenol F epoxy resin Substances 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920003192 poly(bis maleimide) Polymers 0.000 description 2
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- LTVUCOSIZFEASK-MPXCPUAZSA-N (3ar,4s,7r,7as)-3a-methyl-3a,4,7,7a-tetrahydro-4,7-methano-2-benzofuran-1,3-dione Chemical compound C([C@H]1C=C2)[C@H]2[C@H]2[C@]1(C)C(=O)OC2=O LTVUCOSIZFEASK-MPXCPUAZSA-N 0.000 description 1
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 1
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical class C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- SSUJUUNLZQVZMO-UHFFFAOYSA-N 1,2,3,4,8,9,10,10a-octahydropyrimido[1,2-a]azepine Chemical compound C1CCC=CN2CCCNC21 SSUJUUNLZQVZMO-UHFFFAOYSA-N 0.000 description 1
- JNPCNDJVEUEFBO-UHFFFAOYSA-N 1-butylpyrrole-2,5-dione Chemical compound CCCCN1C(=O)C=CC1=O JNPCNDJVEUEFBO-UHFFFAOYSA-N 0.000 description 1
- BQTPKSBXMONSJI-UHFFFAOYSA-N 1-cyclohexylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1CCCCC1 BQTPKSBXMONSJI-UHFFFAOYSA-N 0.000 description 1
- NQDOCLXQTQYUDH-UHFFFAOYSA-N 1-propan-2-ylpyrrole-2,5-dione Chemical compound CC(C)N1C(=O)C=CC1=O NQDOCLXQTQYUDH-UHFFFAOYSA-N 0.000 description 1
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical group ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- QCBSYPYHCJMQGB-UHFFFAOYSA-N 2-ethyl-1,3,5-triazine Chemical compound CCC1=NC=NC=N1 QCBSYPYHCJMQGB-UHFFFAOYSA-N 0.000 description 1
- YTWBFUCJVWKCCK-UHFFFAOYSA-N 2-heptadecyl-1h-imidazole Chemical compound CCCCCCCCCCCCCCCCCC1=NC=CN1 YTWBFUCJVWKCCK-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical compound C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 description 1
- LLEASVZEQBICSN-UHFFFAOYSA-N 2-undecyl-1h-imidazole Chemical compound CCCCCCCCCCCC1=NC=CN1 LLEASVZEQBICSN-UHFFFAOYSA-N 0.000 description 1
- UIDDPPKZYZTEGS-UHFFFAOYSA-N 3-(2-ethyl-4-methylimidazol-1-yl)propanenitrile Chemical compound CCC1=NC(C)=CN1CCC#N UIDDPPKZYZTEGS-UHFFFAOYSA-N 0.000 description 1
- TYOXIFXYEIILLY-UHFFFAOYSA-N 5-methyl-2-phenyl-1h-imidazole Chemical compound N1C(C)=CN=C1C1=CC=CC=C1 TYOXIFXYEIILLY-UHFFFAOYSA-N 0.000 description 1
- MWSKJDNQKGCKPA-UHFFFAOYSA-N 6-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CC(C)=CC2C(=O)OC(=O)C12 MWSKJDNQKGCKPA-UHFFFAOYSA-N 0.000 description 1
- GOYGTBXFJBGGLI-UHFFFAOYSA-N 7a-but-1-enyl-3a-methyl-4,5-dihydro-2-benzofuran-1,3-dione Chemical compound C1=CCCC2(C)C(=O)OC(=O)C21C=CCC GOYGTBXFJBGGLI-UHFFFAOYSA-N 0.000 description 1
- GSXOWIRCKMSAQK-UHFFFAOYSA-N CC(C)(CC(CC)C)C.C1(C=CC(N1)=O)=O Chemical compound CC(C)(CC(CC)C)C.C1(C=CC(N1)=O)=O GSXOWIRCKMSAQK-UHFFFAOYSA-N 0.000 description 1
- 241000202785 Calyptronoma Species 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- GHAZCVNUKKZTLG-UHFFFAOYSA-N N-ethyl-succinimide Natural products CCN1C(=O)CCC1=O GHAZCVNUKKZTLG-UHFFFAOYSA-N 0.000 description 1
- HDFGOPSGAURCEO-UHFFFAOYSA-N N-ethylmaleimide Chemical compound CCN1C(=O)C=CC1=O HDFGOPSGAURCEO-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 150000008064 anhydrides Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- VANNPISTIUFMLH-UHFFFAOYSA-N glutaric anhydride Chemical compound O=C1CCCC(=O)O1 VANNPISTIUFMLH-UHFFFAOYSA-N 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 description 1
- SEEYREPSKCQBBF-UHFFFAOYSA-N n-methylmaleimide Chemical compound CN1C(=O)C=CC1=O SEEYREPSKCQBBF-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- IUURMAINMLIZMX-UHFFFAOYSA-N tris(2-nonylphenyl)phosphane Chemical compound CCCCCCCCCC1=CC=CC=C1P(C=1C(=CC=CC=1)CCCCCCCCC)C1=CC=CC=C1CCCCCCCCC IUURMAINMLIZMX-UHFFFAOYSA-N 0.000 description 1
- WXAZIUYTQHYBFW-UHFFFAOYSA-N tris(4-methylphenyl)phosphane Chemical compound C1=CC(C)=CC=C1P(C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 WXAZIUYTQHYBFW-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Epoxy Resins (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Manufacturing Of Printed Wiring (AREA)
- Adhesive Tapes (AREA)
Description
本発明は、樹脂組成物、フィルム、これらの樹脂組成物またはフィルムから形成される基板、および半導体装置、ならびに熱転写ロール用接着材、および樹脂組成物または熱転写ロール用接着材から形成される事務機器に関する。 The present invention relates to a resin composition, a film, a substrate formed from the resin composition or film thereof, a semiconductor device, an adhesive for a thermal transfer roll, and an office device formed from the resin composition or the adhesive for a thermal transfer roll About.
一般に、電子機器は、小型化・高性能化が進み、用いられる部品の集積度が高まってきている。このため、部品からの発熱を考慮した熱設計への重要度が一層増してきている。また、自動車などのエンジン周りでの部品の動作環境は、より一層高温にさらされる様になってきている。接着剤についても、こうした高温（例えば、１００〜１２５℃）環境下で安定した接着性を保持することは、以前から必要とされていた。近年、さらに高温（例えば、１２５〜２００℃）環境下での接着力安定性が、要求されてきている。一方、液状の接着剤の作業性を改善するため、作業性の良いフィルム状接着剤が要求されている。フィルム状接着剤としては、以下が報告されている。 In general, electronic devices are becoming smaller and more sophisticated, and the degree of integration of components used is increasing. For this reason, the importance of thermal design in consideration of heat generation from parts has further increased. In addition, the operating environment of parts around an engine such as a car is becoming more and more exposed to high temperatures. Also for adhesives, maintaining stable adhesion under such high temperature (e.g., 100-125 [deg.] C.) environment has been previously required. In recent years, adhesive stability under high temperature (for example, 125 to 200 ° C.) environment has been required. On the other hand, in order to improve the workability of a liquid adhesive, a film adhesive having good workability is required. The following is reported as a film adhesive.
まず、所定のイミドオリゴマーと、エポキシ樹脂を含有する熱硬化性樹脂組成物が、支持ベースフィルム上に積層されていることを特徴とする多層プリント配線板用ボンディングシートが報告されている（特許文献１）。しかしながら、このボンディングシートは、イミドオリゴマーが柔軟性に乏しい、イミドオリゴマーの末端がカルボン酸であるので、熱硬化性樹脂組成物のポットライフやボンディングシートのシェルフライフが短い、という問題がある。 First, there has been reported a bonding sheet for a multilayer printed wiring board, characterized in that a thermosetting resin composition containing a predetermined imide oligomer and an epoxy resin is laminated on a supporting base film (patent document) 1). However, this bonding sheet has a problem that the pot life of the thermosetting resin composition and the shelf life of the bonding sheet are short because the imide oligomer is poor in flexibility and the terminal of the imide oligomer is a carboxylic acid.
また、所定の芳香族ポリイミド、所定の末端変性イミドシロキサンオリゴマー、所定のエポキシ樹脂、エポキシ硬化剤が、含有されている耐熱性接着剤組成物も報告されている（特許文献２）。しかしながら、この耐熱性接着剤組成物は、イミドオリゴマーが柔軟性に乏しい、耐熱性接着剤組成物の微細配線等の凹凸への埋め込み性に劣る、という問題がある。 In addition, a heat-resistant adhesive composition in which a predetermined aromatic polyimide, a predetermined terminal-modified imide siloxane oligomer, a predetermined epoxy resin, and an epoxy curing agent are contained has also been reported (Patent Document 2). However, this heat-resistant adhesive composition has a problem that the imide oligomer is poor in flexibility, and the heat-resistant adhesive composition has poor embeddability in the unevenness of fine wiring and the like.
本発明は、上記問題点を解決することを目的とする。すなわち、ワニスにしたときの安定性が高く、塗膜性状がよい樹脂組成物であり、かつ硬化後の接着強度、特に高温保持後にも接着強度を維持できる樹脂組成物を提供することを目的とする。 An object of the present invention is to solve the above-mentioned problems. That is, the object is to provide a resin composition which is high in stability when made into a varnish and has good coating film properties, and which can maintain adhesive strength after curing, particularly after holding at high temperature. Do.
本発明は、以下の構成を有することによって上記問題を解決した樹脂組成物、フィルム、基板、半導体装置、熱転写ロール用接着材、および事務機器である。
〔１〕（Ａ）２５℃で液状であるエポキシ樹脂、
（Ｂ）式（１）：
The present invention is a resin composition, a film, a substrate, a semiconductor device, an adhesive for a thermal transfer roll, and an office equipment which solve the above problems by having the following constitution.
[1] (A) Epoxy resin which is liquid at 25 ° C.,
(B) Formula (1):
（式中、ｎは１〜２５の整数である）で表される末端に酸無水基を有するイミドオリゴマーを、硬化剤１００質量部に対して、７０〜１００質量部含む硬化剤、および
（Ｃ）硬化触媒
を含有することを特徴とする樹脂組成物。
〔２〕（Ａ）成分のエポキシ当量が１００〜１５００である、上記〔１〕記載の樹脂組成物。
〔３〕（Ｃ）成分が、ホスフィン系である、上記〔１〕または〔２〕記載の樹脂組成物。
〔４〕上記〔１〕〜〔３〕のいずれか記載の樹脂組成物から形成される、フィルム。
〔５〕配線パターンが形成された第１の基材の配線パターンと、配線パターンが形成された第２の基材の配線パターンとの間に、上記〔１〕〜〔３〕のいずれか樹脂組成物の硬化物または上記〔４〕記載のフィルムの硬化物を有する、基板。
〔６〕上記〔１〕〜〔３〕の樹脂組成物の硬化物、もしくは上記〔４〕のフィルムの硬化物、または上記〔５〕記載の基板を有する、半導体装置。
〔７〕上記〔４〕記載のフィルムを含む、熱転写ロール用接着材。
〔８〕上記〔７〕記載の熱転写ロール用接着材の硬化物を有する、事務機器。
A curing agent comprising an imide oligomer having an acid anhydride group at the end represented by (wherein n is an integer of 1 to 25), relative to 100 parts by weight of the curing agent, and (C 2.) A resin composition comprising a curing catalyst.
[2] The resin composition according to the above [1], wherein the epoxy equivalent of the component (A) is 100-1500.
[3] The resin composition according to the above [1] or [2], wherein the component (C) is a phosphine type.
[4] A film formed from the resin composition according to any one of the above [1] to [3].
[5] The resin according to any one of the above [1] to [3], between the wiring pattern of the first base on which the wiring pattern is formed and the wiring pattern of the second base on which the wiring pattern is formed. A substrate having a cured product of the composition or a cured product of the film according to the above [4].
[6] A semiconductor device comprising the cured product of the resin composition of the above [1] to [3], the cured product of the film of the above [4], or the substrate of the above [5].
[7] An adhesive for a thermal transfer roll, comprising the film of the above-mentioned [4].
[8] An office machine having the cured product of the adhesive for a thermal transfer roll as described in the above [7].
本発明〔１〕によれば、ワニスにしたときの安定性が高く、塗膜性状がよい樹脂組成物であり、かつ硬化後の接着強度、特に高温保持後にも接着強度を維持できる樹脂組成物を提供することができる。 According to the present invention [1], the resin composition is high in stability when made into a varnish, has good coating film properties, and can maintain adhesive strength after curing, particularly after holding at high temperature. Can be provided.
本発明〔４〕または〔７〕によれば、硬化後の接着強度、特に高温保持後にも接着強度を維持できるフィルムを提供することができる。 According to the invention [4] or [7], it is possible to provide a film capable of maintaining the adhesive strength after curing, particularly the adhesive strength even after holding at high temperature.
本発明〔５〕、〔６〕または〔８〕によれば、接着強度、特に高温保持後にも接着強度を維持できる樹脂組成物の硬化物による高信頼性の基板、半導体装置、事務機器を提供することができる。 According to the present invention [5], [6] or [8], a highly reliable substrate, a semiconductor device and an office machine by a cured product of a resin composition capable of maintaining adhesive strength, particularly adhesive strength even after holding at high temperature. can do.
本発明の樹脂組成物は、
（Ａ）２５℃で液状であるエポキシ樹脂、
（Ｂ）式（１）：
The resin composition of the present invention is
(A) Epoxy resin which is liquid at 25 ° C.
(B) Formula (1):
（式中、ｎは１〜２５の整数である）で表される末端に酸無水基を有するイミドオリゴマーを、硬化剤１００質量部に対して、７０〜１００質量部含む硬化剤、および
（Ｃ）硬化触媒
を含有する。
A curing agent comprising an imide oligomer having an acid anhydride group at the end represented by (wherein n is an integer of 1 to 25), relative to 100 parts by weight of the curing agent, and (C A) containing a curing catalyst.
（Ａ）成分は、樹脂組成物に接着性を付与する。これは、（Ａ）成分であるエポキシ樹脂と（Ｂ）成分であるイミドオリゴマー末端の酸無水基との反応で、ＯＨ基が生じるからである。また、２５℃で液状であると、樹脂組成物の未硬化状態でのフィルム化が可能であり、かつフィルムに可撓性を付与することができる。（Ａ）成分としては、液状ビスフェノールＡ型エポキシ樹脂、液状ビスフェノールＦ型エポキシ樹脂、液状ナフタレン型エポキシ樹脂、液状ノボラック型エポキシ樹脂、液状水添ビスフェノール型エポキシ樹脂、液状脂環式エポキシ樹脂、長鎖炭化水素骨格型液状エポキシ樹脂、液状アルコールエーテル型エポキシ樹脂、液状環状脂肪族型エポキシ樹脂、アミノフェノール型エポキシ樹脂、液状フルオレン型エポキシ樹脂、液状シロキサン系エポキシ樹脂等が挙げられ、樹脂組成物の硬化性、接着性、硬化後の液状エポキシ樹脂組成物の耐熱性、耐久性の観点から、液状ビスフェノールＡ型エポキシ樹脂、液状ビスフェノールＦ型エポキシ樹脂、液状ノボラック型エポキシ樹脂、長鎖炭化水素骨格型液状エポキシ樹脂が、好ましい。耐久性の観点からは、液状水添ビスフェノールＡ型エポキシ樹脂が好ましい。 The component (A) imparts adhesiveness to the resin composition. This is because the OH group is generated by the reaction of the epoxy resin as the component (A) and the acid anhydride group at the end of the imide oligomer as the component (B). Moreover, film formation in the unhardened state of a resin composition is possible as it is liquid at 25 degreeC, and flexibility can be provided to a film. As component (A), liquid bisphenol A epoxy resin, liquid bisphenol F epoxy resin, liquid naphthalene epoxy resin, liquid novolac epoxy resin, liquid hydrogenated bisphenol epoxy resin, liquid alicyclic epoxy resin, long chain Examples thereof include hydrocarbon skeleton type liquid epoxy resin, liquid alcohol ether type epoxy resin, liquid cyclic aliphatic type epoxy resin, aminophenol type epoxy resin, liquid fluorene type epoxy resin, liquid siloxane type epoxy resin and the like, and curing of the resin composition From the viewpoint of heat resistance, adhesiveness, and heat resistance and durability of the liquid epoxy resin composition after curing, liquid bisphenol A epoxy resin, liquid bisphenol F epoxy resin, liquid novolac epoxy resin, long chain hydrocarbon skeleton liquid Epoxy resins are preferred. From the viewpoint of durability, liquid hydrogenated bisphenol A epoxy resin is preferable.
（Ａ）成分のエポキシ当量は、１００〜１５００ｇ／ｅｑであると、硬化性の観点から、好ましい。（Ａ）成分の当量が小さいと、相対的に（Ｂ）成分を多く必要とするため、塗膜性状が悪化しやすくなる。他方、（Ａ）成分の当量が大きいと、相対的に（Ｂ）成分の量が減少するため、耐熱性及び硬化膜性状が悪化しやすくなる。（Ａ）成分の市販品としては、三菱化学製液状ビスフェノールＡ型エポキシ樹脂（品名：ｊｅｒ８２８）、三菱化学製液状水添ビスフェノールＡ型エポキシ樹脂（品名：ＹＬ６８００、ｊｅｒ ＹＸ８０００）、新日鉄住金化学製液状ビスフェノールＦ型エポキシ樹脂（品名：ＹＤＦ８１７０）、三菱化学製液状フェノールノボラック型エポキシ樹脂（品名：ｊｅｒ１５２）、ＤＩＣ製変性ビスフェノールＡ型液状エポキシ樹脂（品名：ＥＸＡ４８５０−１０００）、ＤＩＣ製液状長鎖炭化水素骨格を有する液状エポキシ樹脂（品名：ＥＸＡ４８１６）、三菱化学製液状特殊機能タイプエポキシ樹脂（品名：ＹＬ７１７５−１０００）、三菱化学製アミノフェノール型エポキシ樹脂（グレード：ＪＥＲ６３０、ＪＥＲ６３０ＬＳＤ）、ＤＩＣ製ナフタレン型エポキシ樹脂（品名：ＨＰ４０３２Ｄ）、信越化学製シロキサン系エポキシ樹脂（品名：ＴＳＬ９９０６）等が挙げられる。（Ａ）成分は、単独でも２種以上を併用してもよい。 The epoxy equivalent of the component (A) is preferably 100 to 1500 g / eq from the viewpoint of curability. When the equivalent weight of the component (A) is small, relatively many components (B) are required, and the coating film properties are apt to be deteriorated. On the other hand, when the equivalent of the component (A) is large, the amount of the component (B) relatively decreases, and thus the heat resistance and the properties of the cured film tend to deteriorate. Commercial products of component (A) include liquid bisphenol A epoxy resin (product name: jer 828) manufactured by Mitsubishi Chemical, liquid hydrogenated bisphenol A epoxy resin (product names: YL 6800, jer YX 8000) manufactured by Mitsubishi Chemical, liquid manufactured by Nippon Steel & Sumikin Chemical Bisphenol F type epoxy resin (product name: YDF 8170), Mitsubishi Chemical liquid phenol novolac epoxy resin (product name: jer 152), DIC modified bisphenol A liquid epoxy resin (product name: EXA 4850-1000), DIC liquid long chain hydrocarbon Liquid epoxy resin with skeleton (Product name: EXA4816), Mitsubishi Chemical liquid special function epoxy resin (Product name: YL7175-1000), Mitsubishi Chemical aminophenol type epoxy resin (grade: JER630, JER630LSD), DIC Naphthalene type epoxy resin (product name: HP4032D), Shin-Etsu Chemical Co. siloxane epoxy resin (product name: TSL9906), and the like. The component (A) may be used alone or in combination of two or more.
（Ｂ）成分は、式（１）： The component (B) is represented by the formula (1):
（式中、ｎは１〜２５の整数である）で表される末端に酸無水基を有するイミドオリゴマー（以下、イミドオリゴマーという）を、硬化剤１００質量部に対して、７０〜１００質量部含み、このイミドオリゴマーは、樹脂組成物に、柔軟性、硬化後の樹脂組成物に耐熱性を付与する。柔軟性は、Ａｒ２の構造をもつことで付与される。Ａｒ２中のｎは、２〜１４の整数であることが好ましい。イミドオリゴマーが、硬化剤１００質量部に対して、７０質量部未満では、樹脂組成物の塗膜性状、硬化膜性状等が悪くなってしまう。ここで、塗膜性状とは、樹脂組成物からなる膜が未硬化状態で可とう性を有することをいい、硬化膜性状とは、樹脂組成物からなる膜が硬化状態で可とう性を有することをいう。 (In the formula, n is an integer of 1 to 25) 70 to 100 parts by mass of an imide oligomer having an acid anhydride group at the end (hereinafter referred to as imide oligomer) with respect to 100 parts by mass of a curing agent This imide oligomer imparts flexibility to the resin composition and heat resistance to the resin composition after curing. The flexibility is given by having the structure of Ar2. N in Ar2 is preferably an integer of 2 to 14. If the amount of the imide oligomer is less than 70 parts by mass with respect to 100 parts by mass of the curing agent, the coating film properties, the cured film properties, and the like of the resin composition become worse. Here, the coating film property means that a film made of a resin composition has flexibility in an uncured state, and the cured film property means that a film made of a resin composition has flexibility in a cured state. It means that.
イミドオリゴマーは、重量平均分子量が、１０００〜３０００であると、好ましい。重量平均分子量が、１０００未満では、硬化後の柔軟性が劣りやすくなる。重量平均分子量が、３０００を越えると、組成物のワニス化が困難になり易い。（Ｂ）成分の市販品としては、マナック株式会社製酸無水イミド（品名：ｋ６７８、重量平均分子量：１８８０）が挙げられる。 The imide oligomer preferably has a weight average molecular weight of 1000 to 3,000. When the weight average molecular weight is less than 1000, the flexibility after curing tends to be poor. When the weight average molecular weight exceeds 3,000, the varnishing of the composition tends to be difficult. Examples of commercial products of the component (B) include acid anhydride imides (product name: k678, weight average molecular weight: 1880) manufactured by Manac Corporation.
（Ｂ）成分で、イミドオリゴマー以外に含有される硬化剤としては、特に限定されず、酸無水物、ビスマレイミド、ビフェニルノボラックフェノール等が挙げられる。酸無水物としては、メチルテトラヒドロフタル酸無水物、メチルブテニルテトラヒドロフタル酸無水物、メチルヘキサヒドロフタル酸無水物、アルキル化テトラヒドロフタル酸無水物、ヘキサヒドロフタル酸無水物、メチルハイミック酸無水物、アルケニル基で置換されたコハク酸無水物、メチルナジック酸無水物、グルタル酸無水物等が挙げられる。ビスマレイミドとしては、Ｎ−エチルマレイミド、Ｎ−シクロヘキシルマレイミド、Ｎ−イソプロピルマレイミド、Ｎ−メチルマレイミド、Ｎ−ブチルマレイミド、１，６−ビスマレイミド−（２，２，４−トリメチル)ヘキサン等が挙げられる。イミドオリゴマー以外に含有される硬化剤の市販品としては、三菱化学製酸無水物硬化剤（品名：ＹＨ１１２０）、ケイ・アイ化成製２，２’−ビス−［４−（４−マレイミドフェノキシ）フェニル］プロパン（品名：ＢＭＩ−８０）、１４）、明和化成製ビフェニルノボラックフェノール硬化剤（品名：ＭＥＨ−７８５１）等が挙げられる。（Ｂ）成分は、単独でも２種以上を併用してもよい。 The curing agent contained as component (B) other than the imide oligomer is not particularly limited, and examples thereof include acid anhydride, bismaleimide, biphenyl novolac phenol and the like. As the acid anhydride, methyltetrahydrophthalic anhydride, methylbutenyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, alkylated tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhymic anhydride , Succinic anhydride substituted with an alkenyl group, methyl nadic anhydride, glutaric anhydride and the like. As bismaleimide, N-ethyl maleimide, N-cyclohexyl maleimide, N-isopropyl maleimide, N-methyl maleimide, N-butyl maleimide, 1, 6-bis maleimide- (2, 2, 4- trimethyl) hexane etc. are mentioned. Be As a commercial item of the hardening agent contained other than an imide oligomer, Mitsubishi Chemical make acid anhydride hardening agent (brand name: YH1120), the 2 I 2-bis-[4- (4-maleimido phenoxy) made by KAI and I Kasei Phenyl] propane (product name: BMI-80), 14), and a biphenyl novolac phenol curing agent (product name: MEH-7851) manufactured by Meiwa Kasei Co., Ltd., and the like. The component (B) may be used alone or in combination of two or more.
（Ｃ）成分の硬化触媒は、樹脂組成物に適切な硬化速度を付与する。（Ｃ）成分は、特に限定されず、例えば、ホスフィン系、アミン系、イミダゾール等が挙げられる。ホスフィン系であると、イミダゾール等と比べて、硬化後の樹脂組成物に、高耐熱性（例えば、２００℃保持後の接着強度の経時変化が少ない）、透明性を付与できるので、好ましい。 The curing catalyst of component (C) imparts an appropriate curing rate to the resin composition. The component (C) is not particularly limited, and examples thereof include phosphines, amines, and imidazoles. The phosphine type is preferable because high heat resistance (for example, less change in adhesion strength with time after holding at 200 ° C.) and transparency can be imparted to the resin composition after curing, as compared with imidazole and the like.
ホスフィン系硬化触媒としては、トリフェニルホスフィン、トリブチルホスフィン、トリ（ｐ−メチルフェニル）ホスフィン、トリ（ノニルフェニル）ホスフィン等が挙げられる。アミン系硬化触媒としては、２，４−ジアミノ−６−〔２’―メチルイミダゾリル−（１’）〕エチル−ｓ−トリアジン等のトリアジン化合物、１，８−ジアザビシクロ［５，４，０］ウンデセン−７（ＤＢＵ）、トリエチレンジアミン、ベンジルジメチルアミン、トリエタノールアミン等の第三級アミン化合物が挙げられる。イミダゾール硬化触媒としては、２−メチルイミダゾール、２−ウンデシルイミダゾール、２−ヘプタデシルイミダゾール、２−エチル−４−メチルイミダゾール、２−フェニルイミダゾール、２−フェニル−４−メチルイミダゾール、１−シアノエチル−２−エチル−４−メチルイミダゾール等のイミダゾール化合物が挙げられる。（Ｃ）成分の市販品としては、北興化学工業製テトラフェニルホスホニウムテトラ−ｐ−トリルボレート（ＴＰＰ−ＭＫ）、スリーボンド製ジアミノジフェニルスルフォン（品名：ＤＤＳ）、四国化成製２−エチル−４−メチルイミダゾール（品名：２Ｅ４ＭＺ）、四国化成製１−シアノエチル−２−エチル−４−メチルイミダゾール（品名：２Ｅ４ＭＺ−ＣＮ）が挙げられる。 Examples of phosphine-based curing catalysts include triphenylphosphine, tributylphosphine, tri (p-methylphenyl) phosphine, tri (nonylphenyl) phosphine and the like. As an amine curing catalyst, triazine compounds such as 2,4-diamino-6- [2′-methylimidazolyl- (1 ′)] ethyl-s-triazine, 1,8-diazabicyclo [5,4,0] undecene And tertiary amine compounds such as -7 (DBU), triethylenediamine, benzyldimethylamine and triethanolamine. As the imidazole curing catalyst, 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-cyanoethyl- An imidazole compound such as 2-ethyl-4-methylimidazole can be mentioned. Commercial products of component (C) include tetraphenylphosphonium tetra-p-tolylborate (TPP-MK) manufactured by Hokuko Chemical Co., Ltd., diaminodiphenyl sulfone manufactured by Three Bond (product name: DDS), 2-ethyl-4-methyl manufactured by Shikoku Kasei Co., Ltd. Imidazole (product name: 2E4MZ), Shikoku Chemicals 1-cyanoethyl-2-ethyl-4-methylimidazole (product name: 2E4MZ-CN) may be mentioned.
（Ａ）成分は、硬化性、接着性の観点から、樹脂組成物１００質量部に対して、１０〜６０であると、好ましい。 The component (A) is preferably 10 to 60 per 100 parts by mass of the resin composition from the viewpoint of curability and adhesiveness.
（Ｂ）成分は、（Ａ）成分：１当量に対して、０．１〜１．２当量の比率であると好ましく、０．２〜１．０当量であると、より好ましい。（Ａ）成分の当量はエポキシ当量であり、（Ｂ）成分の当量は、イミドオリゴマーの場合は酸無水基当量である。（Ａ）に対する（Ｂ）の当量比が０．２以上であると、反応性、硬化後の樹脂組成物の高温放置後の接着性が良好である。他方、１．２以上であると、塗膜性状が悪化しやすくなる。 Component (B) is preferably in a ratio of 0.1 to 1.2 equivalents, more preferably 0.2 to 1.0 equivalents, per equivalent of component (A). The equivalent of the component (A) is an epoxy equivalent, and the equivalent of the component (B) is an acid anhydride group equivalent in the case of an imide oligomer. When the equivalent ratio of (B) to (A) is 0.2 or more, the reactivity and the adhesiveness of the cured resin composition after being left at high temperature are good. On the other hand, when it is 1.2 or more, the coating film properties are easily deteriorated.
（Ｃ）成分は、（Ａ）成分：１００質量部に対して、好ましくは０．０５〜５質量部、より好ましくは０．１〜５質量部、さらに好ましくは０．３〜３．０質量部含有される。０．０５質量部以上であると、反応性が良好であり、５質量部以下であると、耐熱性が良好あり、更に増粘倍率が安定である。 Component (C) is preferably 0.05 to 5 parts by mass, more preferably 0.1 to 5 parts by mass, and still more preferably 0.3 to 3.0 parts by mass per 100 parts by mass of component (A). Partly contained. The reactivity is good when it is 0.05 parts by mass or more, the heat resistance is good when it is 5 parts by mass or less, and the thickening ratio is stable.
本発明の樹脂組成物には、本発明の目的を損なわない範囲で、更に必要に応じ、シランカップリング剤等のカップリング剤、シリカフィラー等のフィラー、レベリング剤、消泡剤、搖変剤、酸化防止剤、顔料、染料等の添加剤を配合することができる。 In the resin composition of the present invention, a coupling agent such as a silane coupling agent, a filler such as a silica filler, a leveling agent, an antifoaming agent, an antifoaming agent, and the like as long as the object of the present invention is not impaired. And additives such as antioxidants, pigments and dyes.
樹脂組成物は、ワニス化した際、温度：２５℃での粘度が５０〜１０００ｍＰａ・ｓであると、塗膜性状の観点から好ましい。ここで、粘度は、東機産業社製Ｅ型粘度計（型番：ＴＶＥ−２２Ｈ）で測定する。 It is preferable from the viewpoint of a coating film property that the viscosity at a temperature: 25 ° C. is 50 to 1000 mPa · s when the resin composition is made into a varnish. Here, the viscosity is measured by an E-type viscometer manufactured by Toki Sangyo Co., Ltd. (model number: TVE-22H).
ワニス化した樹脂組成物は、室温で１ヶ月放置しても固化しないことが望ましい。 It is desirable that the varnished resin composition does not solidify even if it is left at room temperature for one month.
本発明の樹脂組成物は、例えば、（Ａ）成分〜（Ｃ）成分およびその他添加剤等を同時にまたは別々に、必要により加熱処理を加えながら、撹拌、溶融、混合、分散させることにより得ることができる。これらの混合、撹拌、分散等の装置としては、特に限定されるものではないが、撹拌、加熱装置を備えたライカイ機、３本ロールミル、ボールミル、プラネタリーミキサー、ビーズミル等を使用することができる。また、これら装置を適宜組み合わせて使用してもよい。 The resin composition of the present invention can be obtained, for example, by stirring, melting, mixing, and dispersing components (A) to (C) and other additives simultaneously or separately, with heat treatment if necessary. Can. An apparatus for mixing, stirring, dispersing and the like is not particularly limited, but a lai-sea machine equipped with stirring and a heating device, a three-roll mill, a ball mill, a planetary mixer, a bead mill, etc. can be used. . Moreover, you may use combining these apparatuses suitably.
本発明の樹脂組成物は、ディスペンサー、印刷機、コーター等で、フィルムや基板、熱転写ローラーの所望の位置に形成・塗布される。 The resin composition of the present invention is formed and applied to a desired position of a film, a substrate, or a thermal transfer roller by a dispenser, a printer, a coater or the like.
本発明の樹脂組成物の硬化は、１２０〜１６０℃で、３０〜６０分間行うことが好ましい。 Curing of the resin composition of the present invention is preferably performed at 120 to 160 ° C. for 30 to 60 minutes.
本発明のフィルムは、例えば、樹脂組成物をコーター等で、ＰＥＴフィルム等の基材上に塗布した後、乾燥して、形成することができる。 The film of the present invention can be formed, for example, by applying the resin composition on a substrate such as a PET film with a coater or the like and then drying.
本発明の基板は、配線パターンが形成された第１の基材の配線パターンと、配線パターンが形成された第２の基材の配線パターンとの間に、上述の樹脂組成物の硬化物または上述のフィルムの硬化物を有する。この基板は、リジッドタイプのものであっても、フレキシブルタイプのものであっても、本発明の効果を発揮するのに適している。また、本発明の半導体装置は、上述の樹脂組成物の硬化物、もしくは上述のフィルムの硬化物、または上述の基板を有する。 The substrate of the present invention is a cured product of the above resin composition or the wiring pattern of the first base on which the wiring pattern is formed and the wiring pattern of the second base on which the wiring pattern is formed. It has a cured product of the above-mentioned film. This substrate, whether of rigid type or flexible type, is suitable for achieving the effects of the present invention. The semiconductor device of the present invention also includes the cured product of the above-described resin composition, or the cured product of the above-described film, or the above-described substrate.
本発明の熱転写ロール用接着材は、上述のフィルムを含み、例えば、ヒーターと固定部材との接着に用いられる。また、本発明の事務機器は、上述の熱転写ロール用接着材の硬化物を有する。ここで、事務機器は、熱転写ロールを有するものであればよく、特に、熱転写ロールの使用温度が２００℃以下のものが本発明の効果を発揮するのに適している。 The adhesive for a thermal transfer roll of the present invention includes the above-mentioned film, and is used, for example, for bonding a heater and a fixing member. Moreover, the office machine of the present invention has a cured product of the above-mentioned adhesive for a thermal transfer roll. Here, the office equipment may be any one having a thermal transfer roll, and in particular, one having a use temperature of 200 ° C. or less of the thermal transfer roll is suitable for exhibiting the effects of the present invention.
本発明について、実施例により説明するが、本発明はこれらに限定されるものではない。なお、以下の実施例において、部、％はことわりのない限り、質量部、質量％を示す。 The present invention will be described by way of examples, but the present invention is not limited thereto. In the following examples, parts and% indicate parts by mass and% by mass unless otherwise specified.
〔実施例１〜１０、比較例１〜５〕
表１、表２に示す配合で、樹脂成分が３０〜６０質量％にとなるようにメチルエチルケトンを加え、星式撹拌脱泡装置を用いて、室温で溶解するまで混合し、ワニス状の樹脂組成物を作製した。
[Examples 1 to 10, Comparative Examples 1 to 5]
Methyl ethyl ketone is added so that the resin component is 30 to 60% by mass in the formulations shown in Table 1 and Table 2, and it is mixed until dissolved at room temperature using a star stirring degassing apparatus, and the resin composition in the form of varnish The object was made.
〔相溶性の評価〕
作製した樹脂組成物の外観を目視で観察し、均一であった場合を「○」、濁りがあった場合を「△」、分離した場合を「×」とした。相溶性は、○が好ましい。表１、表２に結果を示す。
[Evaluation of compatibility]
The appearance of the produced resin composition was visually observed, and the case where it was uniform was made into "(circle)", the case where there was turbidity was made into "(triangle | delta)", and the case where it separated was made into "x". The compatibility is preferably ○. The results are shown in Table 1 and Table 2.
〔ワニス安定性の評価〕
作製したワニス状の樹脂組成物を、密閉容器で１ヶ月室温放置した。１ヶ月放置したワニスを目視で観察し、作製当初とほぼ同じ液状態が保たれている場合を「○」、作製当初より５倍以上粘度が上昇した場合を「△」、固化した場合を「×」とした。ワニス安定性は、○または△が好ましい。表１、表２に結果を示す。
[Evaluation of varnish stability]
The produced varnish-like resin composition was left in a closed container for 1 month at room temperature. The varnish left to stand for one month is visually observed, and the case where the liquid state is maintained almost the same as the preparation initial is "○", the case where the viscosity is increased 5 times or more from the preparation initial is "Δ", the solidified case " X. The varnish stability is preferably ○ or △. The results are shown in Table 1 and Table 2.
〔塗膜性状の評価〕
上述のように作製したワニスを、ＰＥＴフィルムの基材上に、厚さ２５μｍで塗布して、塗膜を作製し、塗膜を１００℃で１０分間乾燥し、フィルムを得た。フィルムに可とう性がある場合を「○」、フィルムに可とう性が無く、割れやすい場合を「△」、フィルムが基材上で割れた場合を「×」とした。塗膜性状は、○または△が好ましい。表１、表２に結果を示す。
[Evaluation of coating film properties]
The varnish prepared as described above was coated on a PET film substrate to a thickness of 25 μm to prepare a coating, and the coating was dried at 100 ° C. for 10 minutes to obtain a film. The case where the film is flexible is referred to as “o”, the case where the film is not flexible and is easily broken is referred to as “Δ”, and the case where the film is broken on the substrate is referred to as “x”. The coating film properties are preferably ○ or Δ. The results are shown in Table 1 and Table 2.
〔硬化膜性状の評価〕
上述のように作製したフィルムを、１６０℃で６０分間硬化させた。硬化させたフィルムに可とう性（柔軟性）があった場合を「○」、折り曲げ後のフィルムに曇りが発生した場合を「△」、フィルムに可とう性（柔軟性）が無く割れやすい場合を「×」とした。硬化膜性状は、○が好ましい。表１、表２に結果を示す。
[Evaluation of cured film properties]
The film prepared as described above was cured at 160 ° C. for 60 minutes. "○" when the cured film has flexibility (flexibility), "△" when clouding occurs in the film after bending, and when the film has no flexibility (flexibility) and is easily broken "X". The cured film property is preferably ○. The results are shown in Table 1 and Table 2.
〔接着強度の評価〕
《接着強度１》
２枚の銅箔１８μｍ（ＣＦ−Ｔ８：福田金属箔粉工業製）の粗化面の間に、上述のように作製したフィルムを挟んだ後、１６０℃、３０分プレス（圧力：１ＭＰａ）で貼り付けし、評価用試料を作製した。オートグラフを用い、ＪＩＳ Ｋ６８５４に準じた条件で、２枚の銅箔のうち１枚を１８０°の方向に引き剥がした時の引きはがし強度を測定した。接着強度１は、７Ｎ／ｃｍ以上が好ましい。表１、表２に、結果を示す。
[Evaluation of adhesive strength]
Bonding Strength 1
After sandwiching the film prepared as described above between the roughened surfaces of two copper foils 18 μm (CF-T8: manufactured by Fukuda Metal Foil Powder Industry), press at 160 ° C. for 30 minutes (pressure: 1 MPa) It stuck and produced the sample for evaluation. Using an autograph, the peeling strength was measured when one of the two copper foils was peeled off in the direction of 180 ° under the conditions according to JIS K6854. The adhesive strength 1 is preferably 7 N / cm or more. Tables 1 and 2 show the results.
《接着強度２》
２枚のポリイミドフィルム（カプトン１００Ｈ：東レ・デュポン製）の間に、上述のように作製したフィルムを挟んだ後、１６０℃、３０分プレス（圧力：１ＭＰａ）で貼り付けし、評価用試料を作製した。オートグラフを用い、ＪＩＳ Ｋ６８５４に準じた条件で、２枚のポリイミドフィルムのうち１枚を１８０°の方向に引き剥がした時の引きはがし強度を測定した。ポリイミドフィルムが破断した場合を「○」とした。接着強度２は、○か１Ｎ／ｃｍ以上が好ましい。表１、表２に、結果を示す。
Bonding Strength 2
After sandwiching the film prepared as described above between two polyimide films (Kapton 100H: made by Toray Dupont), it is pasted at 160 ° C. for 30 minutes with a press (pressure: 1 MPa), and the sample for evaluation is Made. Using an autograph, the peeling strength was measured when one of the two polyimide films was peeled off in the direction of 180 ° under the conditions according to JIS K6854. The case where the polyimide film was broken was taken as "o". The adhesive strength 2 is preferably ○ or 1 N / cm or more. Tables 1 and 2 show the results.
《熱処理後接着強度》
２枚のポリイミドフィルム（カプトン１００Ｈ：東レ・デュポン製）の間に、上述のように作製したフィルムを挟んだ後、１６０℃、３０分プレス（圧力：１ＭＰａ）で貼り付けした。この後、２００℃で１００時間の熱処理し、評価用試料を作製した。オートグラフを用い、ＪＩＳ Ｋ６８５４に準じた条件で、２枚のポリイミドフィルムのうち１枚を１８０°の方向に引き剥がした時の引きはがし強度を測定した。ポリイミドフィルムが破断した場合を「○」とした。熱処理後接着強度は、○か、１Ｎ／ｃｍ以上が好ましい。評価用試料に膨れが発生した場合を「×」とした。表１、表２に、結果を示す。
接着 Adhesive strength after heat treatment》
After sandwiching the film produced as described above between two polyimide films (Kapton 100H: manufactured by Toray Dupont), the films were pasted at 160 ° C. for 30 minutes using a pressure (pressure: 1 MPa). After this, heat treatment was performed at 200 ° C. for 100 hours to prepare a sample for evaluation. Using an autograph, the peeling strength was measured when one of the two polyimide films was peeled off in the direction of 180 ° under the conditions according to JIS K6854. The case where the polyimide film was broken was taken as "o". The adhesive strength after heat treatment is preferably ○ or 1 N / cm or more. The case where swelling occurred in the sample for evaluation was made into "x". Tables 1 and 2 show the results.
表１、表２からわかるように、実施例１〜１０の全てで、相溶性、ワニス安定性、塗膜性状、硬化膜性状、接着強度において、結果が良好であった。特に、（Ｃ）成分にホスフィン系を使用した実施例１は、特に良好な結果であった。また、表１には記載していないが、（Ｃ）成分にホスフィン系を使用した実施例１は、硬化後および熱処理後の樹脂組成物の透明性も優れていた。これに対して、（Ｂ）成分の代わりにビフェニルノボラックフェノールを使用した比較例１は、ワニス安定性、硬化膜性状、熱処理後接着強度の結果が悪かった。（Ａ）成分の代わりに、固形エポキシ樹脂を用いた比較例２は、塗膜性状が悪く、接着強度の評価ができなかった。酸無水イミドの含有量が低すぎる比較例３は、塗膜性状と硬化膜性状の結果が悪かった。（Ａ）成分の代わりに、固形エポキシ樹脂を用い、酸無水イミドの含有量が低すぎる比較例４は、塗膜性状と硬化膜性状の結果が悪かった。（Ｂ）成分の代わりに酸無水物を使用した比較例５は、熱処理後接着強度の結果が悪かった。 As can be seen from Tables 1 and 2, in all of Examples 1 to 10, the results were good in compatibility, varnish stability, coating film properties, cured film properties, and adhesive strength. In particular, Example 1 using a phosphine type for the component (C) gave particularly good results. Moreover, although not described in Table 1, Example 1 using a phosphine type for the component (C) was also excellent in the transparency of the resin composition after curing and after heat treatment. On the other hand, Comparative Example 1 in which biphenyl novolac phenol was used instead of the component (B) had poor results of varnish stability, cured film properties, and adhesive strength after heat treatment. In Comparative Example 2 in which a solid epoxy resin was used instead of the component (A), the coating film properties were poor, and the adhesive strength could not be evaluated. In Comparative Example 3 in which the content of the acid anhydride imide was too low, the results of the coating film properties and the cured film properties were poor. In Comparative Example 4 in which the content of acid anhydride imide is too low using a solid epoxy resin instead of the component (A), the results of the coating film properties and the cured film properties were poor. The comparative example 5 which used the acid anhydride instead of (B) component had the bad result of the adhesive strength after heat processing.
上記のように、本発明の樹脂組成物は、ワニスにしたときの安定性が高く、塗膜性状がよい樹脂組成物であり、かつ硬化後の接着強度、特に高温保持後にも接着強度が維持される。このため、リジッドタイプやフレキシブルタイプの基板の接着用、熱転写ロールの接着用に好適である。 As described above, the resin composition of the present invention is a resin composition having high stability when made into a varnish and good coating film properties, and adhesive strength after curing, particularly maintaining adhesive strength even after high temperature holding Be done. For this reason, it is suitable for adhesion of substrates of rigid type or flexible type, and adhesion of thermal transfer rolls.
Claims (8)
（Ｂ）式（１）：
（Ｃ）硬化触媒
を含有することを特徴とする樹脂組成物。 (A) Epoxy resin which is liquid at 25 ° C.
(B) Formula (1):
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