JP4875794B2 - Resin composition - Google Patents
Resin composition Download PDFInfo
- Publication number
- JP4875794B2 JP4875794B2 JP28255498A JP28255498A JP4875794B2 JP 4875794 B2 JP4875794 B2 JP 4875794B2 JP 28255498 A JP28255498 A JP 28255498A JP 28255498 A JP28255498 A JP 28255498A JP 4875794 B2 JP4875794 B2 JP 4875794B2
- Authority
- JP
- Japan
- Prior art keywords
- polyimide
- resin composition
- general formula
- minutes
- adhesive
- 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.)
- Expired - Lifetime
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- 239000011342 resin composition Substances 0.000 title claims description 24
- 229920001721 polyimide Polymers 0.000 claims description 46
- 239000004642 Polyimide Substances 0.000 claims description 34
- 229920005575 poly(amic acid) Polymers 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000010521 absorption reaction Methods 0.000 claims description 15
- -1 ester dianhydride Chemical class 0.000 claims description 15
- 239000003822 epoxy resin Substances 0.000 claims description 13
- 229920000647 polyepoxide Polymers 0.000 claims description 13
- 150000004985 diamines Chemical class 0.000 claims description 11
- 239000002798 polar solvent Substances 0.000 claims description 8
- NHJNWRVCOATWGF-UHFFFAOYSA-N 3-(3-amino-2-phenoxyphenyl)sulfonyl-2-phenoxyaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C(=C(N)C=CC=2)OC=2C=CC=CC=2)=C1OC1=CC=CC=C1 NHJNWRVCOATWGF-UHFFFAOYSA-N 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 36
- 239000000853 adhesive Substances 0.000 description 20
- 230000001070 adhesive effect Effects 0.000 description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 239000011521 glass Substances 0.000 description 14
- 238000000034 method Methods 0.000 description 13
- 239000002904 solvent Substances 0.000 description 13
- 239000000126 substance Substances 0.000 description 11
- 239000002966 varnish Substances 0.000 description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 9
- 239000011889 copper foil Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 229910000679 solder Inorganic materials 0.000 description 9
- 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 8
- 239000000843 powder Substances 0.000 description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000004843 novolac epoxy resin Substances 0.000 description 4
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 0 CC(O)=C(c(c1c2)cc*2[N+]([O-])O*O[N+](*(C=C2)C=CC(C(O3)=O)=C2C3=O)[O-])OC1O Chemical compound CC(O)=C(c(c1c2)cc*2[N+]([O-])O*O[N+](*(C=C2)C=CC(C(O3)=O)=C2C3=O)[O-])OC1O 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 239000002253 acid Substances 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 239000012024 dehydrating agents Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 235000013824 polyphenols Nutrition 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- ITQTTZVARXURQS-UHFFFAOYSA-N 3-methylpyridine Chemical compound CC1=CC=CN=C1 ITQTTZVARXURQS-UHFFFAOYSA-N 0.000 description 2
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000012790 adhesive layer Substances 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 239000004760 aramid Substances 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 229920003235 aromatic polyamide Polymers 0.000 description 2
- 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 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- CCAFPWNGIUBUSD-UHFFFAOYSA-N diethyl sulfoxide Chemical compound CCS(=O)CC CCAFPWNGIUBUSD-UHFFFAOYSA-N 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 2
- 239000002648 laminated material Substances 0.000 description 2
- AJFDBNQQDYLMJN-UHFFFAOYSA-N n,n-diethylacetamide Chemical compound CCN(CC)C(C)=O AJFDBNQQDYLMJN-UHFFFAOYSA-N 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 2
- 150000003462 sulfoxides Chemical class 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- 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 1
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- 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 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000004959 Rilsan Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000003522 acrylic cement Substances 0.000 description 1
- 239000011825 aerospace material Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 1
- 229930188620 butyrolactone Natural products 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 1
- 239000011353 cycloaliphatic epoxy resin Substances 0.000 description 1
- 125000006159 dianhydride group Chemical group 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920006332 epoxy adhesive Polymers 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000004845 glycidylamine epoxy resin Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
- Adhesives Or Adhesive Processes (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、比較的低温で接着硬化でき、溶媒に可溶で耐熱性及び接着性に優れた樹脂組成物に関する。本発明の樹脂組成物は、フレキシブル印刷回路基板、ＴＡＢ（Ｔａｐｅ Ａｕｔｏｍａｔｅｄ ｂｏｎｄｉｎｇ）用テープ、複合リードフレーム、積層材料等に用いられる耐熱性及び接着性に優れた接着剤として有用である。
【０００２】
【従来の技術】
近年、電子機器の高機能化、高性能化、小型化が進んでおり、それらに伴って用いられる電子部品に対する小型化、軽量化が求められてきている。そのため半導体素子パッケージ方法やそれらを実装する配線材料又は配線部品も、より高密度、高機能、かつ、高性能なものが求められるようになってきた。特に、半導体パッケージ、ＣＯＬ及びＬＯＣパッケージ、ＭＣＭ(Multi Chip Module) 等の高密度実装材料や多層ＦＰＣ等のプリント配線板材料、さらには航空宇宙材料として好適に用いることのできる、良好な接着性を示す材料が求められている。
【０００３】
従来、半導体パッケージやその他実装材料において、良好な機械的特性や耐熱特性、絶縁特性を示す接着材料として、アクリル系、フェノール系、エポキシ系、ポリイミド系等の接着剤が知られている。
【０００４】
ところが、フェノール系及びエポキシ系の接着剤は、接着性は優れているが、柔軟性に劣る。柔軟性のあるアクリル系の接着剤は耐熱性が低いという問題が生じていた。
【０００５】
【発明が解決しようとする課題】
これらを解決するために、ポリイミドが用いられている。ポリイミドは、種々の有機ポリマーの中でも耐熱性に優れているため、宇宙、航空分野から電子通信分野まで幅広く用いられ、接着材料としても用いられている。しかし、耐熱性の高いポリイミド系接着剤は、接着するために３００℃前後の高温と高圧力を要し、接着力もそれほど高いとはいえない。また、従来のポリイミド系接着剤は吸水率が高く、例えば、このポリイミド系接着剤を使用したリードフレームを半田浴に浸漬する際、膨れ等を生じやすいといった問題を有していた。
【０００６】
【課題を解決するための手段】
本発明は、低吸水率で半田耐熱性に優れ、かつ耐熱性、接着性ともに優れ、２５０℃以下の低温で接着可能な樹脂組成物を提供するものである。
【０００７】
本発明の要旨とするところは、一般式（１）化４
【０００８】
【化４】
で表されるエステル酸二無水物と式（２）化５
【００１０】
【化５】
のジアミンからなるポリイミド及びエポキシ樹脂とからなる樹脂組成物を内容とする。
【００１２】
また、一般式（２）で表されるジアミンにおいて、特に一般式（３）化６
【００１３】
【化６】
で表されることを特徴とする前記樹脂組成物に関する。
【００１５】
また、硬化後の吸水率が１．５％以下であることを特徴とする前記樹脂組成物に関する。
【００１６】
【発明の実施の形態】
本発明は、一般式（１）
（式中、Ｘは芳香環を含む二価の基を示す。）で表されるエステル酸二無水物と、式（２）または式（３）のジアミンからなる樹脂組成物である。
【００１７】
本発明にかかるポリイミド組成物に用いられる酸二無水物は、一般式（１）化７
【００１８】
【化７】
（式中、Ｘは２価の有機基である。）
で表されるエステル酸二無水物を使用することを必須とする。
【００２０】
一般式（１）で表されるエステル酸二無水物を用いたポリイミド組成物は、優れた低吸水率を有するため、半田耐熱性に優れた特性を有する。
【００２１】
また、一般式（２）化８
【００２２】
【化８】
（式中、Ｙは−Ｃ（＝Ｏ）−、−ＳＯ2 −、−Ｏ−、−Ｓ−、−（ＣＨ2 ）m −、−ＮＨＣＯ−、−Ｃ（ＣＨ3 ）2 −、−Ｃ（ＣＦ3 ）2 −、−Ｃ（＝Ｏ）Ｏ−、または結合を示す。ｍ及びｎは１以上５以下の整数である）で表されるジアミンを用いることを必須とする。
【００２４】
また、一般式（２）において、複数個のＹは同一または２種以上の置換基であり得る。また、各ベンゼン環の水素は、当業者の考え得る範囲内で、種々の置換基で適宜置換され得る。例えば、メチル基、エチル基、Ｂｒ，Ｃｌ等のハロゲン基をあげることができるが、これらの置換基に限定されない。
【００２５】
さらに、本発明者らは、一般式（２）で表されるジアミンのアミノ基がメタ位に結合していることにより、これを用いたポリイミド組成物の溶媒に対する溶解性が上がることを見出し、接着剤として用いる際に優れた有用性を示すことに着目した。
【００２６】
具体的には、ジアミンとして、一般式（２）において、特にアミノ基が一般式（３）化９
【００２７】
【化９】
（式中、Ｙは−Ｃ（＝Ｏ）−、−ＳＯ2 −、−Ｏ−、−Ｓ−、−（ＣＨ2 ）m −、−ＮＨＣＯ−、−Ｃ（ＣＨ3 ）2 −、−Ｃ（ＣＦ3 ）2 −、−Ｃ（＝Ｏ）Ｏ−、または結合を示す。ｍ及びｎは１以上５以下の整数である。）に示すように、メタ位についているのが好ましい。メタ位にアミノ基があることにより、生成されるポリイミドの有機溶媒への溶解性がより良好となり、加工性が優れる。
【００２９】
一般式（２）または一般式（３）で表されるジアミンは、１種または２種以上混合して用いうる。
【００３０】
本発明にかかる樹脂組成物に用いられるポリイミドは、その前駆体であるポリアミド酸重合体を脱水閉環して得られる。このポリアミド酸溶液は、上記一般式（１）で表されるエステル酸二無水物及び上記一般式（２）または（３）で表される１種以上のジアミン成分を実質的に等モル使用し、有機極性溶媒中で重合して得られる。
【００３１】
このポリイミドは、まず、アルゴン、窒素などの不活性雰囲気中において、一般式（２）および／または一般式（３）で表される１種以上のジアミンと、一般式（１）で表されるエステル酸二無水物より選択される酸二無水物を有機極性溶媒中に溶解または拡散させポリアミド酸重合体の溶液を得る。
【００３２】
各モノマーの添加順序としては、一般式（１）を有機極性溶媒中に先に加えておき、ジアミン成分である上記一般式（２）及び／または一般式（３）を添加し、ポリアミド酸重合体の溶液としてもよい。
【００３３】
ポリアミド酸溶液の生成反応に用いられる有機極性溶剤としては、例えば、ジメチルスルホキシド、ジエチルスルホキシドなどのスルホキシド系溶媒、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジエチルホルムアミド等のホルムアミド系溶媒、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ，Ｎ−ジエチルアセトアミド等のアセトアミド系溶媒、Ｎ−メチルー２ーピロリドンなどのピロリドン系溶媒、フェノール、ｏ−，ｐ−，ｍ−，またはｐ−クレゾール、キシノール、ハロゲン化フェノール、カテコールなどのフェノール系溶媒、あるいはヘキサメチルホスホルアミド、γーブチロラクトンなどをあげることができる。さらに必要に応じて、これらの有機極性溶媒とキシレンあるいはトルエンなどの芳香族炭化水素とを組み合わせて用いることもできる。
【００３４】
上記得られたポリアミド酸重合体は、熱的または化学的方法により、脱水閉環し、ポリイミドを得る。イミド化の方法は、ポリアミド酸溶液を熱処理して脱水する熱的方法、脱水剤を用いて脱水する化学的方法のいずれも用いられる。
【００３５】
熱的に脱水閉環する方法は、上記ポリアミド酸溶液の溶媒を蒸発させ、また化学的に脱水閉環する方法は、上記ポリアミド酸溶液に化学量論以上の脱水剤と触媒を加え有機溶媒を蒸発させ、熱的方法、化学的方法ともに、加熱して乾燥させつつイミド化させ本発明にかかる樹脂組成物を構成するポリイミドを得る。有機溶媒の蒸発は、１５０℃以下の温度で約５分から９０分の時間の範囲内で行うのが好ましい。また、イミド化のための加熱温度は、常温〜約２５０℃まで適宜選択し、徐々に加熱する。化学的方法による脱水剤としては、例えば、無水酢酸等の脂肪族酸無水物、および芳香族酸無水物があげられる。また、触媒としては、トリエチルアミンなどの脂肪族第３級アミン類、ジメチルアニリン等の芳香族第３級アミン類、ピリジン、イソキノリン等の複素環第３級アミン類などがあげられる。
【００３６】
このうち、化学的方法によると、上記加熱温度が低温であり、イミド化に要する時間が短縮され、生成するポリイミドの伸び、あるいは引っ張り強度等の機械特性にも影響がないため好ましい。熱的方法および化学的方法との併用も用い得る。
【００３７】
上記得られたポリイミドは、低吸水性を有し、またガラス転移温度を比較的低温において有するため、低吸水性及び低温接着を可能とする優れた接着材料として用い得る樹脂組成物の構成成分として用いることができる。従って、本発明にかかる樹脂組成物の硬化時において、１．５％以下、好ましくは１．３％以下、特に好ましくは１．０％以下という優れた低吸水率を発現することを可能とする。
【００３８】
本発明にかかる樹脂組成物は、上記エステル酸二無水物とジアミンとからなるポリイミドにエポキシ樹脂を混合することを特徴とする。本発明にかかる樹脂組成物は、エポキシ樹脂を用いることにより、本発明に用いられるポリイミドの有する優れた耐熱性及び低吸水率等の特性に、さらに良好な接着性を付与することができる。
【００３９】
本発明に使用されるエポキシ樹脂としては、ビスフェノール系エポキシ樹脂、ハロゲン化ビスフェノール系エポキシ樹脂、フェノールノボラック系エポキシ樹脂、ハロゲン化フェノールノボラック系エポキシ樹脂、アルキルフェノールノボラック系エポキシ樹脂、ポリフェノール系エポキシ樹脂、ポリグリコール系エポキシ樹脂、環状脂肪族エポキシ樹脂、クレゾールノボラック系エポキシ樹脂、グリシジルアミン系エポキシ樹脂、ウレタン変性エポキシ樹脂、ゴム変性エポキシ樹脂、エポキシ変性ポリシロキサン等が用いることができる。
【００４０】
エポキシ樹脂の混合割合は、ポリイミド１００部に対して１〜５０部、好ましくは５〜３０部加えるのが望ましい。少なすぎると接着強度が低く、多すぎると柔軟性、耐熱性に劣るものとなる。
【００４１】
さらに、吸水性、耐熱性、接着性等必要に応じて、酸二無水物系、アミン系、イミダゾール系等の一般に用いられるエポキシ硬化剤、促進剤や種々のカップリング剤を併用し得る。また、エポキシ樹脂以外の熱硬化性樹脂、フェノール樹脂、シアナート樹脂等も用い得る。
【００４２】
従来のポリイミド系接着剤は、銅箔等の金属およびポリイミド等の樹脂フィルムに対して接着性が十分でなく、またエポキシ樹脂との混合は、その難溶性より困難であったが、本発明にかかる樹脂組成物は、銅箔等の金属箔やポリイミドフィルムとの接着性が良好であり、またその有機溶媒に対する溶解性が良好であるという特性をも併せ有することより、使用に際し加工性に優れる。例えばポリアミド酸重合体溶液をイミド化した溶液を、直接シート状に形成した状態またはワニスの状態として用いることができ、さらには、固体状としてから適宜有機溶媒に溶解してワニスとしても用いうる。
【００４３】
本発明の樹脂組成物の接着材料としての具体的な使用態様は、当業者が実施しうる範囲内で種々の方法があるが、例えば、あらかじめシート状に成形しておき、シート状接着剤として用い得る。また、本発明の樹脂組成物は、ガラス布、ガラスマット、芳香族ポリアミド繊維布、芳香族ポリアミド繊維マット等にワニスとして含浸し、樹脂を半硬化させ、繊維強化型のシート状接着剤として用いることも可能である。
【００４４】
さらに、本発明の樹脂組成物を溶媒に溶解し、ワニスとしてそのまま用いることもできる。具体的にはポリイミドフィルムの片面もしくは両面に樹脂組成物を溶解したワニスを塗布、乾燥し、銅箔・アルミ箔、４２合金箔等の金属箔やポリイミドフィルム、印刷回路基板等を加熱加圧して接着しても良い。この場合のポリイミドフィルムの種類は特に限定されない。溶解する有機溶媒としては、特に限定されないが、ポリアミド酸溶液の生成反応に用いられる有機極性溶剤が好ましい。例えば、ジメチルスルホキシド、ジエチルスルホキシドなどのスルホキシド系溶媒、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジエチルホルムアミド等のホルムアミド系溶媒、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ，Ｎ−ジエチルアセトアミド等のアセトアミド系溶媒、Ｎ−メチルー２ーピロリドンなどのピロリドン系溶媒、フェノール、ｏ−，ｐ−，ｍ−，またはｐ−クレゾール、キシノール、ハロゲン化フェノール、カテコールなどのフェノール系溶媒、あるいはヘキサメチルホスホルアミド、γーブチロラクトンなどをあげることができる。さらに必要に応じて、これらの有機極性溶媒とキシレンあるいはトルエンなどの芳香族炭化水素とを組み合わせて用い得るが、これらに限定されるものではない。また、この場合の接着条件としては、接着硬化するために必要十分である接着条件であればよく、具体的には加熱温度１５０℃〜２５０℃、圧力０．１〜１０ＭＰａで加熱時間５〜２０分程度の条件がで加熱加圧することが好ましい。
【００４５】
上記のようにして得られる本発明にかかる樹脂組成物は、電子機器、特にフレキシブル印刷回路基板、ＴＡＢ用テープ、複合リードフレーム、積層材料等に好適に用いられ得る特性を有する。すなわち、具体的には、１．５％以下、好ましくは、１．３％以下、特に好ましくは、１．０％以下という優れた低吸水率を示し、また半田耐熱性に優れ、かつ耐熱性、接着性ともに優れており、接着剤として使用する際約２５０℃以下の温度で接着可能である。
【００４６】
【実施例】
以下、実施例により本発明を具体的に説明するが、これら実施例は、本発明を説明するものであり、限定するためのものではない。当業者は、本発明の範囲を逸脱することなく、種々の変更、修正、及び改変を行い得る。
【００４７】
（実施例１）
容量５００ｍｌのガラス製フラスコに，ジメチルホルムアミド（以下、ＤＭＦという。）２８０ｇに３、３’−ビス（アミノフェノキシフェニル）プロパン（メタ型: 以下、ＢＡＰＰ−Ｍという。）０．１４８７ｍｏｌを仕込み窒素雰囲気下で撹拌溶解する。さらにフラスコ内を窒素置換雰囲気下、溶液を氷水で冷却しつつ撹拌し、２，２−ビス（４−ヒドロキシフェニル）プロパンジベンゾエート−３，３’，４，４’−テトラカルボン酸二無水物（以下、ＥＳＤＡという。）０．１４８７ｍｏｌを粘度に注目しながら徐々に添加した。粘度が１５００poise に達したところでＥＳＤＡの添加をやめポリアミド酸重合体溶液を得た。
【００４９】
このポリアミド酸溶液に、ＤＭＦ１５０、βーピコリン３５ｇ、無水酢酸６０ｇを加え１時間攪拌した後、さらに１００℃下で１時間攪拌し、イミド化させた。その後、高速で攪拌したメタノール中にこの溶液を少しづつ垂らした。メタノール中に析出した糸状のポリイミドを１００℃で３０分乾燥後、ミキサーで粉砕し、メタノールでソックスレー洗浄を行い、１００℃で２時間乾燥させ、ポリイミド粉末を得た。
【００５０】
上記で得たポリイミド粉末を２０ｇ、ビスフェノールＡ系のエポキシ樹脂；エピコート８２８（油化シェル社製）を５ｇ、硬化促進剤として２−エチル−４−メチルイミダゾール０．０１５ｇを８３ｇのＤＭＦに溶解した。得られたワニスをガラス板上に流延し、１００℃で１０分間乾燥後、ガラス板より引き剥し、鉄枠に固定しさらに１５０℃で２０分乾燥し、厚み２５μm のシートを得た。得られたシートをポリイミドフィルム（アピカル５０ＡＨ、鐘淵化学工業社製）と厚さ２５μm の銅箔で挟み込み、温度２００℃、圧力３ＭＰａで２０分加熱加圧し、銅張フレキシブル積層板を得た。
【００５１】
（実施例２）
実施例１で得たワニスをポリイミドフィルム（アピカル５０ＡＨ、鐘淵化学工業株式会社製）に塗布して、１００℃で１０分、さらに１５０℃で２０分加熱乾燥させ厚み２５μm の接着剤層を形成した。得られた接着剤層付き片面ポリイミドフィルムと２５μm 銅箔を温度２００℃、圧力３ＭＰａで２０分間加熱し、銅張フレキシブル積層板を得た。
【００５２】
（実施例３）
実施例１で得たポリイミド粉末２０ｇ、グリシジルアミン型エポキシ樹脂；ＴＥＴＲＡＤ−Ｃ（三菱瓦斯化学株式会社製）５ｇを８３ｇのＤＭＦに溶解した。得られたワニスをガラス板上に流延し、１００℃で１０分間乾燥後、ガラス板より引き剥し、鉄枠に固定しさらに１５０℃で２０分乾燥し、厚み２５μm のシートを得た。得られたシートをポリイミドフィルム（アピカル５０ＡＨ、鐘淵化学工業株式会社製）と厚さ２５μm の銅箔で挟み込み、温度２００℃、圧力３ＭＰａで２０分加熱加圧し、銅張フレキシブル積層板を得た。
【００５７】
（実施例４）
ジアミン成分を３、３'−ビス（アミノフェノキシフェニル）スルフォン（ＢＡＰＳ−Ｍ）とする以外は、実施例１と同様にして、ポリアミド酸重合体溶液を得、ポリイミド粉末を得た。
【００５８】
上記で得たポリイミド粉末を、実施例１と同様にして、銅張フレキシブル積層板を得た。
【００５９】
（比較例１）
容量５００ｍｌのガラス製フラスコにジメチルホルムアミド（ＤＭＦ）２８０ｇに３、３’−ビス（アミノフェノキシフェニル）プロパン（以下、ＢＡＰＰ−Ｍという）０．１４８７ｍｏｌを仕込み窒素雰囲気下で撹拌溶解する。さらに溶液を氷水で冷やしつつ、かつフラスコ内の雰囲気を窒素置換しながら撹拌しながらベンゾフェノンテトラカルボン酸二無水物（以下、ＢＴＤＡという）０．１４８７ｍｏｌを粘度に注目しながら徐々に添加した。粘度が１５００poise に達したところでＢＴＤＡの添加をやめポリアミド酸重合体溶液を得た。
【００６０】
このポリアミド酸溶液にＤＭＦ１５０ｇ、β−ピコリン３５ｇ、無水酢酸６０ｇを加え１時間撹拌した後、さらに１００℃下で１時間撹拌し、イミド化させた。その後、高速で撹拌したメタノール中にこの溶液を少しづつ垂らした。メタノール中に析出した糸状のポリイミドを１００℃で３０分乾燥後、ミキサーで粉砕し、メタノールでソックスレー洗浄を行い、１００℃で２時間乾燥させ、ポリイミド粉末を得た。
【００６１】
上記で得たポリイミド粉末を２０ｇ、エピコート８２８（油化シェル社製）を５ｇ、２−エチル−４−メチルイミダゾール０．０１５ｇを８３ｇのＤＭＦに溶解した。得られたワニスをガラス板上に流延し、１００℃で１０分間乾燥後、ガラス板より引き剥し、鉄枠に固定しさらに１５０℃で２０分乾燥し、厚み２５μm のシートを得た。得られたシートをポリイミドフィルム（アピカル５０ＡＨ、鐘淵化学工業社製）と２５μm の銅箔で挟み込み、温度２００℃、圧力３ＭＰａで２０分加熱加圧し、銅張フレキシブル積層板を得た。
【００６２】
（比較例２）
実施例１で得たポリイミド粉末２０ｇを８３ｇのＤＭＦに溶解した。得られたワニスをガラス板上に流延し、１００℃で１０分間乾燥後、ガラス板より引き剥し、鉄枠に固定しさらに１５０℃で２０分乾燥し、厚み２５μm のシートを得た。得られたシートをポリイミドフィルム（アピカル５０ＡＨ、鐘淵化学工業社製）と２５μm の銅箔で挟み込み、温度２００℃、圧力３ＭＰａで２０分加熱加圧し、銅張フレキシブル積層板を得た。
【００６３】
（比較例３）
プラタボンドＭ１２７６（共重合ナイロン、日本リルサン社製）を１０ｇ、エピコート８２８（油化シェル社製）を２０ｇ、ジアミノジフェニルサルフォンを１ｇを８３ｇのＤＭＦに溶解した。得られたワニスをガラス板上に流延し、１００℃で１０分間乾燥後、ガラス板より引き剥し、鉄枠に固定しさらに１５０℃で２０分乾燥し、厚み２５μm のシートを得た。得られたシートをポリイミドフィルム（アピカル５０ＡＨ、鐘淵化学工業社製）と２５μm の銅箔で挟み込み、温度２００℃、圧力３ＭＰａで２０分加熱加圧し、銅張フレキシブル積層板を得た。
【００６４】
以上の各実施例及び比較例で得られたフレキシブル銅張積層板について引き剥し強度、半田耐熱性を評価した。また、各接着シートの吸水率も併せて評価した。その結果を表１に示す。
【００６５】
【表１】
なお、引き剥がし強度は、ＪＩＳＣ ６４８１に準拠した。また、半田耐熱性は、２６０℃半田浴に１０秒浸漬したときの外観評価が、膨れがなく良好のものを○とした。
【００６７】
また、吸水率は、ＡＳＴＭ Ｄ５７０に基づいた測定により算出した。フィルムを１５０℃で３０分間乾燥させたものの重量をＷ1 とし、２４時間蒸留水に浸したあと表面を拭き取ったものの重量をＷ2 とし、下記式により算出した。
吸水率( ％）＝（Ｗ2 −Ｗ1 ）÷Ｗ1 ×１００
【００６８】
【発明の効果】
本発明の樹脂組成物は、接着剤として使用するときに２５０℃程度の温度で接着可能である。従来の耐熱接着剤と異なり、接着に高温を要せず、ポリイミドフィルムに対しても高い接着力を示し、高温まで高い接着力を保持する。さらに１．５％以下という低吸水率であるため、半田浴に浸漬する際の膨れ等を生じない半田耐熱性を有する。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a resin composition that can be adhesively cured at a relatively low temperature, is soluble in a solvent, and has excellent heat resistance and adhesiveness. The resin composition of the present invention is useful as an adhesive excellent in heat resistance and adhesiveness used for flexible printed circuit boards, TAB (Tape Automated Bonding) tapes, composite lead frames, laminated materials and the like.
[0002]
[Prior art]
In recent years, electronic devices have been improved in function, performance, and size, and accordingly, electronic components used are required to be reduced in size and weight. Therefore, semiconductor device packaging methods and wiring materials or wiring components for mounting them have been required to have higher density, higher functionality, and higher performance. In particular, it has good adhesion that can be suitably used as a semiconductor package, COL and LOC packages, high-density mounting materials such as MCM (Multi Chip Module), printed wiring board materials such as multilayer FPC, and aerospace materials. There is a need for materials to show.
[0003]
Conventionally, acrylic, phenolic, epoxy, and polyimide adhesives are known as adhesive materials that exhibit good mechanical characteristics, heat resistance characteristics, and insulation characteristics in semiconductor packages and other mounting materials.
[0004]
However, phenolic and epoxy adhesives are excellent in adhesiveness but inferior in flexibility. A flexible acrylic adhesive has a problem of low heat resistance.
[0005]
[Problems to be solved by the invention]
In order to solve these problems, polyimide is used. Polyimide is excellent in heat resistance among various organic polymers, and is therefore widely used from the space and aviation fields to the electronic communication field, and is also used as an adhesive material. However, a polyimide adhesive with high heat resistance requires a high temperature of about 300 ° C. and a high pressure for bonding, and the adhesive strength is not so high. Further, the conventional polyimide adhesive has a high water absorption rate, and has a problem that, for example, when a lead frame using this polyimide adhesive is immersed in a solder bath, it tends to swell.
[0006]
[Means for Solving the Problems]
The present invention provides a resin composition having a low water absorption, excellent solder heat resistance, excellent heat resistance and adhesion, and capable of bonding at a low temperature of 250 ° C. or lower.
[0007]
The gist of the present invention lies in the general formula (1)
[0008]
[Formula 4]
And an ester dianhydride represented by the formula (2)
[0010]
[Chemical formula 5]
The resin composition which consists of the polyimide which consists of diamine, and an epoxy resin is made into the content.
[0012]
In the diamine represented by the general formula (2), the general formula (3)
[0013]
[Chemical 6]
It is related with the said resin composition characterized by these.
[0015]
Further, the water absorption after curing is 1 . The resin composition is characterized by being 5% or less.
[0016]
DETAILED DESCRIPTION OF THE INVENTION
The present invention relates to a general formula (1)
(Wherein X represents a divalent group containing an aromatic ring) and a resin composition comprising the dianhydride ester represented by formula (2) or formula (3).
[0017]
The acid dianhydride used in the polyimide composition according to the present invention has the general formula (1)
[0018]
[Chemical 7]
(In the formula, X is a divalent organic group.)
It is essential to use an ester dianhydride represented by:
[0020]
Since the polyimide composition using the ester dianhydride represented by the general formula (1) has an excellent low water absorption, the polyimide composition has excellent solder heat resistance.
[0021]
Further, the general formula (2)
[0022]
[Chemical 8]
(In the formula, Y represents —C (═O) —, —SO 2 —, —O—, —S—, — (CH 2 ) m —, —NHCO—, —C (CH 3 ) 2 —, —C (CF 3 ) 2 —, —C (═O) O—, or a bond, and m and n are integers of 1 or more and 5 or less).
[0024]
Moreover, in General formula (2), several Y may be the same or 2 or more types of substituents. In addition, the hydrogen of each benzene ring can be appropriately substituted with various substituents within the range conceivable by those skilled in the art. For example, halogen groups such as a methyl group, an ethyl group, Br, and Cl can be exemplified, but the substituent is not limited thereto.
[0025]
Furthermore, the present inventors have found that the solubility of the polyimide composition using the diamine represented by the general formula (2) in the meta position is increased due to bonding to the meta position, It paid attention to showing the outstanding usefulness when using as an adhesive agent.
[0026]
Specifically, as the diamine, in the general formula (2), particularly the amino group is represented by the general formula (3)
[0027]
[Chemical 9]
(In the formula, Y represents —C (═O) —, —SO 2 —, —O—, —S—, — (CH 2 ) m —, —NHCO—, —C (CH 3 ) 2 —, —C (CF 3 ) 2 —, —C (═O) O—, or a bond. M and n are integers of 1 or more and 5 or less. By having an amino group at the meta position, the solubility of the produced polyimide in an organic solvent becomes better, and the processability is excellent.
[0029]
The diamine represented by general formula (2) or general formula (3) may be used alone or in combination of two or more.
[0030]
The polyimide used in the resin composition according to the present invention is obtained by dehydrating and ring-closing the polyamic acid polymer that is a precursor thereof. The polyamic acid solution uses substantially equimolar amounts of the ester dianhydride represented by the general formula (1) and one or more diamine components represented by the general formula (2) or (3). Obtained by polymerization in an organic polar solvent.
[0031]
This polyimide is first represented by general formula (1) and one or more diamines represented by general formula (2) and / or general formula (3) in an inert atmosphere such as argon or nitrogen. An acid dianhydride selected from ester dianhydrides is dissolved or diffused in an organic polar solvent to obtain a polyamic acid polymer solution.
[0032]
As the addition order of each monomer, the general formula (1) is added to the organic polar solvent first, the above general formula (2) and / or the general formula (3) as the diamine component is added, and the polyamic acid weight is added. A combined solution may be used.
[0033]
Examples of the organic polar solvent used in the reaction for forming the polyamic acid solution include sulfoxide solvents such as dimethyl sulfoxide and diethyl sulfoxide, formamide solvents such as N, N-dimethylformamide and N, N-diethylformamide, and N, N. -Acetamide solvents such as dimethylacetamide, N, N-diethylacetamide, pyrrolidone solvents such as N-methyl-2-pyrrolidone, phenol, o-, p-, m-, or p-cresol, xinol, halogenated phenol, catechol Examples thereof include phenol solvents such as hexamethylphosphoramide, γ-butyrolactone, and the like. Further, if necessary, these organic polar solvents can be used in combination with an aromatic hydrocarbon such as xylene or toluene.
[0034]
The obtained polyamic acid polymer is dehydrated and closed by a thermal or chemical method to obtain a polyimide. As the imidization method, either a thermal method in which a polyamic acid solution is heat-treated for dehydration or a chemical method for dehydration using a dehydrating agent is used.
[0035]
The method of thermally dehydrating and cyclizing evaporates the solvent of the polyamic acid solution, and the method of chemically dehydrating and cyclizing evaporates the organic solvent by adding a dehydrating agent and a catalyst that are more than stoichiometric to the polyamic acid solution. Both the thermal method and the chemical method are heated and dried to imidize to obtain a polyimide constituting the resin composition according to the present invention. The evaporation of the organic solvent is preferably performed at a temperature of 150 ° C. or less for a time period of about 5 to 90 minutes. The heating temperature for imidization is appropriately selected from room temperature to about 250 ° C., and is gradually heated. Examples of the dehydrating agent by a chemical method include aliphatic acid anhydrides such as acetic anhydride, and aromatic acid anhydrides. Examples of the catalyst include aliphatic tertiary amines such as triethylamine, aromatic tertiary amines such as dimethylaniline, and heterocyclic tertiary amines such as pyridine and isoquinoline.
[0036]
Among these, the chemical method is preferable because the heating temperature is low, the time required for imidization is shortened, and the mechanical properties such as elongation or tensile strength of the resulting polyimide are not affected. Combinations with thermal and chemical methods can also be used.
[0037]
The polyimide obtained above has a low water absorption and has a glass transition temperature at a relatively low temperature, and therefore, as a component of a resin composition that can be used as an excellent adhesive material that enables low water absorption and low-temperature bonding. Can be used. Accordingly, when the resin composition according to the present invention is cured, 1 . 5% or less, preferably 1 . 3% or less, particularly preferably 1 . It is possible to develop an excellent low water absorption of 0% or less.
[0038]
The resin composition concerning this invention mixes an epoxy resin with the polyimide which consists of the said ester dianhydride and diamine, It is characterized by the above-mentioned. By using an epoxy resin, the resin composition according to the present invention can impart better adhesive properties to the excellent heat resistance and low water absorption properties of the polyimide used in the present invention.
[0039]
Examples of the epoxy resin used in the present invention include bisphenol epoxy resins, halogenated bisphenol epoxy resins, phenol novolac epoxy resins, halogenated phenol novolac epoxy resins, alkylphenol novolac epoxy resins, polyphenol epoxy resins, polyglycols. Epoxy resins, cycloaliphatic epoxy resins, cresol novolac epoxy resins, glycidylamine epoxy resins, urethane-modified epoxy resins, rubber-modified epoxy resins, epoxy-modified polysiloxanes, and the like can be used.
[0040]
The mixing ratio of the epoxy resin is 1 to 50 parts, preferably 5 to 30 parts with respect to 100 parts of polyimide. If the amount is too small, the adhesive strength is low. If the amount is too large, the flexibility and heat resistance are poor.
[0041]
Furthermore, generally used epoxy curing agents such as acid dianhydrides, amines, and imidazoles, accelerators, and various coupling agents may be used in combination as required, such as water absorption, heat resistance, and adhesiveness. Moreover, thermosetting resins other than epoxy resins, phenol resins, cyanate resins, and the like can also be used.
[0042]
Conventional polyimide-based adhesives have insufficient adhesion to metals such as copper foil and resin films such as polyimide, and mixing with epoxy resins has been more difficult than its poor solubility. Such a resin composition has excellent adhesion to metal foil such as copper foil and polyimide film, and also has excellent solubility in an organic solvent, so that it is excellent in workability in use. . For example, a solution obtained by imidizing a polyamic acid polymer solution can be used directly in a sheet form or in a varnish state, and can also be used as a varnish after being dissolved in an organic solvent as appropriate after being solid.
[0043]
There are various methods of using the resin composition of the present invention as an adhesive material within a range that can be carried out by those skilled in the art. For example, the resin composition is molded into a sheet in advance and used as a sheet adhesive. Can be used. The resin composition of the present invention is used as a fiber-reinforced sheet-like adhesive by impregnating glass cloth, glass mat, aromatic polyamide fiber cloth, aromatic polyamide fiber mat, etc. as a varnish, semi-curing the resin. It is also possible.
[0044]
Furthermore, the resin composition of the present invention can be dissolved in a solvent and used as it is as a varnish. Specifically, a varnish in which a resin composition is dissolved is applied to one or both sides of a polyimide film, dried, and heated and pressed on a metal foil such as copper foil / aluminum foil, 42 alloy foil, polyimide film, printed circuit board, etc. It may be adhered. The kind of polyimide film in this case is not particularly limited. Although it does not specifically limit as an organic solvent to melt | dissolve, The organic polar solvent used for the production | generation reaction of a polyamic acid solution is preferable. For example, sulfoxide solvents such as dimethyl sulfoxide and diethyl sulfoxide, formamide solvents such as N, N-dimethylformamide and N, N-diethylformamide, and acetamide solvents such as N, N-dimethylacetamide and N, N-diethylacetamide , Pyrrolidone solvents such as N-methyl-2-pyrrolidone, phenol solvents such as phenol, o-, p-, m-, or p-cresol, xinol, halogenated phenol, catechol, or hexamethylphosphoramide, γ- Examples include butyrolactone. Further, if necessary, these organic polar solvents and aromatic hydrocarbons such as xylene or toluene can be used in combination, but are not limited thereto. Further, the bonding conditions in this case may be any bonding conditions that are necessary and sufficient for adhesive curing. Specifically, the heating temperature is 150 ° C. to 250 ° C., the pressure is 0.1 to 10 MPa, and the heating time is 5 to 20. It is preferable to heat and press under the condition of about minutes.
[0045]
The resin composition according to the present invention obtained as described above has characteristics that can be suitably used for electronic devices, particularly flexible printed circuit boards, TAB tapes, composite lead frames, laminated materials and the like. Specifically, 1 . 5% or less, preferably 1 . 3% or less, particularly preferably 1 . It exhibits an excellent low water absorption of 0% or less, excellent solder heat resistance, excellent heat resistance and adhesion, and can be bonded at a temperature of about 250 ° C. or less when used as an adhesive.
[0046]
【Example】
Hereinafter, the present invention will be specifically described by way of examples. However, these examples are intended to illustrate the present invention and are not intended to limit the present invention. Those skilled in the art may make various changes, modifications, and alterations without departing from the scope of the present invention.
[0047]
Example 1
A glass flask with a capacity of 500 ml was charged with 0.1487 mol of 3,3′-bis (aminophenoxyphenyl) propane (meta type: hereinafter referred to as BAPP-M) in 280 g of dimethylformamide (hereinafter referred to as DMF) and a nitrogen atmosphere. Dissolve under stirring. Further, the flask was stirred while cooling the solution with ice water under a nitrogen-substituted atmosphere, and 2,2-bis (4-hydroxyphenyl) propanedibenzoate-3,3 ′, 4,4′-tetracarboxylic dianhydride (Hereinafter referred to as ESDA) 0.1487 mol was gradually added while paying attention to the viscosity. When the viscosity reached 1500 poise, the addition of ESDA was stopped to obtain a polyamic acid polymer solution.
[0049]
To this polyamic acid solution, DMF150, 35 g of β-picoline and 60 g of acetic anhydride were added and stirred for 1 hour, and further stirred at 100 ° C. for 1 hour to imidize. Then, this solution was dropped little by little in methanol stirred at high speed. The filamentous polyimide deposited in methanol was dried at 100 ° C. for 30 minutes, pulverized with a mixer, washed with Soxhlet with methanol, and dried at 100 ° C. for 2 hours to obtain polyimide powder.
[0050]
20 g of the polyimide powder obtained above, 5 g of bisphenol A epoxy resin; 5 g of Epicoat 828 (manufactured by Yuka Shell), and 0.015 g of 2-ethyl-4-methylimidazole as a curing accelerator were dissolved in 83 g of DMF. . The obtained varnish was cast on a glass plate, dried at 100 ° C. for 10 minutes, peeled off from the glass plate, fixed to an iron frame, and further dried at 150 ° C. for 20 minutes to obtain a sheet having a thickness of 25 μm. The obtained sheet was sandwiched between a polyimide film (Apical 50AH, manufactured by Kaneka Chemical Co., Ltd.) and a copper foil having a thickness of 25 μm, and heated and pressurized at a temperature of 200 ° C. and a pressure of 3 MPa for 20 minutes to obtain a copper-clad flexible laminate.
[0051]
(Example 2)
The varnish obtained in Example 1 was applied to a polyimide film (Apical 50AH, Kaneka Chemical Co., Ltd.) and dried by heating at 100 ° C. for 10 minutes and further at 150 ° C. for 20 minutes to form an adhesive layer having a thickness of 25 μm. did. The obtained single-sided polyimide film with an adhesive layer and 25 μm copper foil were heated at a temperature of 200 ° C. and a pressure of 3 MPa for 20 minutes to obtain a copper-clad flexible laminate.
[0052]
(Example 3)
20 g of the polyimide powder obtained in Example 1, glycidylamine type epoxy resin; 5 g of TETRAD-C (manufactured by Mitsubishi Gas Chemical Co., Inc.) were dissolved in 83 g of DMF. The obtained varnish was cast on a glass plate, dried at 100 ° C. for 10 minutes, peeled off from the glass plate, fixed to an iron frame, and further dried at 150 ° C. for 20 minutes to obtain a sheet having a thickness of 25 μm. The obtained sheet was sandwiched between a polyimide film (Apical 50AH, Kaneka Chemical Co., Ltd.) and a copper foil with a thickness of 25 μm, and heated and pressurized at a temperature of 200 ° C. and a pressure of 3 MPa for 20 minutes to obtain a copper-clad flexible laminate. .
[0057]
(Example 4 )
A polyamic acid polymer solution was obtained in the same manner as in Example 1 except that the diamine component was 3,3′-bis (aminophenoxyphenyl) sulfone (BAPS-M) to obtain a polyimide powder.
[0058]
A copper-clad flexible laminate was obtained in the same manner as Example 1 using the polyimide powder obtained above.
[0059]
(Comparative Example 1)
In a glass flask having a capacity of 500 ml, 0.1487 mol of 3,3′-bis (aminophenoxyphenyl) propane (hereinafter referred to as BAPP-M) is charged in 280 g of dimethylformamide (DMF) and dissolved under stirring in a nitrogen atmosphere. Further, 0.1487 mol of benzophenone tetracarboxylic dianhydride (hereinafter referred to as BTDA) was gradually added while paying attention to viscosity while stirring the solution while cooling the solution with ice water and replacing the atmosphere in the flask with nitrogen. When the viscosity reached 1500 poise, the addition of BTDA was stopped to obtain a polyamic acid polymer solution.
[0060]
To this polyamic acid solution, 150 g of DMF, 35 g of β-picoline and 60 g of acetic anhydride were added and stirred for 1 hour, and further stirred at 100 ° C. for 1 hour to imidize. Then, this solution was dropped little by little in methanol stirred at high speed. The filamentous polyimide deposited in methanol was dried at 100 ° C. for 30 minutes, pulverized with a mixer, washed with Soxhlet with methanol, and dried at 100 ° C. for 2 hours to obtain polyimide powder.
[0061]
20 g of the polyimide powder obtained above, 5 g of Epicoat 828 (manufactured by Yuka Shell), and 0.015 g of 2-ethyl-4-methylimidazole were dissolved in 83 g of DMF. The obtained varnish was cast on a glass plate, dried at 100 ° C. for 10 minutes, peeled off from the glass plate, fixed to an iron frame, and further dried at 150 ° C. for 20 minutes to obtain a sheet having a thickness of 25 μm. The obtained sheet was sandwiched between a polyimide film (Apical 50AH, Kaneka Chemical Co., Ltd.) and a 25 μm copper foil, and heated and pressurized at a temperature of 200 ° C. and a pressure of 3 MPa for 20 minutes to obtain a copper-clad flexible laminate.
[0062]
(Comparative Example 2)
20 g of the polyimide powder obtained in Example 1 was dissolved in 83 g of DMF. The obtained varnish was cast on a glass plate, dried at 100 ° C. for 10 minutes, peeled off from the glass plate, fixed to an iron frame, and further dried at 150 ° C. for 20 minutes to obtain a sheet having a thickness of 25 μm. The obtained sheet was sandwiched between a polyimide film (Apical 50AH, Kaneka Chemical Co., Ltd.) and a 25 μm copper foil, and heated and pressurized at a temperature of 200 ° C. and a pressure of 3 MPa for 20 minutes to obtain a copper-clad flexible laminate.
[0063]
(Comparative Example 3)
10 g of Platabond M1276 (copolymerized nylon, manufactured by Nippon Rilsan), 20 g of Epicoat 828 (manufactured by Yuka Shell), and 1 g of diaminodiphenylsulfone were dissolved in 83 g of DMF. The obtained varnish was cast on a glass plate, dried at 100 ° C. for 10 minutes, peeled off from the glass plate, fixed to an iron frame, and further dried at 150 ° C. for 20 minutes to obtain a sheet having a thickness of 25 μm. The obtained sheet was sandwiched between a polyimide film (Apical 50AH, Kaneka Chemical Co., Ltd.) and a 25 μm copper foil, and heated and pressurized at a temperature of 200 ° C. and a pressure of 3 MPa for 20 minutes to obtain a copper-clad flexible laminate.
[0064]
The flexible copper-clad laminates obtained in the above examples and comparative examples were evaluated for peel strength and solder heat resistance. Moreover, the water absorption rate of each adhesive sheet was also evaluated. The results are shown in Table 1.
[0065]
[Table 1]
The peeling strength was in accordance with JISC 6481. The solder heat resistance was evaluated as ◯ when the appearance evaluation when immersed in a 260 ° C. solder bath for 10 seconds was free from swelling.
[0067]
Further, the water absorption was calculated by measurement based on ASTM D570. The weight of the film dried at 150 ° C. for 30 minutes was defined as W 1, and the weight of the film wiped off after being soaked in distilled water for 24 hours was defined as W 2 .
Water absorption rate (%) = (W 2 −W 1 ) ÷ W 1 × 100
[0068]
【Effect of the invention】
The resin composition of the present invention can be bonded at a temperature of about 250 ° C. when used as an adhesive. Unlike conventional heat-resistant adhesives, it does not require high temperature for bonding, exhibits high adhesion to polyimide films, and maintains high adhesion to high temperatures. Furthermore, since it has a low water absorption of 1.5% or less, it has solder heat resistance that does not cause swelling when immersed in a solder bath.
Claims (2)
３、３'−ビス（アミノフェノキシフェニル）プロパン、
３、３'−ビス（アミノフェノキシフェニル）スルフォン
から選択される１種以上のジアミンを実質的に等モル使用し、有機極性溶媒中で重合して得られるポリアミド酸溶液からなるポリイミド及びエポキシ樹脂とからなる樹脂組成物。General formula (1)
3,3′-bis (aminophenoxyphenyl) propane,
3,3′-bis (aminophenoxyphenyl) sulfone
A resin composition comprising a polyimide and an epoxy resin comprising a polyamic acid solution obtained by polymerizing in an organic polar solvent using substantially one mole of one or more diamines selected from
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28255498A JP4875794B2 (en) | 1998-10-05 | 1998-10-05 | Resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28255498A JP4875794B2 (en) | 1998-10-05 | 1998-10-05 | Resin composition |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
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| JP2008148766A Division JP2009001793A (en) | 2008-06-06 | 2008-06-06 | Adhesive |
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| JP2000109645A JP2000109645A (en) | 2000-04-18 |
| JP4875794B2 true JP4875794B2 (en) | 2012-02-15 |
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| JP28255498A Expired - Lifetime JP4875794B2 (en) | 1998-10-05 | 1998-10-05 | Resin composition |
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Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE60016217T2 (en) * | 1999-04-09 | 2005-04-07 | Kaneka Corp. | POLYIMIDE RESIN COMPOSITION WITH IMPROVED MOISTURE RESISTANCE, GLUE SOLUTION, MULTILAYER ADHESIVE FILM AND METHOD FOR THE PRODUCTION THEREOF |
| JP4796687B2 (en) * | 2000-08-04 | 2011-10-19 | 株式会社カネカ | Adhesive composition |
| JP2002069420A (en) * | 2000-08-30 | 2002-03-08 | Kanegafuchi Chem Ind Co Ltd | Adhesive film for FPC reinforcement board |
| JP2002080815A (en) * | 2000-09-05 | 2002-03-22 | Kanegafuchi Chem Ind Co Ltd | Polyimide adhesive solution and film-like laminated member obtained using the same |
| JP2002121207A (en) * | 2000-10-16 | 2002-04-23 | Kanegafuchi Chem Ind Co Ltd | Composition, photosensitive composition and coverlay using the same |
| JP2003011308A (en) * | 2001-07-03 | 2003-01-15 | Kanegafuchi Chem Ind Co Ltd | Film-shaped laminated member |
| JP2003027014A (en) * | 2001-07-17 | 2003-01-29 | Kanegafuchi Chem Ind Co Ltd | Adhesive film |
| CN1309786C (en) * | 2002-03-08 | 2007-04-11 | 钟渊化学工业株式会社 | Thermosetting resin composition and laminates and circuit board substrates made by using same |
| WO2005080466A1 (en) * | 2004-02-25 | 2005-09-01 | Kaneka Corporation | Thermosetting resin composition and use thereof |
| JP5054516B2 (en) * | 2005-04-28 | 2012-10-24 | 株式会社野田スクリーン | Thermosetting resin composition |
| CN115197421A (en) | 2017-01-27 | 2022-10-18 | 积水化学工业株式会社 | Curable resin composition, adhesive, imide oligomer composition, and curing agent |
| JP7168326B2 (en) * | 2018-01-26 | 2022-11-09 | 積水化学工業株式会社 | Curable resin composition, cured product, adhesive, adhesive film, and circuit board |
| US12139576B2 (en) | 2018-03-28 | 2024-11-12 | Sekisui Chemical Co., Ltd. | Curable resin composition, adhesive agent, adhesive film, circuit substrate, interlayer insulating material, and printed wiring board |
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1998
- 1998-10-05 JP JP28255498A patent/JP4875794B2/en not_active Expired - Lifetime
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