JP4503239B2 - Flame-retardant adhesive composition, flexible copper-clad laminate, coverlay and adhesive film - Google Patents
Flame-retardant adhesive composition, flexible copper-clad laminate, coverlay and adhesive film Download PDFInfo
- Publication number
- JP4503239B2 JP4503239B2 JP2003128622A JP2003128622A JP4503239B2 JP 4503239 B2 JP4503239 B2 JP 4503239B2 JP 2003128622 A JP2003128622 A JP 2003128622A JP 2003128622 A JP2003128622 A JP 2003128622A JP 4503239 B2 JP4503239 B2 JP 4503239B2
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- adhesive composition
- wiring board
- printed wiring
- adhesive
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- 239000000853 adhesive Substances 0.000 title claims description 44
- 230000001070 adhesive effect Effects 0.000 title claims description 44
- 239000000203 mixture Substances 0.000 title claims description 38
- 239000002313 adhesive film Substances 0.000 title claims description 15
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims description 8
- 239000003063 flame retardant Substances 0.000 title claims description 8
- 239000012787 coverlay film Substances 0.000 title description 2
- 239000005001 laminate film Substances 0.000 title 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 34
- 229920000647 polyepoxide Polymers 0.000 claims description 33
- 239000003822 epoxy resin Substances 0.000 claims description 29
- 239000004593 Epoxy Substances 0.000 claims description 19
- 235000010290 biphenyl Nutrition 0.000 claims description 17
- 239000004305 biphenyl Substances 0.000 claims description 17
- -1 glycidyl compound Chemical class 0.000 claims description 13
- 239000013034 phenoxy resin Substances 0.000 claims description 13
- 229920006287 phenoxy resin Polymers 0.000 claims description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 229920005989 resin Polymers 0.000 claims description 11
- 239000011347 resin Substances 0.000 claims description 11
- 229920001721 polyimide Polymers 0.000 claims description 10
- 229920003051 synthetic elastomer Polymers 0.000 claims description 8
- 239000005061 synthetic rubber Substances 0.000 claims description 8
- 239000011889 copper foil Substances 0.000 claims description 7
- 239000011256 inorganic filler Substances 0.000 claims description 7
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical group C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 6
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 6
- 230000003014 reinforcing effect Effects 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 39
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 36
- 229920000459 Nitrile rubber Polymers 0.000 description 19
- 238000001723 curing Methods 0.000 description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 9
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 9
- 150000001412 amines Chemical class 0.000 description 9
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 9
- 238000002844 melting Methods 0.000 description 9
- 230000008018 melting Effects 0.000 description 9
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 8
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 239000000758 substrate Substances 0.000 description 7
- 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 6
- 239000012046 mixed solvent Substances 0.000 description 6
- 230000003712 anti-aging effect Effects 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000010408 film Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 229920003986 novolac Polymers 0.000 description 5
- VETPHHXZEJAYOB-UHFFFAOYSA-N 1-n,4-n-dinaphthalen-2-ylbenzene-1,4-diamine Chemical compound C1=CC=CC2=CC(NC=3C=CC(NC=4C=C5C=CC=CC5=CC=4)=CC=3)=CC=C21 VETPHHXZEJAYOB-UHFFFAOYSA-N 0.000 description 4
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 4
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 4
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical class C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- KCSOBOZCMQBPFM-UHFFFAOYSA-N 4-n,4-n-dinaphthalen-2-ylbenzene-1,4-diamine Chemical compound C1=CC(N)=CC=C1N(C=1C=C2C=CC=CC2=CC=1)C1=CC=C(C=CC=C2)C2=C1 KCSOBOZCMQBPFM-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229910000679 solder Inorganic materials 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 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
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-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
- 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
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- ZZLCFHIKESPLTH-UHFFFAOYSA-N 4-Methylbiphenyl Chemical compound C1=CC(C)=CC=C1C1=CC=CC=C1 ZZLCFHIKESPLTH-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Substances FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 150000002013 dioxins Chemical class 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 239000005350 fused silica glass Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical compound CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Non-Metallic Protective Coatings For Printed Circuits (AREA)
- Structure Of Printed Boards (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、ハロゲンフリーの難燃性接着剤組成物ならびにそれを用いたフレキシブル銅張積層板、カバーレイおよび接着フィルムに関し、さらには、これらを用いて製造されたプリント配線板に関する。
【０００２】
【従来の技術】
近年、世界的な環境問題、人体に対する安全性についての関心の高まりに伴なって、電気・電子機器については、従来からの難燃性に加えて、より少ない有害性、より高い安全性という要求が増大している。すなわち、電気・電子機器は、単に燃えにくいだけでなく、燃焼時に有害ガスや有害煙塵などの発生が少ないことが要望されている。従来、電気・電子機器の配線に使用するフレキシブルプリント配線板は、フレキシブル銅張積層板、カバーレイ及び接着フィルムにより構成されるが、そこに使用されている接着剤には、難燃剤として作用する臭素が含まれる臭素化エポキシ樹脂、特にテトラブロモビスフェノールＡ型エポキシ樹脂が一般に使用されている。
【０００３】
このような臭素化エポキシ樹脂は、良好な難燃性を有するものの、燃焼時に有害なハロゲン化ガス（臭化水素）等を発生することや、ブロモ化ダイオキシン、ブロモ化フラン類を発生する可能性が懸念されているため、その使用が抑制されつつある。
【０００４】
一方、カバーレイ、接着フィルムでは硬化前の状態でのハンドリング性が重要であり、このためには、合成ゴムが一般に配合されているが、これを多く含有する接着剤は難燃性に劣り、難燃成分を多く配合する必要があった。
【０００５】
【発明が解決しようとする課題】
本発明の目的は、ハロゲンを含まずに良好な難燃性を示す（ハロゲンフリー）とともに、耐熱性、耐折性、電気絶縁性、また、カバーレイ、接着フィルムといった硬化前の状態でのハンドリング性等に優れた接着剤組成物を提供することにある。
【０００６】
さらに、本発明は、そのような難燃性接着剤組成物を用いたフレキシブル銅張積層板、カバーレイおよび接着フィルム並びにこれらを用いて製造されたフレキシブルプリント配線板を提供することをも目的とする。
【０００７】
【課題を解決するための手段】
本発明者らは、上記の目的を達成しようと鋭意研究を重ねた結果、特定の構造を有するエポキシ樹脂を使用し、接着剤組成物中にホスファゼン化合物、無機充填剤を添加することと、可とう成分として合成ゴムとともにフェノキシ樹脂を配合することで、上記目的が達成されることを見いだし、本発明を完成させたものである。
【０００８】
即ち、本発明は、
（Ａ）下記一般式に示すビフェニル骨格及びフェノール骨格を有する多官能樹脂のグリシジル化合物であるエポキシ樹脂、
【化２】
（Ｂ）エポキシ用硬化剤、
（Ｃ）硬化促進剤、
（Ｄ）合成ゴム、
（Ｅ）重量平均分子量５０００〜１０００００であるフェノキシ樹脂、
（Ｆ）少なくとも１種のホスファゼン化合物および
（Ｇ）無機充填剤
を必須成分とし、フェノキシ樹脂がビフェニル骨格又はビスフェノールＦ骨格を有することを特徴とするハロゲンフリーの難燃性接着剤組成物である。また、上記ハロゲンフリーの難燃性接着剤組成物を用いたフレキシブル銅張積層板、カバーレイおよび接着フィルム並びにこれらを用いて製造されたフレキシブルプリント配線板である。
【０００９】
以下、本発明を詳細に説明する。
【００１０】
本発明に用いる（Ａ）エポキシ樹脂としては、前記の式化２で示されるビフェニル骨格を含有するような多官能のエポキシ樹脂が好ましく使用できる。またこのエポキシ樹脂は、必要に応じて、１分子中に２個以上のエポキシ基を有するエポキシ樹脂、例えば、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ノボラック型エポキシ樹脂、グリシジルエーテル型エポキシ樹脂、脂環式エポキシ樹脂、複素環型エポキシ樹脂等のエポキシ樹脂と混合して使用することができる。これらのエポキシ樹脂は、通常、溶剤に溶解して使用することができる。その溶剤は、エポキシ樹脂、エポキシ用硬化剤、エポキシ用硬化促進剤、エラストマーおよびホスファゼンを溶解するものであればよいが、接着剤の塗布乾燥工程において溶剤が残留しないように沸点１６０℃以下の溶剤であることが望ましい。具体的な溶剤としてはメチルエチルケトン、トルエン、アセトン、エチルセロソルブ、メチルセロソルブ、シクロヘキサノン等が挙げられ、これらは単独又は２種以上混合して使用することができる。
【００１１】
本発明に用いる（Ｂ）エポキシ用硬化剤としては、通常、エポキシ樹脂の硬化剤に使用されている化合物であれば特に制限なく使用でき、例えば、アミン硬化系としては、ジシアンジアミド（ＤＩＣＹ）、芳香族ジアミン等が挙げられ、フェノール硬化系としては、フェノールノボラック樹脂、クレゾールノボラック樹脂、ビスフェノールＡ型ノボラック樹脂、トリアジン変性フェノールノボラック樹脂等が挙げられ、これらは単独又は２種以上混合して使用することができる。
【００１２】
本発明に用いる（Ｃ）エポキシ用硬化促進剤としては、通常、エポキシ樹脂の硬化促進剤に使用されているものであり、例えば、２−エチル−４−メチル−イミダゾール、１−ベンジル−２−メチルイミダゾール等のイミダゾール化合物、三フッ化ホウ素アミン錯体、トリフェニルホスフィン等が挙げられ、これらは単独又は２種以上混合して使用することができる。
【００１３】
本発明に用いる（Ｄ）合成ゴムとしては、特に制限なく接着剤用として用いられているものは広く使用することができる。具体的なものとしては、アクリルゴム、アクリロニトリルブタジエンゴム、カルボキシ含有アクリロニトリルブタジエンゴム等の各種合成ゴムが挙げられ、これらは単独又は２種以上混合して使用することができる。これらの中で、屈曲性、耐折強さに優れるアクリロニトリルブタジエンゴムおよびその変性ゴムが特に好ましく使用される。
【００１４】
本発明に用いる（Ｅ）フェノキシ樹脂としては、重量平均分子量５０００〜１０００００で、ビフェニル骨格又はビスフェノールＦ骨格を含有するものが好ましく使用できる。このフェノキシ樹脂は、接着剤組成物の可とう性の向上と難燃性低下防止の目的で配合される。このフェノキシ樹脂の重量平均分子量が５０００未満では可とう性付与に効果が小さく、また１０００００を超えると必須成分である（Ｄ）合成ゴムとの相溶性が悪くなり、接着剤溶液の分離を起こしやすく好ましくない。
【００１５】
本発明に用いる（Ｆ）ホスファゼン化合物としては、実質的にハロゲンを含まないもので、耐熱性、耐湿性、難燃性、耐薬品性等の点から、融点が８０℃以上であるホスファゼン化合物を好ましく使用することができる。具体的な例として、下記化学式に示すシクロホスファゼンオリゴマー等が挙げられる。
【００１６】
【化３】
シクロホスファゼンオリゴマーにおけるハロゲンを含まない有機基Ｘとしては、アルコキシ基、フェノキシ基、アミノ基、アリル基等が挙げられる。該（Ｆ）ホスファゼン化合物の配合割合は、接着剤組成物全体に対して２〜２０重量％が好ましい。２重量％未満では十分な難燃性が得られず、また２０重量％を超えると接着力が低下して好ましくない。
【００１７】
本発明に用いる（Ｇ）無機充填剤としては特に制限はなく、タルク、アルミナ、水酸化アルミニウム、水酸化マグネシウム、溶融シリカ、合成シリカ等が挙げられ、これらは単独又は２種以上混合して使用することができる。該無機充填剤の配合割合は、接着剤組成物中の５〜５０重量％の割合で配合することが好ましい。配合量が５重量％未満では、十分な難燃性が得られず、また、５０重量％を超えると接着剤組成物が硬く脆くなるため、ポリイミドフィルムとの接着力が低下し好ましくない。
【００１８】
本発明の接着剤組成物は上述した（Ａ）ビフェニル骨格を含有するような多官能のエポキシ樹脂、（Ｂ）エポキシ用硬化剤、（Ｃ）エポキシ用硬化促進剤、（Ｄ）合成ゴム、（Ｅ）重量平均分子量５０００〜１０００００であるフェノキシ樹脂、（Ｆ）少なくとも１種のホスファゼン化合物および（Ｇ）無機充填剤を必須成分とするが、本発明の目的に反しない限度において、また必要に応じて、微粉末の無機質または有機質の充填剤、顔料、劣化防止剤等を添加配合することができる。上述したこれらの各成分は、メチルエチルケトン、トルエン等の溶剤を用いて、均一に溶解して容易にＦＰＣ基板用の接着剤組成物を製造することができる。
【００１９】
以上述べた本発明の接着剤組成物は、これをメチルエチルケトン、トルエン、アセトン、エチルセロソルブ、メチルセロソルブ、シクロヘキサノン等の好適な有機溶剤で希釈して樹脂溶液となし、これをポリイミドフィルム上に塗布し、熱ロールで銅箔を片面または両面に貼り合わせた後、加熱硬化するという通常の方法によりフレキシブル銅張積層板を製造することができる。
【００２０】
また、本発明の接着剤組成物は、これをメチルエチルケトン、トルエン、アセトン、エチルセロソルブ、メチルセロソルブ、シクロヘキサノン等の好適な有機溶剤で希釈して樹脂溶液となし、これをポリイミドフィルム上に塗布し、加熱乾燥するという通常の方法によりカバーレイを製造することができる。
【００２１】
また、本発明の接着剤組成物は、これをメチルエチルケトン、トルエン、アセトン、エチルセロソルブ、メチルセロソルブ、シクロヘキサノン等の好適な有機溶剤で希釈して樹脂溶液となし、キャリアフィルム上に塗布し、加熱乾燥して剥離するという通常の方法により接着フィルムを製造することができる。
【００２２】
また、該フレキシブル銅張積層板に回路を形成し、必要であれば穴明けスルーホールメッキを施し、ついで所定箇所に穴を明けた該カバーレイを重ねて加熱加圧成形するという通常の方法でフレキシブルプリント配線板を製造することができる。更にこのフレキシブルプリント配線板に該接着フィルムを介して補強板を重ね合わせ、加熱加圧成形するという通常の方法で補強板付きフレキシブルプリント配線板を製造することができる。
【００２３】
また、多層プリント配線板は、該フレキシブルプリント配線板に該接着フィルムを介して該フレキシブル銅張積層板またはハロゲンを含まないガラスエポキシ銅張積層板などを重ね合わせ、加熱加圧成形し、スルーホールを形成し、スルーホールメッキを行った後、所定の回路を形成するという通常の方法により製造することができる。
【００２４】
【発明の実施の形態】
以下、本発明を実施例により説明するが、本発明はこれらの実施例によって限定されるものではない。以下の実施例および比較例において「部」とは「重量部」を意味する。
【００２５】
実施例１
カルボキシ含有アクリロニトリルブタジエンゴムのニポール１０７２（日本ゼオン社製商品名）２７部、ビフェニル骨格含有多官能型エポキシ樹脂のＮＣ−３０００−Ｈ（日本化薬社製商品名、エポキシ当量２８８）３４部、４，４′−ジアミノジフェニルスルホン（アミン当量６２）５．３部、２−エチル−４−メチルイミダゾール０．３部、テトラメチルタイプのビフェニル型エポキシＸＹ−４０００（ジャパンエポキシレジン社製、商品名）とビスフェノールＳからなるフェノキシ樹脂溶液ＹＬ６７４６ＢＨ３０（ジャパンエポキシレジン社製商品名、不揮発分３０重量％、重量平均分子量約３００００）７６．７部、水酸化アルミニウム１０部、シクロフェノキシホスファゼンオリゴマー（融点１００℃）１０部および老化防止剤のＮ，Ｎ′−ジ−２−ナフチル−ｐ−フェニレンジアミン１部を、メチルエチルケトン／トルエン＝６／４の混合溶剤に溶解希釈し、固形分３０％のＦＰＣ基板用の接着剤組成物を製造した。
【００２６】
実施例２
カルボキシ含有アクリロニトリルブタジエンゴムのニポール１０７２（日本ゼオン社製商品名）２７部、ビフェニル骨格含有多官能型エポキシ樹脂のＮＣ−３０００−Ｈ（日本化薬社製商品名、エポキシ当量２８８）３４部、４，４′−ジアミノジフェニルスルホン（アミン当量６２）５．３部、２−エチル−４−メチルイミダゾール０．２９部、テトラメチルタイプのビフェニル型エポキシＸＹ−４０００（ジャパンエポキシレジン社製、商品名）とビスフェノールＡからなるフェノキシ樹脂溶液ＹＬ６７４２Ｂ４０（ジャパンエポキシレジン社製商品名、不揮発分４０重量％、重量平均分子量約３００００）５７．５部、水酸化アルミニウム１０部、シクロフェノキシホスファゼンオリゴマー（融点１００℃）１０部および老化防止剤のＮ，Ｎ′−ジ−２−ナフチル−ｐ−フェニレンジアミン１部を、メチルエチルケトン／トルエン＝６／４の混合溶剤に溶解希釈し、固形分３０％のＦＰＣ基板用の接着剤組成物を製造した。
【００２７】
実施例３
カルボキシ含有アクリロニトリルブタジエンゴムのニポール１０７２（日本ゼオン社製商品名）２７部、ビフェニル骨格含有多官能型エポキシ樹脂のＮＣ−３０００−Ｈ（日本化薬社製商品名、エポキシ当量２８８）３４．５部、４，４′−ジアミノジフェニルスルホン（アミン当量６２）５．３部、２−エチル−４−メチルイミダゾール０．３部、ビスフェノールＦ骨格とビスフェノールＡ骨格とからなるフェノキシ樹脂ＹＰ−７０（東都化成社製商品名、重量平均分子量約５００００）２３部、水酸化アルミニウム１０部、シクロフェノキシホスファゼンオリゴマー（融点１００℃）１０部および老化防止剤のＮ，Ｎ′−ジ−２−ナフチル−ｐ−フェニレンジアミン１部を、メチルエチルケトン／トルエン＝６／４の混合溶剤に溶解希釈し、固形分３０％のＦＰＣ基板用の接着剤組成物を製造した。
【００２８】
実施例４
カルボキシ含有アクリロニトリルブタジエンゴムのニポール１０７２（日本ゼオン社製商品名）２７部、ビフェニル骨格含有多官能型エポキシ樹脂のＮＣ−３０００−Ｈ（日本化薬社製商品名、エポキシ当量２８８）３４．５部、４，４′−ジアミノジフェニルスルホン（アミン当量６２）５．４部、２−エチル−４−メチルイミダゾール０．２９部、ビスフェノールＦ骨格からなるフェノキシ樹脂ＺＸ−１３９５０（東都化成社製商品名、重量平均分子量約４００００）２３部、水酸化アルミニウム１０部、シクロフェノキシホスファゼンオリゴマー（融点１００℃）１０部および老化防止剤のＮ，Ｎ′−ジ−２−ナフチル−ｐ−フェニレンジアミン１部を、メチルエチルケトン／トルエン＝６／４の混合溶剤に溶解希釈し、固形分３０％のＦＰＣ基板用の接着剤組成物を製造した。
【００２９】
比較例１
カルボキシ含有アクリロニトリルブタジエンゴムのニポール１０７２（日本ゼオン社製、商品名）２７部、ビフェニル骨格含有多官能型エポキシ樹脂のＮＣ−３０００−Ｈ（日本化薬社製商品名、エポキシ当量２８８）３４部、４，４′−ジアミノジフェニルスルホン（アミン当量６２）５．３部、２−エチル−４−メチルイミダゾール０．２９部、ビスフェノールＡ骨格からなるフェノキシ樹脂溶液エピコート１２５６Ｂ４０（ジャパンエポキシレジン社製商品名、不揮発分４０重量％、重量平均分子量約５００００）５７．５部、水酸化アルミニウム１０部、シクロフェノキシホスファゼンオリゴマー（融点１００℃）１０部および老化防止剤のＮ，Ｎ′−ジ−２−ナフチル−ｐ−フェニレンジアミン１部を、メチルエチルケトン／トルエン＝６／４の混合溶剤に溶解希釈し、固形分３０％のＦＰＣ基板用の接着剤組成物を製造した。
【００３０】
比較例２
カルボキシ含有アクリロニトリルブタジエンゴムのニポール１０７２（日本ゼオン社製、商品名）２７部、ビフェニル骨格含有多官能型エポキシ樹脂のＮＣ−３０００−Ｈ（日本化薬社製商品名、エポキシ当量２８８）５５部、４，４′−ジアミノジフェニルスルホン（アミン当量６２）８．２部、２−エチル−４−メチルイミダゾール０．２７部、水酸化アルミニウム１０部、シクロフェノキシホスファゼンオリゴマー（融点１００℃）１０部および老化防止剤のＮ，Ｎ′−ジ−２−ナフチル−ｐ−フェニレンジアミン１部を、メチルエチルケトン／トルエン＝６／４の混合溶剤に溶解希釈し、固形分３０％のＦＰＣ基板用の接着剤組成物を製造した。
【００３１】
比較例３
カルボキシ含有アクリロニトリルブタジエンゴムのニポール１０７２（日本ゼオン社製、商品名）５４部、ビフェニル骨格含有多官能型エポキシ樹脂のＮＣ−３０００−Ｈ（日本化薬社製商品名、エポキシ当量２８８）３１部、４，４′−ジアミノジフェニルスルホン（アミン当量６２）４．７部、２−エチル−４−メチルイミダゾール０．１５部、水酸化アルミニウム１０部、シクロフェノキシホスファゼンオリゴマー（融点１００℃）１０部および老化防止剤のＮ，Ｎ′−ジ−２−ナフチル−ｐ−フェニレンジアミン１部を、メチルエチルケトン／トルエン＝６／４の混合溶剤に溶解希釈し、固形分３０％のＦＰＣ基板用の接着剤組成物を製造した。
【００３２】
比較例４
カルボキシ含有アクリロニトリルブタジエンゴムのニポール１０７２（日本ゼオン社製、商品名）５４部、ビフェニル骨格含有多官能型エポキシ樹脂のＮＣ−３０００−Ｈ（日本化薬社製商品名、エポキシ当量２８８）３１部、４，４′−ジアミノジフェニルスルホン（アミン当量６２）４．７部、２−エチル−４−メチルイミダゾール０．１５部、水酸化アルミニウム１０部、シクロフェノキシホスファゼンオリゴマー（融点１００℃）３０部および老化防止剤のＮ，Ｎ′−ジ−２−ナフチル−ｐ−フェニレンジアミン１部を、メチルエチルケトン／トルエン＝６／４の混合溶剤に溶解希釈し、固形分３０％のＦＰＣ基板用の接着剤組成物を製造した。
【００３３】
実施例１〜４および比較例１〜４で製造したＦＰＣ基板用の接着剤組成物を厚さ２５μｍのポリイミドフィルムのカプトン（東レデュポン社製、商品名）にロールコーターで乾燥後の厚さが１５μｍになるように塗布乾燥し、その接着剤面と銅箔（３５μｍ）の処理面とを重ね合わせて１２０℃のラミネートロールで圧着した後、オーブンで１００℃，３時間、１３０℃，３時間、１６０℃，３時間処理し、接着剤を硬化させて８種類のフレキシブル銅張積層板を得た。
【００３４】
実施例１〜４および比較例１〜４で製造したＦＰＣ基板用の接着剤組成物を、厚さ２５μｍのポリイミドフィルムのカプトン（東レデュポン社製、商品名）にロールコーターで乾燥後の厚さが３５μｍになるように塗布乾燥し、半硬化させて８種類のカバーレイを作製した。このカバーレイを、実施例１〜４および比較例１〜４で製造したそれぞれの接着剤組成物を用いて作製したフレキシブル銅張積層板に重ね合わせ、熱プレスで１６０℃，４ＭＰａ，１時間加熱加圧接着し、８種類の評価用のカバーレイ付きフレキシブル基板を作製した。
【００３５】
次いで、実施例１〜４および比較例１〜４で製造したＦＰＣ基板用の接着剤組成物を、厚さ４０μｍのポリプロピレンフィルムに、乾燥後の厚さが５０μｍとなるようにロールコーターで塗布乾燥し、半硬化させて８種類の接着フィルムを作製した。この接着フィルムを厚さ１２５μｍのポリイミド補強板に１２０℃のラミネートロールで圧着した後、キャリアフィルムのポリプロピレンフィルムを剥がし、実施例１〜４および比較例１〜４で製造したそれぞれの接着剤組成物を用いて作製したフレキシブル銅張積層板のフィルム面に重ね合わせ、熱プレスで１６０℃，０．５ＭＰａ，１時間加熱加圧接着し、８種類の評価用の補強板付きフレキシブル基板を作製した。
【００３６】
実施例１〜４および比較例１〜４で製造したＦＰＣ基板用の接着剤組成物を用いて得られた８種類の基板についての特性評価を行ったので、実施例１〜４の結果を表１に、比較例１〜４の結果を表２に示す。
【００３７】
【表１】
【００３８】
＊２：２６０℃、２８０℃および３００℃の半田浴に１分間フロートさせて、フクレの有無を確認した。○印…フクレなし、×印…フクレあり。
【００３９】
＊３：ＩＰＣ−ＦＣ−２４０Ｂによる。
【００４０】
＊４：１ｍｍ間隔クシ型テストパターンで測定。
【００４１】
＊５：プレス前のカバーレイの状態で折り曲げ、ポリイミドフィルムからの接着剤の剥がれ具合を確認した。○印…ハガレなし、×印…ハガレ発生。
【００４２】
【表２】
【００４３】
＊２：２６０℃、２８０℃および３００℃の半田浴に１分間フロートさせて、フクレの有無を確認した。○印…フクレなし、×印…フクレあり。
【００４４】
＊３：ＩＰＣ−ＦＣ−２４０Ｂによる。
【００４５】
銅張積層板とカバーレイの組合せで作製したフレキシブル基板のカバーレイを剥離して作製。
【００４６】
＊４：１ｍｍ間隔クシ型テストパターンで測定。
【００４７】
＊５：プレス前のカバーレイの状態で折り曲げ、ポリイミドフィルムからの接着剤の剥がれ具合を確認した。○印…ハガレなし、×印…ハガレ発生。
【００４８】
【発明の効果】
以上の説明および表１、２から明らかなように、本発明によれば、塩素、臭素を実質的に含有しないで優れた難燃性を示し、しかもカバーレイ、接着剤フィルムなどの硬化前の状態でハドリング性に優れる接着剤が提供される。このような材料を用いれば、良好な環境特性を付与し、かつ種々の特性に優れたフレキシブルプリント配線板を製造することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a halogen-free flame-retardant adhesive composition, a flexible copper-clad laminate using the same, a coverlay and an adhesive film, and further to a printed wiring board produced using these.
[0002]
[Prior art]
In recent years, with the growing concern about global environmental issues and human safety, electrical and electronic devices require less harmfulness and higher safety in addition to conventional flame retardancy. Has increased. That is, electrical / electronic devices are not only difficult to burn, but are also required to generate less harmful gases and harmful smoke during combustion. Conventionally, a flexible printed wiring board used for wiring of electric / electronic devices is composed of a flexible copper-clad laminate, a coverlay and an adhesive film, but acts as a flame retardant on the adhesive used there. Brominated epoxy resins containing bromine, particularly tetrabromobisphenol A type epoxy resins are generally used.
[0003]
Although such brominated epoxy resins have good flame retardancy, they may generate harmful halogenated gas (hydrogen bromide), etc. during combustion, and may generate brominated dioxins and brominated furans. The use is being suppressed because of concerns.
[0004]
On the other hand, handling properties in the state before curing are important for coverlays and adhesive films, and for this purpose, synthetic rubber is generally blended, but adhesives containing many of these are inferior in flame retardancy, It was necessary to add a lot of flame retardant components.
[0005]
[Problems to be solved by the invention]
The object of the present invention is to display good flame retardancy without halogen (halogen-free), heat resistance, folding resistance, electrical insulation, and handling before curing such as coverlay and adhesive film It is providing the adhesive composition excellent in property etc.
[0006]
Furthermore, the present invention also aims to provide a flexible copper-clad laminate, a coverlay and an adhesive film using such a flame-retardant adhesive composition, and a flexible printed wiring board produced using these. To do.
[0007]
[Means for Solving the Problems]
As a result of intensive research aimed at achieving the above object, the present inventors have used an epoxy resin having a specific structure, added a phosphazene compound and an inorganic filler into the adhesive composition, and It has been found that the above object can be achieved by blending a phenoxy resin together with a synthetic rubber as a component, and the present invention has been completed.
[0008]
That is, the present invention
(A) an epoxy resin that is a glycidyl compound of a polyfunctional resin having a biphenyl skeleton and a phenol skeleton represented by the following general formula:
[Chemical 2]
(B) a curing agent for epoxy,
(C) a curing accelerator,
(D) synthetic rubber,
(E) a phenoxy resin having a weight average molecular weight of 5,000 to 100,000,
(F) A halogen-free flame-retardant adhesive composition comprising at least one phosphazene compound and (G) an inorganic filler as essential components, wherein the phenoxy resin has a biphenyl skeleton or a bisphenol F skeleton. The present invention also provides a flexible copper-clad laminate, a coverlay and an adhesive film using the halogen-free flame-retardant adhesive composition, and a flexible printed wiring board produced using these.
[0009]
Hereinafter, the present invention will be described in detail.
[0010]
As the (A) epoxy resin used in the present invention, a polyfunctional epoxy resin containing a biphenyl skeleton represented by the above formula 2 can be preferably used. The epoxy resin may be an epoxy resin having two or more epoxy groups in one molecule, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolac type epoxy resin, glycidyl ether type epoxy resin, if necessary. It can be used by mixing with an epoxy resin such as an alicyclic epoxy resin or a heterocyclic epoxy resin. These epoxy resins can usually be used by dissolving in a solvent. The solvent may be any solvent that dissolves epoxy resin, epoxy curing agent, epoxy curing accelerator, elastomer and phosphazene, but has a boiling point of 160 ° C. or lower so that the solvent does not remain in the coating and drying process of the adhesive. It is desirable that Specific examples of the solvent include methyl ethyl ketone, toluene, acetone, ethyl cellosolve, methyl cellosolve, and cyclohexanone, and these can be used alone or in combination of two or more.
[0011]
The (B) epoxy curing agent used in the present invention can be used without particular limitation as long as it is usually a compound used as an epoxy resin curing agent. Examples of amine curing systems include dicyandiamide (DICY), aromatic Examples of phenolic curing systems include phenol novolak resins, cresol novolak resins, bisphenol A type novolak resins, triazine-modified phenol novolak resins, and the like. These may be used alone or in combination of two or more. Can do.
[0012]
The (C) epoxy curing accelerator used in the present invention is usually used as an epoxy resin curing accelerator. Examples thereof include 2-ethyl-4-methyl-imidazole and 1-benzyl-2- Examples thereof include imidazole compounds such as methylimidazole, boron trifluoride amine complex, and triphenylphosphine, and these can be used alone or in combination of two or more.
[0013]
As the synthetic rubber (D) used in the present invention, those used for adhesives without particular limitation can be widely used. Specific examples include various synthetic rubbers such as acrylic rubber, acrylonitrile butadiene rubber, and carboxy-containing acrylonitrile butadiene rubber, and these can be used alone or in combination of two or more. Among these, acrylonitrile butadiene rubber excellent in flexibility and bending strength and its modified rubber are particularly preferably used.
[0014]
As the (E) phenoxy resin used in the present invention, a resin having a weight average molecular weight of 5,000 to 100,000 and containing a biphenyl skeleton or a bisphenol F skeleton can be preferably used. This phenoxy resin is blended for the purpose of improving the flexibility of the adhesive composition and preventing flame retardancy. If the weight average molecular weight of the phenoxy resin is less than 5,000, the effect of imparting flexibility is small, and if it exceeds 100,000, the compatibility with the essential component (D) synthetic rubber is deteriorated and the adhesive solution is easily separated. It is not preferable.
[0015]
As the phosphazene compound (F) used in the present invention, a phosphazene compound which is substantially free of halogen and has a melting point of 80 ° C. or higher from the viewpoint of heat resistance, moisture resistance, flame retardancy, chemical resistance and the like. It can be preferably used. Specific examples include cyclophosphazene oligomers represented by the following chemical formula.
[0016]
[Chemical 3]
Examples of the halogen-free organic group X in the cyclophosphazene oligomer include an alkoxy group, a phenoxy group, an amino group, and an allyl group. The blending ratio of the (F) phosphazene compound is preferably 2 to 20% by weight with respect to the entire adhesive composition. If it is less than 2% by weight, sufficient flame retardancy cannot be obtained, and if it exceeds 20% by weight, the adhesive strength is lowered, which is not preferable.
[0017]
There is no restriction | limiting in particular as an inorganic filler (G) used for this invention, A talc, an alumina, aluminum hydroxide, magnesium hydroxide, a fused silica, a synthetic silica etc. are mentioned, These are used individually or in mixture of 2 or more types. can do. It is preferable to mix | blend the mixture ratio of this inorganic filler in the ratio of 5 to 50 weight% in an adhesive composition. If the blending amount is less than 5% by weight, sufficient flame retardancy cannot be obtained. If the blending amount exceeds 50% by weight, the adhesive composition becomes hard and brittle.
[0018]
The adhesive composition of the present invention comprises (A) a polyfunctional epoxy resin containing a biphenyl skeleton, (B) a curing agent for epoxy, (C) a curing accelerator for epoxy, (D) a synthetic rubber, ( E) A phenoxy resin having a weight average molecular weight of 5,000 to 100,000, (F) at least one phosphazene compound, and (G) an inorganic filler as essential components, but as long as they do not contradict the purpose of the present invention, and as necessary In addition, finely divided inorganic or organic fillers, pigments, deterioration inhibitors and the like can be added and blended. These components described above can be dissolved uniformly using a solvent such as methyl ethyl ketone and toluene, and an adhesive composition for an FPC board can be easily produced.
[0019]
The adhesive composition of the present invention described above is diluted with a suitable organic solvent such as methyl ethyl ketone, toluene, acetone, ethyl cellosolve, methyl cellosolve, cyclohexanone to form a resin solution, which is applied onto a polyimide film. A flexible copper-clad laminate can be manufactured by the usual method of sticking copper foil on one or both sides with a heat roll and then heat-curing.
[0020]
Further, the adhesive composition of the present invention is diluted with a suitable organic solvent such as methyl ethyl ketone, toluene, acetone, ethyl cellosolve, methyl cellosolve, cyclohexanone to form a resin solution, which is applied onto a polyimide film, A coverlay can be manufactured by the usual method of drying by heating.
[0021]
In addition, the adhesive composition of the present invention is diluted with a suitable organic solvent such as methyl ethyl ketone, toluene, acetone, ethyl cellosolve, methyl cellosolve, cyclohexanone to form a resin solution, which is applied onto a carrier film and dried by heating. Then, an adhesive film can be produced by a usual method of peeling.
[0022]
In addition, a circuit is formed on the flexible copper-clad laminate, and through-hole plating is performed if necessary, and then the cover lay with holes formed in predetermined positions is stacked and heated and pressed. A flexible printed wiring board can be manufactured. Further, a flexible printed wiring board with a reinforcing plate can be manufactured by a normal method of superimposing a reinforcing plate on the flexible printed wiring board via the adhesive film, followed by heat and pressure molding.
[0023]
In addition, the multilayer printed wiring board is formed by superposing the flexible copper-clad laminate or the halogen-free glass epoxy copper-clad laminate on the flexible printed wiring board via the adhesive film, heating and pressing, and through holes. After a through hole plating is performed, a predetermined circuit can be formed by a normal method.
[0024]
DETAILED DESCRIPTION OF THE INVENTION
EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited by these Examples. In the following Examples and Comparative Examples, “parts” means “parts by weight”.
[0025]
Example 1
27 parts Nipol 1072 (trade name, manufactured by Nippon Zeon Co., Ltd.) of carboxy-containing acrylonitrile butadiene rubber, 34 parts of NC-3000-H (trade name, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 288), a polyfunctional epoxy resin containing biphenyl skeleton, 4 parts , 4'-diaminodiphenylsulfone (amine equivalent 62) 5.3 parts, 2-ethyl-4-methylimidazole 0.3 parts, tetramethyl type biphenyl type epoxy XY-4000 (trade name, manufactured by Japan Epoxy Resin Co., Ltd.) And bisphenol S phenoxy resin solution YL6746BH30 (trade name, Japan Epoxy Resin, trade name, nonvolatile content 30% by weight, weight average molecular weight about 30000) 76.7 parts, aluminum hydroxide 10 parts, cyclophenoxyphosphazene oligomer (melting point 100 ° C.) 10 parts and anti-aging agent The N'- di-2-naphthyl -p- phenylenediamine, 1 part Methyl ethyl ketone / toluene = 6/4 mixture was dissolved diluted in a solvent, to produce an adhesive composition for a solid content of 30% FPC substrate.
[0026]
Example 2
27 parts Nipol 1072 (trade name, manufactured by Nippon Zeon Co., Ltd.) of carboxy-containing acrylonitrile butadiene rubber, 34 parts of NC-3000-H (trade name, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 288), a polyfunctional epoxy resin containing biphenyl skeleton, 4 parts , 4′-diaminodiphenylsulfone (amine equivalent 62) 5.3 parts, 2-ethyl-4-methylimidazole 0.29 parts, tetramethyl type biphenyl type epoxy XY-4000 (trade name, manufactured by Japan Epoxy Resin Co., Ltd.) And bisphenol A phenoxy resin solution YL6742B40 (trade name, manufactured by Japan Epoxy Resin Co., Ltd., non-volatile content 40% by weight, weight average molecular weight about 30000) 57.5 parts, aluminum hydroxide 10 parts, cyclophenoxyphosphazene oligomer (melting point 100 ° C.) 10 parts and anti-aging agent The N'- di-2-naphthyl -p- phenylenediamine, 1 part Methyl ethyl ketone / toluene = 6/4 mixture was dissolved diluted in a solvent, to produce an adhesive composition for a solid content of 30% FPC substrate.
[0027]
Example 3
27 parts of Nipol 1072 (trade name, manufactured by Nippon Zeon Co., Ltd.) of carboxy-containing acrylonitrile butadiene rubber, 34.5 parts of NC-3000-H (trade name, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 288) of polyfunctional epoxy resin containing biphenyl skeleton , 4,4'-diaminodiphenylsulfone (amine equivalent 62) 5.3 parts, 2-ethyl-4-methylimidazole 0.3 parts, phenoxy resin YP-70 (Tohto Kasei Co., Ltd.) comprising bisphenol F skeleton and bisphenol A skeleton Product name, weight average molecular weight of about 50000) 23 parts, aluminum hydroxide 10 parts, cyclophenoxyphosphazene oligomer (melting point 100 ° C.) 10 parts and anti-aging agent N, N′-di-2-naphthyl-p-phenylene 1 part of diamine is dissolved and diluted in a mixed solvent of methyl ethyl ketone / toluene = 6/4 It was prepared an adhesive composition for a solid content of 30% FPC substrate.
[0028]
Example 4
27 parts of Nipol 1072 (trade name, manufactured by Nippon Zeon Co., Ltd.) of carboxy-containing acrylonitrile butadiene rubber, 34.5 parts of NC-3000-H (trade name, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 288) of polyfunctional epoxy resin containing biphenyl skeleton , 4,4'-diaminodiphenylsulfone (amine equivalent 62) 5.4 parts, 2-ethyl-4-methylimidazole 0.29 parts, phenoxy resin ZX-13950 (trade name, manufactured by Tohto Kasei Co., Ltd., Weight average molecular weight of about 40,000) 23 parts, aluminum hydroxide 10 parts, cyclophenoxyphosphazene oligomer (melting point 100 ° C.) 10 parts and anti-aging agent N, N′-di-2-naphthyl-p-phenylenediamine 1 part, Dissolved and diluted in a mixed solvent of methyl ethyl ketone / toluene = 6/4, solid content 30% The adhesive composition of the FPC board was produced.
[0029]
Comparative Example 1
27 parts of Nipol 1072 (trade name, manufactured by Nippon Zeon Co., Ltd.) of carboxy-containing acrylonitrile butadiene rubber, 34 parts of NC-3000-H (trade name, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 288) of polyfunctional epoxy resin containing biphenyl skeleton, Phenoxy resin solution Epicoat 1256B40 consisting of 5.3 parts of 4,4'-diaminodiphenylsulfone (amine equivalent 62), 0.29 parts of 2-ethyl-4-methylimidazole and bisphenol A skeleton (trade name, manufactured by Japan Epoxy Resin Co., Ltd.) Non-volatile content 40% by weight, weight average molecular weight of about 50000) 57.5 parts, aluminum hydroxide 10 parts, cyclophenoxyphosphazene oligomer (melting point 100 ° C.) 10 parts and anti-aging agent N, N′-di-2-naphthyl- 1 part of p-phenylenediamine is added to methyl ethyl ketone / torr Was dissolved diluted in a mixed solvent of emission = 6/4 was prepared an adhesive composition for a solid content of 30% FPC substrate.
[0030]
Comparative Example 2
27 parts of Nipol 1072 (trade name, manufactured by Nippon Zeon Co., Ltd.) of carboxy-containing acrylonitrile butadiene rubber, 55 parts of NC-3000-H (trade name, epoxy equivalent 288, manufactured by Nippon Kayaku Co., Ltd.) containing a biphenyl skeleton-containing polyfunctional epoxy resin, 8.2 parts of 4,4′-diaminodiphenylsulfone (amine equivalent 62), 0.27 parts of 2-ethyl-4-methylimidazole, 10 parts of aluminum hydroxide, 10 parts of cyclophenoxyphosphazene oligomer (melting point 100 ° C.) and aging 1 part of N, N'-di-2-naphthyl-p-phenylenediamine as an inhibitor is dissolved and diluted in a mixed solvent of methyl ethyl ketone / toluene = 6/4, and an adhesive composition for an FPC board having a solid content of 30% Manufactured.
[0031]
Comparative Example 3
54 parts of Nipol 1072 (trade name, manufactured by Nippon Zeon Co., Ltd.) of carboxy-containing acrylonitrile butadiene rubber, 31 parts of NC-3000-H (trade name, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 288) of polyfunctional epoxy resin containing biphenyl skeleton, 4.7 parts of 4,4′-diaminodiphenylsulfone (amine equivalent 62), 0.15 parts of 2-ethyl-4-methylimidazole, 10 parts of aluminum hydroxide, 10 parts of cyclophenoxyphosphazene oligomer (melting point 100 ° C.) and aging 1 part of N, N'-di-2-naphthyl-p-phenylenediamine as an inhibitor is dissolved and diluted in a mixed solvent of methyl ethyl ketone / toluene = 6/4, and an adhesive composition for an FPC board having a solid content of 30% Manufactured.
[0032]
Comparative Example 4
54 parts of Nipol 1072 (trade name, manufactured by Nippon Zeon Co., Ltd.) of carboxy-containing acrylonitrile butadiene rubber, 31 parts of NC-3000-H (trade name, manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 288) of polyfunctional epoxy resin containing biphenyl skeleton, 4.7 parts of 4,4′-diaminodiphenylsulfone (amine equivalent 62), 0.15 parts of 2-ethyl-4-methylimidazole, 10 parts of aluminum hydroxide, 30 parts of cyclophenoxyphosphazene oligomer (melting point 100 ° C.) and aging 1 part of N, N'-di-2-naphthyl-p-phenylenediamine as an inhibitor is dissolved and diluted in a mixed solvent of methyl ethyl ketone / toluene = 6/4, and an adhesive composition for an FPC board having a solid content of 30% Manufactured.
[0033]
The adhesive composition for FPC boards produced in Examples 1 to 4 and Comparative Examples 1 to 4 has a thickness after drying with a roll coater on a 25 μm thick polyimide film Kapton (trade name, manufactured by Toray DuPont). After coating and drying to 15 μm, the adhesive surface and the treated surface of copper foil (35 μm) are overlapped and pressure-bonded with a laminate roll at 120 ° C., and then oven is 100 ° C., 3 hours, 130 ° C., 3 hours. The adhesive was cured by treating at 160 ° C. for 3 hours to obtain 8 types of flexible copper-clad laminates.
[0034]
The thickness of the adhesive composition for FPC boards produced in Examples 1 to 4 and Comparative Examples 1 to 4 after being dried with a roll coater on a 25 μm thick polyimide film Kapton (trade name, manufactured by Toray DuPont) Was coated and dried so as to be 35 μm, and semi-cured to prepare 8 types of coverlays. This coverlay was overlaid on the flexible copper clad laminate produced using each adhesive composition produced in Examples 1 to 4 and Comparative Examples 1 to 4, and heated at 160 ° C., 4 MPa for 1 hour with a hot press. Pressure bonding was performed to prepare eight types of flexible substrates with coverlays for evaluation.
[0035]
Next, the FPC board adhesive compositions produced in Examples 1 to 4 and Comparative Examples 1 to 4 were applied and dried on a 40 μm thick polypropylene film with a roll coater so that the thickness after drying was 50 μm. And semi-cured to prepare 8 types of adhesive films. Each adhesive composition produced in Examples 1 to 4 and Comparative Examples 1 to 4 was prepared by pressure-bonding the adhesive film to a polyimide reinforcing plate having a thickness of 125 μm with a laminate roll at 120 ° C. and then removing the polypropylene film of the carrier film. Was laminated on the film surface of the flexible copper-clad laminate produced using the above, and heat-press bonded for 1 hour at 160 ° C., 0.5 MPa by hot pressing to produce 8 types of flexible substrates with reinforcing plates for evaluation.
[0036]
Since the characteristic evaluation about 8 types of board | substrates obtained using the adhesive composition for FPC boards manufactured in Examples 1-4 and Comparative Examples 1-4 was performed, the result of Examples 1-4 is represented. Table 1 shows the results of Comparative Examples 1 to 4.
[0037]
[Table 1]
[0038]
* 2: Float in a solder bath at 260 ° C., 280 ° C. and 300 ° C. for 1 minute to confirm the presence or absence of swelling. ○: No blister, x: Buff.
[0039]
* 3: According to IPC-FC-240B.
[0040]
* 4: Measured with a 1 mm spacing comb type test pattern.
[0041]
* 5: It was bent in the state of the cover lay before pressing, and the degree of peeling of the adhesive from the polyimide film was confirmed. ○ mark: no peeling, x mark: peeling.
[0042]
[Table 2]
[0043]
* 2: Float in a solder bath at 260 ° C., 280 ° C. and 300 ° C. for 1 minute to confirm the presence or absence of swelling. ○: No blister, x: Buff.
[0044]
* 3: According to IPC-FC-240B.
[0045]
Fabricated by peeling the coverlay of a flexible board made from a combination of copper-clad laminate and coverlay.
[0046]
* 4: Measured with a 1 mm spacing comb type test pattern.
[0047]
* 5: It was bent in the state of the cover lay before pressing, and the degree of peeling of the adhesive from the polyimide film was confirmed. ○ mark: no peeling, x mark: peeling.
[0048]
【The invention's effect】
As is apparent from the above description and Tables 1 and 2, according to the present invention, excellent flame retardancy is exhibited without substantially containing chlorine and bromine, and before curing of the coverlay, adhesive film, etc. An adhesive having excellent hadling properties in a state is provided. By using such a material, it is possible to produce a flexible printed wiring board that imparts favorable environmental characteristics and is excellent in various characteristics.
Claims (7)
（Ｂ）エポキシ用硬化剤、
（Ｃ）硬化促進剤、
（Ｄ）合成ゴム、
（Ｅ）重量平均分子量５０００〜１０００００であるビフェニル骨格又はビスフェノールＦ骨格を有するフェノキシ樹脂、
（Ｆ）少なくとも１種のホスファゼン化合物および
（Ｇ）無機充填剤
を必須成分とすることを特徴とするハロゲンフリーの難燃性接着剤組成物。(A) an epoxy resin that is a glycidyl compound of a polyfunctional resin having a biphenyl skeleton and a phenol skeleton represented by the following general formula:
(B) a curing agent for epoxy,
(C) a curing accelerator,
(D) synthetic rubber,
(E) a phenoxy resin having a biphenyl skeleton or a bisphenol F skeleton having a weight average molecular weight of 5000 to 100,000,
(F) A halogen-free flame-retardant adhesive composition comprising at least one phosphazene compound and (G) an inorganic filler as essential components.
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| JP2003128622A JP4503239B2 (en) | 2003-05-07 | 2003-05-07 | Flame-retardant adhesive composition, flexible copper-clad laminate, coverlay and adhesive film |
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|---|---|---|---|
| JP2003128622A JP4503239B2 (en) | 2003-05-07 | 2003-05-07 | Flame-retardant adhesive composition, flexible copper-clad laminate, coverlay and adhesive film |
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| JP4503239B2 true JP4503239B2 (en) | 2010-07-14 |
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Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4600640B2 (en) * | 2003-11-10 | 2010-12-15 | 信越化学工業株式会社 | Acrylic adhesive sheet |
| JP4584619B2 (en) * | 2004-04-30 | 2010-11-24 | 信越化学工業株式会社 | Flame-retardant adhesive composition and adhesive sheet using the same |
| JP2006316234A (en) * | 2005-04-13 | 2006-11-24 | Shin Etsu Chem Co Ltd | Flame retardant adhesive composition, adhesive sheet using the same, cover lay film and flexible copper clad laminate |
| JP5516657B2 (en) * | 2005-05-27 | 2014-06-11 | 日立化成株式会社 | Metal foil with adhesion aid, printed wiring board using the same, and method for producing the same |
| JP2007224162A (en) * | 2006-02-23 | 2007-09-06 | Matsushita Electric Works Ltd | Flame-retardant resin composition, prepreg, resin sheet, and molded product |
| TWI445790B (en) * | 2007-02-28 | 2014-07-21 | Nippon Steel & Sumikin Chem Co | A flame retardant adhesive resin composition, and a flexible printed circuit board material using the same |
| JP2008208311A (en) * | 2007-02-28 | 2008-09-11 | Kyocera Chemical Corp | Adhesive composition for flexible printed wiring board and flexible printed wiring board using the same |
| KR100959746B1 (en) | 2007-10-23 | 2010-05-25 | 제일모직주식회사 | Adhesive film composition using phenoxy resin and ester-based thermoplastic resin for semiconductor assembly and bonding film therefrom |
| JP5485521B2 (en) * | 2008-05-26 | 2014-05-07 | 新日鉄住金化学株式会社 | Flame-retardant adhesive resin composition and adhesive film, coverlay film and flexible copper-clad laminate using the same |
| WO2012007992A1 (en) * | 2010-07-14 | 2012-01-19 | 京セラケミカル株式会社 | Flexible wiring board, dry film for coverlay, and production method for flexible wiring board |
| CN102311612B (en) * | 2011-04-03 | 2013-05-01 | 广东生益科技股份有限公司 | Resin composition and resin coated copper foil made of same |
| CN103694639B (en) * | 2013-12-19 | 2016-03-09 | 广东生益科技股份有限公司 | A kind of Halogen ageing-resistant epoxy resin composition and prepare the method for mulch film with this resin combination |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0823165A (en) * | 1994-07-08 | 1996-01-23 | Hitachi Chem Co Ltd | Manufacture of metal cored wiring board using copper foil with insulating bonding agent |
| JPH09302313A (en) * | 1996-05-09 | 1997-11-25 | Hitachi Chem Co Ltd | Metallic foil with adhesive, bonding sheet and multilayered wiring board |
| JP2001019930A (en) * | 1999-07-12 | 2001-01-23 | Toshiba Chem Corp | Flame-retardant adhesive composition, flexible copper- clad laminate, cover lay and adhesive film |
| JP2001181375A (en) * | 1999-10-13 | 2001-07-03 | Ajinomoto Co Inc | Epoxy resin composition, adhesive film and pre-preg thereby, multilayer printed circuit board using same and its producing method |
| JP2002194310A (en) * | 2000-12-25 | 2002-07-10 | Toray Ind Inc | Adhesive composition for semiconductor apparatus, adhesive sheet for semiconductor apparatus and cover lay film using the same |
| JP2003100953A (en) * | 2001-06-29 | 2003-04-04 | Hitachi Chem Co Ltd | Adhesive member |
-
2003
- 2003-05-07 JP JP2003128622A patent/JP4503239B2/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0823165A (en) * | 1994-07-08 | 1996-01-23 | Hitachi Chem Co Ltd | Manufacture of metal cored wiring board using copper foil with insulating bonding agent |
| JPH09302313A (en) * | 1996-05-09 | 1997-11-25 | Hitachi Chem Co Ltd | Metallic foil with adhesive, bonding sheet and multilayered wiring board |
| JP2001019930A (en) * | 1999-07-12 | 2001-01-23 | Toshiba Chem Corp | Flame-retardant adhesive composition, flexible copper- clad laminate, cover lay and adhesive film |
| JP2001181375A (en) * | 1999-10-13 | 2001-07-03 | Ajinomoto Co Inc | Epoxy resin composition, adhesive film and pre-preg thereby, multilayer printed circuit board using same and its producing method |
| JP2002194310A (en) * | 2000-12-25 | 2002-07-10 | Toray Ind Inc | Adhesive composition for semiconductor apparatus, adhesive sheet for semiconductor apparatus and cover lay film using the same |
| JP2003100953A (en) * | 2001-06-29 | 2003-04-04 | Hitachi Chem Co Ltd | Adhesive member |
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