JPH0552873B2 - - Google Patents
Info
- Publication number
- JPH0552873B2 JPH0552873B2 JP60202536A JP20253685A JPH0552873B2 JP H0552873 B2 JPH0552873 B2 JP H0552873B2 JP 60202536 A JP60202536 A JP 60202536A JP 20253685 A JP20253685 A JP 20253685A JP H0552873 B2 JPH0552873 B2 JP H0552873B2
- Authority
- JP
- Japan
- Prior art keywords
- resin
- adhesive composition
- printed wiring
- flexible printed
- manufactured
- 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 - Fee Related
Links
- 230000001070 adhesive effect Effects 0.000 claims description 50
- 239000000853 adhesive Substances 0.000 claims description 48
- 229920005989 resin Polymers 0.000 claims description 29
- 239000011347 resin Substances 0.000 claims description 29
- 239000000203 mixture Substances 0.000 claims description 28
- 239000003822 epoxy resin Substances 0.000 claims description 14
- 229920000647 polyepoxide Polymers 0.000 claims description 14
- 229920000800 acrylic rubber Polymers 0.000 claims description 10
- 229920000058 polyacrylate Polymers 0.000 claims description 10
- 229920002554 vinyl polymer Polymers 0.000 claims description 9
- 125000003700 epoxy group Chemical group 0.000 claims description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- 239000011256 inorganic filler Substances 0.000 claims description 6
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 125000000524 functional group Chemical group 0.000 claims description 4
- 230000031709 bromination Effects 0.000 claims description 3
- 238000005893 bromination reaction Methods 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims 1
- 229920001568 phenolic resin Polymers 0.000 claims 1
- 239000005011 phenolic resin Substances 0.000 claims 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 15
- 230000006866 deterioration Effects 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- 239000011248 coating agent Substances 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- 239000011888 foil Substances 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 8
- 238000001723 curing Methods 0.000 description 8
- 239000002184 metal Substances 0.000 description 7
- 239000011889 copper foil Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
- 238000000465 moulding Methods 0.000 description 6
- 229920003002 synthetic resin Polymers 0.000 description 6
- 239000000057 synthetic resin Substances 0.000 description 6
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 5
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 description 5
- 229920001721 polyimide Polymers 0.000 description 5
- 229910000679 solder Inorganic materials 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 4
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000012787 coverlay film Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000005476 soldering Methods 0.000 description 4
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- 229910002016 Aerosil® 200 Inorganic materials 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 230000032683 aging Effects 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
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 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 description 1
- FUGYGGDSWSUORM-UHFFFAOYSA-N 4-hydroxystyrene Chemical compound OC1=CC=C(C=C)C=C1 FUGYGGDSWSUORM-UHFFFAOYSA-N 0.000 description 1
- 229910002012 Aerosil® Inorganic materials 0.000 description 1
- 230000005856 abnormality 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
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 230000000116 mitigating effect Effects 0.000 description 1
- 229910001120 nichrome Inorganic materials 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C66/00—General aspects of processes or apparatus for joining preformed parts
- B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
- B29C66/71—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the composition of the plastics material of the parts to be joined
Description
［発明の技術分野］
本発明は、フレキシブル印刷配線板における、
金属箔と合成樹脂薄葉材料との強固な接着性、優
れた耐熱性と耐熱劣化性、さらに耐湿性と難燃性
を具備し、かつ加工特性に優れたフレキシブル印
刷配線板用接着剤組成物に関する。
［発明の技術的背景とその問題点］
近年、電子機器の高密度化、軽薄短小化に伴つ
て、軽量で立体的な配線又は機能を実装できるフ
レキシブル印刷配線板の需要が増大している。ま
た民生機器においては、特に安全性の立場から材
料の難燃化および耐熱劣化後の接着性の要求が強
化されてきている。そして、フレキシブルプリン
ト配線板用接着剤は、合成樹脂薄葉材料と金属箔
処理面との接着ばかりでなく、パターン形成をし
た配線板の金属箔のシヤイン面（研磨面）に回路
の絶縁用および保護用のカバーレイフイルムを接
着するのに使用できることが望ましい。特にカバ
ーレイフイルム接着用のためには、金属箔にシヤ
イン面に強固に接着し、かつランド部分への流れ
出しを少量に抑えることができ、パターン回路間
の埋込み性が良好でなければならない。その上、
保存寿命は、少なくとも室温で１カ月、５℃で３
カ月以上が要求される。更に、生産性向上および
寸法精度を悪くしないために低温で、かつ短時間
で加熱、圧着できるという加工性が要求されてい
る。
ところが従来のフレキシブル印刷配線板用接着
剤は、ベース薄葉材料として耐熱性、難燃性に優
れるポリイミドフイルムを使用した場合でも、前
記加工特性の他に接着性、耐熱性、線間絶縁抵抗
性、耐熱劣化性および難燃性等を兼備させること
は極めて困難であつた。従来、フレキシブルプリ
ント配線板用接着剤として、ニトリルゴム系接着
剤（特開昭51−135936号、特開昭57−3877号）、
ポリアミド系接着剤（特開昭54−125285号）、ポ
リエステル系接着剤（特開昭50−16866号、特開
昭54−7441号）、ポリアクリル系接着剤（特開昭
54−162736号）等数多く提案されている。しかし
ながら前記ニトリルゴム系は、耐熱劣化後の接着
性で劣り、150℃で10日間の気中劣化試験後、極
端に固くなりやすいという難点があり、またポリ
アミド系は、吸湿性がやや大きい欠点がある。ポ
リエステル系は、ポリイミドフイルムに対し接着
力が弱い欠点があり、またポリアクリル系は加熱
成形に高温度、かつ長時間を要し、成形温度を下
げ時間を短縮すると、耐湿性に劣る欠点があつ
た。
［発明の目的］
本発明の目的は、前記の難点および欠点を解消
するためになされたもので、接着性、耐熱劣化
性、難燃性、耐湿性に優れ、かつカバーレイフイ
ルム接着用として加工特性のよいフレキシブル印
刷配線板用接着剤組成物を提供しようとするもの
である。
［発明の概要］
本発明者等は、上記目的を達成しようと鋭意検
討を重ねた結果、後述する接着剤組成物がフレキ
シブル印刷配線板の接着剤として好適であること
を見いだし、本発明に至つたものである。
即ち本発明は、
(A) エポキシ基、カルボキシル基およびヒドロキ
シル基の群から選ばれた１種又は２種以上の官
能基を有するアクリルエラストマー、
(B) ポリパラビニルフエノール樹脂、
(C) エポキシ樹脂、
(D) ポリビニルホルマール樹脂、
(E) 硬化剤促進剤および
(F) 無機充填剤
を必須成分とすることを特徴とするフレキシブル
印刷配線板用接着剤組成物である。
本発明に用いる(A)エポキシ基、カルボキシ基お
よびヒドロキシル基の群から選ばれた１種又は２
種以上の官能基を有するアクリルエラストマーと
しては、例えばアロンタツクＳ−1511L、Ｓ−
1511X、Ｓ−1015、Ｓ−1017（東亜合成化学社製、
商品名）、AR−51（日本ゼオン社製、商品名）、
ノツクスタイトPA−501、PA−502（日本メクト
ロン社製、商品名）、テイサンレジンWSO23、
SG51、SG80、SG90（帝国化学産業社製、商品
名）等が挙げられ、これらは単独又は２種以上混
合して用いる。このアクリルエラストマーはエポ
キシ基、カルボキシル基、ヒドロキシル基のいず
れかの官能基を有しているものでよいが、そのな
かで低温で反応するということからエポキシ基を
有するものが特に利用される。このアクリルエラ
ストマーの配合量は、接着剤組成物の樹脂成分
［(A)＋(B)＋(C)＋(D)］に対して30〜70重量％である
ことが望ましい。配合量が30重量％未満では可と
う性が悪く、また70重量％を超えると可とう性は
良くなるものの加湿後の半田耐熱性や難燃性が劣
り好ましくない。
本発明に用いる(B)ポリパラビニルフエノール樹
脂としては、例えばマルゼンレジンＭ、マルゼン
レジンMB（丸善石油社製、商品名）等が挙げら
れ、これらは所望する難燃性によつて単独又は２
種以上混合して用いる。ポリパラビニルフエノー
ル樹脂は分子構造的には熱可塑性ポリスチレン樹
脂に類似しており、パラオキシスチレン樹脂とも
呼称されるがパラ位の水酸基の作用によりエポキ
シ樹脂との架橋性に富んでいる。
(B)ポリパラビニルフエノール樹脂の配合量は、
そのフエノール性水酸基(b)と(c)エポキシ樹脂のエ
ポキシ基(c)との当量比［(b)／(c)］が0.5〜7.0の範
囲内であることが望ましい。この当量比が0.5未
満の場合は加湿後の半田耐熱性が低下し、7.0を
超えると接着性が低下し、耐熱劣化性が悪く好ま
しくない。
臭素化は臭素化ポリパラビニルフエノール樹
脂、臭素化エポキシ樹脂又はそれらの両者を導入
して行われるが、臭素化率は接着剤組成物の樹脂
成分に対して８重量％以上であることが望まし
い。８重量％未満では難燃性に効果が少ないから
である。
本発明に用いる(C)エポキシ樹脂としては、特に
制限がなくすべてのエポキシ樹脂が使用される。
例えばビスフエノールＡ型エポキシ樹脂、ノボラ
ツクエポキシ樹脂やそれらを臭素化したエポキシ
樹脂等が挙げられ、これらは単独もしくは２種以
上混合して用いる。
本発明に用いる(D)ポリビニルホルマール樹脂と
しては、例えばデンカホルマール＃20、＃30、
＃100（電気化学工業社製、商品名）、ビニレツク
ＦのＬ、Ｋ、Ｅ（チツソ社製、商品名）等が挙げ
られ、これらは単独又は２種以上混合して用い
る。ポリパラビニルホルマール樹脂は、硬化後の
接着剤組成物の中で海−島構造をとり、エポキシ
樹脂の固さを緩和し耐衝撃性を向上させると考え
られる。フレキシブル印刷配線板用接着剤組成物
の場合、固さが緩和され、特に耐熱劣化性を向上
させるのに顕著な効果があることを見いだしたも
のである。ポリビニルホルマール樹脂の配合量
は、接着剤組成物の樹脂成分に対して0.5〜5.0重
量％であることが望ましい。配合量が0.5重量％
未満の場合、耐熱劣化性に効果なく、5.0重量％
を超えると耐湿性および接着力が低下し好ましく
ない。
本発明に用いる(E)硬化促進剤としては、例えば
ジシアンジアミド、エピキユアYPH−201（油化
シエルエポキシ社製、商品名）、BF3のイミダゾ
ール錯体AC−4Bシリーズ（丸善石油社製、商品
名）、イミダゾール等を挙げることができ、これ
らは単独もしくは２種以上混合して用いる。エポ
キシ樹脂の架橋は、パラビニルフエノール樹脂お
よびアクリルエラストマーによつてもそれぞれ行
われるため、成形条件によつてはエポキシ樹脂の
硬化促進剤を必要としない場合もあるが、低温で
短時間成形を行うためには硬化促進剤を用いつ必
要がある。配合量は採用する成形条件あるいは所
望する保存寿命によつて決定する。
本発明に用いる(F)無機充填剤としては、超微粒
子無水シリカや水酸化アルミニウム等が挙げら
れ、単独又は２種以上混合して用いる。無機充填
剤の効果としては、表面タツク（粘着）の調整と
ともに、半田処理等の高温における接着剤組成物
の膨脹収縮を緩和する効果を発揮する。無機充填
剤の配合量は、接着剤組成物の固形分に対して３
〜65重量％であることが望ましい。配合量が３重
量％未満では、表面タツクが強く、加工性が悪
く、また65重量％を超えるとベースとなる薄葉材
料との塗れ性が悪く、接着性が低下して好ましく
ない。
以上の各成分を必須成分とする接着剤組成物の
溶媒としては、メチルエチルケトン、アセトン、
トルエン、エチレングリコールモノメチルエーテ
ル、エチレングリコールモノエチルエーテル、ジ
オキサン、メチルセロソルブアセテートおよびそ
れらの混合物が使用できる。接着剤組成物は溶媒
に溶解し、溶液状態で塗布されるが、溶解前の樹
脂成分はそれぞれの原料を混合して調製すること
も、或いは予備硬化を進めて調製することもでき
る。
接着剤組成物を介して、合成樹脂薄葉材料と金
属箔とのラミネートは、合成樹脂薄葉材料或いは
金属箔の少なくともいずれか一方に接着剤組成物
を溶液状態で塗布した後、熱風炉中で乾燥し溶剤
を揮散し或いは予備硬化を行い、次いで加熱プレ
スを使用して加熱圧着する方法が採用できる。或
いは連続的に塗布乾燥を行い、引きつづき連続的
に加熱ロールを通過させ、加熱圧着して巻き取
り、後加熱硬化を行う方法などの任意の方法も採
用できる。合成樹脂薄葉材料としては、ポリイミ
ドフイルムや極薄積層板等が挙げられ、金属箔と
しては、銅箔、アルミニウム箔、ニクロム箔等が
使用される。一方カバーレイフイルムの接着に使
用するには、前記溶液を通常の塗布装置で合成樹
脂薄葉材料の面上に15〜35μｍの膜厚となるよう
に塗布し、乾燥させて溶媒を揮散し或いは予備硬
化を行う。しかる後、フレキシブル印刷配線板に
適合するようにパターンを形成した後の配線板と
重ね合わせ、150〜180℃の温度、20〜40Kg／cm2の
圧力で加熱加圧して接着してラミネートする。
［発明の実施例］
次に本発明を実施例によつて具体的に説明す
る。実施例および比較例において「部」とは「重
量部」を意味する。
実施例 １
アクリルエラストマーSG90（帝国化学産業社
製、商品名）をメチルエチルケトン／トルエン＝
１／１の混合溶媒に溶解した25％溶液400部、
YDB−400（東都化成社製、商品名）の60％トル
エン溶液50部、Ｒ−140（三井石油化学エポキシ社
製、商品名）28.8部、ポリビニルホルマール樹脂
ビニレツクＦのＫ（チツソ社製、商品名）3.2部、
臭素化ポリパラビニルフエノール樹脂マルゼンレ
ジンMB（丸善石油社製、商品名）38部、キユア
ゾールC17Z（四国化成社製、商品名）1.66部、Ｈ
−43M（昭和軽金属社製、商品名）10.6部、メチ
ルセロソルブ160部およびジオキサン118部をそれ
ぞれ秤量、仕込み、高速撹拌機で十分撹拌し、
100メツシユの金網で濾過して、樹脂成分の臭素
含有率16〜17重量％のフレキシブル印刷配線板用
の接着剤溶液を調製した。
次いで厚さ50μｍのカプトン（デユポン社製、
ポリイミドフイルム商品名）に前記の接着剤溶液
を、乾燥後約22μｍの厚さになるように塗布し、
100℃で５分間、さらに150℃で２分間乾燥した。
その後接着剤取塗面に35μｍの電解銅箔（福田金
属工業社製）を重ね合わせ、熱圧プレスを使用し
てプレス温度160±２℃、圧力30Kg／cm2、加熱時
間60分間の条件でラミネートし、フレキシブル印
刷配線用基板を製造した。得られた基板の引剥が
し強さ、耐熱劣化後の接着性、半田耐熱性、難燃
性について試験をした。その結果を第１表に示し
たが、本発明の効果が確認された。
比較例 １
実施例１においてポリビニルホルマール樹脂ビ
ニレツクＬのＫ（チツソ社製、商品名）を添加し
ないで、またエポキシ樹脂としてＲ−140の30.4
部を用いた以外は、実施例１と同一条件で接着剤
溶液およびこれを用いたフレシキブル印刷配線板
用基板を製造した。次いで実施例１と同様な諸試
験を行つたので、その結果を第１表に示した。
[Technical field of the invention] The present invention relates to a flexible printed wiring board,
An adhesive composition for flexible printed wiring boards that has strong adhesion between metal foil and thin synthetic resin material, excellent heat resistance and heat deterioration resistance, moisture resistance and flame retardancy, and has excellent processing characteristics. . [Technical Background of the Invention and Problems Therewith] In recent years, as electronic devices have become more dense, lighter, thinner, and smaller, there has been an increasing demand for lightweight, flexible printed wiring boards that can mount three-dimensional wiring or functions. In addition, in consumer electronics, from the viewpoint of safety in particular, demands for flame retardant materials and adhesive properties after heat deterioration are becoming stronger. Adhesives for flexible printed wiring boards are used not only to bond thin synthetic resin materials and the treated surface of metal foil, but also to insulate and protect circuits on the shear (polished) surface of the metal foil of patterned wiring boards. It is desirable that it can be used to adhere coverlay films for use in other applications. In particular, for coverlay film adhesion, it must be able to firmly adhere to the sheared surface of the metal foil, suppress flow to the land portion to a small amount, and have good embedding properties between pattern circuits. On top of that,
Shelf life is at least 1 month at room temperature and 3 months at 5°C.
More than a month is required. Furthermore, in order to improve productivity and maintain dimensional accuracy, there is a need for workability that allows for heating and compression bonding at low temperatures and in a short time. However, conventional adhesives for flexible printed wiring boards, even when polyimide film with excellent heat resistance and flame retardancy is used as the base thin material, have poor adhesion, heat resistance, line insulation resistance, and It has been extremely difficult to achieve both heat deterioration resistance and flame retardancy. Conventionally, as adhesives for flexible printed wiring boards, nitrile rubber adhesives (JP-A-51-135936, JP-A-57-3877),
Polyamide adhesive (JP-A-54-125285), polyester adhesive (JP-A-50-16866, JP-A-54-7441), polyacrylic adhesive (JP-A-54-125285)
54-162736) and many others have been proposed. However, the nitrile rubber type has the disadvantage that it has poor adhesion after heat-resistant aging and tends to become extremely hard after a 10-day air aging test at 150°C, and the polyamide type has the disadvantage of slightly high hygroscopicity. be. Polyester-based materials have the disadvantage of weak adhesive strength compared to polyimide films, and polyacrylic-based materials require high temperatures and long periods of time for heat molding, and if the molding temperature is lowered and the molding time shortened, they have the disadvantage of poor moisture resistance. Ta. [Object of the Invention] The object of the present invention has been made to solve the above-mentioned difficulties and disadvantages, and has excellent adhesiveness, heat deterioration resistance, flame retardance, and moisture resistance, and can be processed as a coverlay film adhesive. The present invention aims to provide an adhesive composition for flexible printed wiring boards with good properties. [Summary of the Invention] As a result of intensive studies aimed at achieving the above object, the present inventors have discovered that the adhesive composition described below is suitable as an adhesive for flexible printed wiring boards, and have arrived at the present invention. It is ivy. That is, the present invention provides (A) an acrylic elastomer having one or more functional groups selected from the group of epoxy groups, carboxyl groups, and hydroxyl groups, (B) polyparavinylphenol resin, and (C) epoxy resin. , (D) a polyvinyl formal resin, (E) a curing agent accelerator, and (F) an inorganic filler as essential components. (A) One or two selected from the group of epoxy groups, carboxy groups and hydroxyl groups used in the present invention
Examples of acrylic elastomers having more than one type of functional group include Arontak S-1511L and S-
1511X, S-1015, S-1017 (manufactured by Toagosei Kagaku Co., Ltd.,
(Product name), AR-51 (manufactured by Nippon Zeon Co., Ltd., Product name),
Noxtite PA-501, PA-502 (manufactured by Nippon Mectron Co., Ltd., product name), Teisan Resin WSO23,
Examples include SG51, SG80, and SG90 (manufactured by Teikoku Kagaku Sangyo Co., Ltd., trade name), and these may be used alone or in a mixture of two or more. This acrylic elastomer may have a functional group such as an epoxy group, a carboxyl group, or a hydroxyl group, but among these, those having an epoxy group are particularly used because they react at low temperatures. The amount of this acrylic elastomer blended is preferably 30 to 70% by weight based on the resin component [(A)+(B)+(C)+(D)] of the adhesive composition. If the amount is less than 30% by weight, the flexibility will be poor, and if it exceeds 70% by weight, the flexibility will be improved but the soldering heat resistance and flame retardance after humidification will be poor, which is not preferable. Examples of the polyparavinylphenol resin (B) used in the present invention include Maruzen Resin M, Maruzen Resin MB (manufactured by Maruzen Oil Co., Ltd., trade name), and these may be used alone or in combination depending on the desired flame retardancy.
Use by mixing more than one species. Polyparavinylphenol resin has a molecular structure similar to thermoplastic polystyrene resin, and is also called paraoxystyrene resin, but it has excellent crosslinkability with epoxy resins due to the action of the hydroxyl group at the para position. (B) The blending amount of polyparavinylphenol resin is
It is desirable that the equivalent ratio [(b)/(c)] between the phenolic hydroxyl group (b) and the epoxy group (c) of the epoxy resin (c) is within the range of 0.5 to 7.0. If this equivalence ratio is less than 0.5, the soldering heat resistance after humidification will decrease, and if it exceeds 7.0, the adhesiveness will decrease and the heat deterioration resistance will be poor, which is not preferable. Bromination is carried out by introducing a brominated polyparavinylphenol resin, a brominated epoxy resin, or both, and the bromination rate is preferably 8% by weight or more based on the resin component of the adhesive composition. . This is because if the amount is less than 8% by weight, the effect on flame retardancy will be small. The epoxy resin (C) used in the present invention is not particularly limited, and all epoxy resins can be used.
Examples include bisphenol A type epoxy resins, novolak epoxy resins, and brominated epoxy resins thereof, and these may be used alone or in combination of two or more. Examples of the polyvinyl formal resin (D) used in the present invention include Denka formal #20, #30,
#100 (manufactured by Denki Kagaku Kogyo Co., Ltd., trade name), Vinylec F L, K, E (manufactured by Chitsuso Co., Ltd., trade name), etc., and these may be used alone or in a mixture of two or more. It is believed that the polyparavinyl formal resin takes a sea-island structure in the adhesive composition after curing, softens the hardness of the epoxy resin, and improves impact resistance. In the case of an adhesive composition for a flexible printed wiring board, it has been found that the hardness is alleviated and that it has a remarkable effect particularly on improving heat deterioration resistance. The amount of polyvinyl formal resin blended is preferably 0.5 to 5.0% by weight based on the resin component of the adhesive composition. Compounding amount is 0.5% by weight
If it is less than 5.0% by weight, there is no effect on heat deterioration resistance.
Exceeding this is not preferable because moisture resistance and adhesive strength decrease. Examples of the curing accelerator (E) used in the present invention include dicyandiamide, Epicure YPH-201 (manufactured by Yuka Ciel Epoxy Co., Ltd., trade name), BF 3 imidazole complex AC-4B series (manufactured by Maruzen Sekiyu Co., Ltd., trade name) , imidazole, etc., and these can be used alone or in a mixture of two or more. Crosslinking of epoxy resin is also carried out by paravinylphenol resin and acrylic elastomer, so depending on the molding conditions, a curing accelerator for the epoxy resin may not be necessary, but molding can be carried out at low temperatures for a short time. For this purpose, it is necessary to use a curing accelerator. The amount to be added is determined depending on the molding conditions employed or the desired shelf life. Examples of the inorganic filler (F) used in the present invention include ultrafine anhydrous silica and aluminum hydroxide, which may be used alone or in combination of two or more. The inorganic filler has the effect of adjusting surface tack (adhesion) and mitigating expansion and contraction of the adhesive composition at high temperatures such as during soldering. The blending amount of the inorganic filler is 3% based on the solid content of the adhesive composition.
~65% by weight is desirable. If the amount is less than 3% by weight, the surface tackiness will be strong and processability will be poor, and if it exceeds 65% by weight, the coating properties with the base thin material will be poor and the adhesion will be reduced, which is not preferable. Examples of solvents for adhesive compositions containing the above components as essential components include methyl ethyl ketone, acetone,
Toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, dioxane, methyl cellosolve acetate and mixtures thereof can be used. The adhesive composition is dissolved in a solvent and applied in a solution state, but the resin component before being dissolved can be prepared by mixing the respective raw materials or by proceeding with preliminary curing. The lamination of the synthetic resin thin material and the metal foil via the adhesive composition is achieved by applying the adhesive composition in a solution state to at least either the synthetic resin thin material or the metal foil, and then drying it in a hot air oven. A method can be adopted in which the solvent is volatilized or preliminary curing is performed, and then heat and pressure bonding is performed using a hot press. Alternatively, any method can be adopted, such as continuously coating and drying, then continuously passing through heated rolls, heat-pressing, winding, and post-heat curing. Examples of thin synthetic resin materials include polyimide films and ultra-thin laminates, and examples of metal foils include copper foil, aluminum foil, nichrome foil, and the like. On the other hand, in order to use the solution for adhering a coverlay film, apply the solution to a thickness of 15 to 35 μm on the surface of a thin synthetic resin material using an ordinary coating device, dry it to volatilize the solvent, or use a preliminary coating. Perform curing. Thereafter, it is stacked on a wiring board after forming a pattern to match the flexible printed wiring board, and is bonded and laminated by heating and pressing at a temperature of 150 to 180°C and a pressure of 20 to 40 kg/cm 2 . [Examples of the Invention] Next, the present invention will be specifically explained using Examples. In Examples and Comparative Examples, "parts" means "parts by weight." Example 1 Acrylic elastomer SG90 (manufactured by Teikoku Kagaku Sangyo Co., Ltd., trade name) was mixed with methyl ethyl ketone/toluene =
400 parts of a 25% solution dissolved in a 1/1 mixed solvent,
50 parts of a 60% toluene solution of YDB-400 (manufactured by Toto Kasei Co., Ltd., trade name), 28.8 parts of R-140 (manufactured by Mitsui Petrochemical Epoxy Co., Ltd., trade name), K of polyvinyl formal resin Vinylec F (manufactured by Chitsuso Corporation, trade name) name) 3.2 parts,
Brominated polyparavinylphenol resin Maruzen Resin MB (manufactured by Maruzen Oil Co., Ltd., trade name) 38 parts, Kyuazol C17Z (manufactured by Shikoku Kasei Co., Ltd., trade name) 1.66 parts, H
-43M (manufactured by Showa Light Metal Co., Ltd., trade name) 10.6 parts, methyl cellosolve 160 parts and dioxane 118 parts were weighed and prepared, and thoroughly stirred with a high-speed stirrer.
An adhesive solution for flexible printed wiring boards having a bromine content of 16 to 17% by weight in the resin component was prepared by filtration through a 100-mesh wire mesh. Next, Kapton with a thickness of 50 μm (manufactured by DuPont,
Apply the above adhesive solution to a polyimide film (trade name) to a thickness of approximately 22 μm after drying,
It was dried at 100°C for 5 minutes and then at 150°C for 2 minutes.
After that, a 35 μm electrolytic copper foil (manufactured by Fukuda Metal Industry Co., Ltd.) was placed on the adhesive coated surface, and a hot press was used at a press temperature of 160±2℃, a pressure of 30Kg/cm 2 and a heating time of 60 minutes. This was laminated to produce a flexible printed wiring board. The peel strength of the obtained substrate, adhesion after heat deterioration, soldering heat resistance, and flame retardance were tested. The results are shown in Table 1, and the effects of the present invention were confirmed. Comparative Example 1 In Example 1, K of polyvinyl formal resin Vinylec L (manufactured by Chitsuso Co., Ltd., trade name) was not added, and 30.4 of R-140 was added as an epoxy resin.
An adhesive solution and a substrate for a flexible printed wiring board using the adhesive solution were manufactured under the same conditions as in Example 1, except that the adhesive solution was used in Example 1. Next, various tests similar to those in Example 1 were conducted, and the results are shown in Table 1.
【表】
実施例 ２
アクリルエラストマーAR−51（日本ゼオン社
製、商品名）をメチルエチルケトン／トルエン＝
１／１の混合溶媒に溶解した25％溶液360部、
YDB−400（東都化成社製、商品名）の60％トル
エン溶液25部、Ｒ−140（三井石油化学エポキシ社
製、商品名）14.4部、ポリビニルホルマール樹脂
＃100（電気化学工業社製、商品名）1.6部、マル
ゼンレジンMB（丸善石油社製、商品名）19部、
AC−4B50（丸善石油社製、商品名）0.84部、Ｈ
−43M（昭和軽金属社製、商品名）90部、アエロ
ジル200（日本アエロジル社製、商品名）３部、メ
チルセロソルブアセテート200部、エチルセロソ
ルブ100部およびジオキサン100部をそれぞれ秤
量、仕込み、高速撹拌機で十分撹拌し、100メツ
シユ金網で濾過して、樹脂成分中の臭素含有率11
〜12重量％の接着溶剤液を調製した。
次いで厚さ25μｍのカプトン（デユポン社製、
ポリイミドフイルム商品名）に前記の接着剤溶液
を、乾燥後約35μｍの厚さになるように塗布し、
120℃で５分間、さらに150℃で２分間乾燥した。
次いでUL規格Ｖ−０のカプトンベース銅張板
（銅箔35μｍ）を評価用にエツチング加工した銅
箔のシヤイン面に重ね合わせ、熱圧プレスを使用
して、プレス温度160±２℃、圧力40Kg／cm2、加
熱時間20分の条件でラミネートした。得られたカ
バーレイ被覆について引剥がし強さ、耐熱劣化後
の接着性、半田耐熱性、難燃性、加湿後の耐半田
性、線間絶縁抵抗を試験したので、その結果を第
２表に示した。
実施例 ３
アクリルエラストマーSG−80（帝国化学産業社
製、商品名）をメチルエチルケトン／トルエン＝
１／１の混合溶媒に溶解した20％溶液300.3部、
アロンタツクＳ−1015（東亜合成化学社製、商品
名）９部、Ｒ−140（前出）3.5部、ポリビニルホ
ルマール樹脂ビニレツクＦのＥ（チツソ社製、商
品名）2.0部、マルゼンレジンMB（前出）27部、
ジシアンジアミド１部、エピキユアYPH−201
（油化シエルエポキシ社製、商品名）0.25部、Ｈ
−43M（前出）152.34部、メチルセロソルブ300
部、ジオキサン200部およびメチルエチルケトン
289部をそれぞれ秤量、仕込み、高速撹拌機で十
分撹拌し、100メツシユ金網で濾過して、樹脂成
分に対して臭素含有率12〜13％の接着剤溶液を調
製した。
次いで厚さ25μｍのカプトン（前出）に前記接
着剤溶液を、乾燥後約35μｍの厚さになるように
塗布し、120℃で５分間、さらに150℃で２分間乾
燥した後、UL規格Ｖ−０のカプトンベース銅張
板（銅箔35μｍ）を評価用にエチツング加工した
銅箔のシヤイン面に重ね合わせ、熱圧プレスを使
用してプレス温度170±２℃、圧力40Kg／cm2、加
熱時間45分の条件でラミネートしカバーレイ被覆
を行つた。得たれたカバーレイ被覆について引剥
がし強さ、耐熱劣化後の接着性、半田耐熱性、難
燃性、加湿後耐半田性、線間絶縁抵抗、加工性に
ついて試験したので、その結果を第２表に示し
た。
比較例 ２
実施例２においてマルゼンレジンMB（前出）
19部をフエノールノボラツク樹脂TD−2093（大
日本インキ化学工業社製、商品名）8.95部に代替
した以外は、実施例２と同一条件で接着剤溶液を
調製し、ラミネートした。こうして得られたカバ
ーレイ被覆について実施例２と同様の試験を行つ
たので、その結果を第２表に示した。
比較例 ３
実施例２においてＨ−43M（前出）90部および
アエロジル200（前出）３部を添加しない以外は、
すべて実施例２と同一条件で接着剤溶液を調製
し、ラミネートした。こうして得られたカバーレ
イ被覆について、実施例２と同様に試験を行つた
ので、その結果を第２表に示した。[Table] Example 2 Acrylic elastomer AR-51 (manufactured by Nippon Zeon Co., Ltd., trade name) was mixed with methyl ethyl ketone/toluene =
360 parts of a 25% solution dissolved in a 1/1 mixed solvent,
25 parts of 60% toluene solution of YDB-400 (manufactured by Toto Kasei Co., Ltd., trade name), 14.4 parts of R-140 (manufactured by Mitsui Petrochemical Epoxy Co., Ltd., trade name), polyvinyl formal resin #100 (manufactured by Denki Kagaku Kogyo Co., Ltd., trade name) name) 1.6 parts, Maruzen Resin MB (manufactured by Maruzen Oil Co., Ltd., trade name) 19 parts,
AC-4B50 (manufactured by Maruzen Oil Co., Ltd., trade name) 0.84 parts, H
-43M (manufactured by Showa Light Metal Co., Ltd., trade name) 90 parts, Aerosil 200 (manufactured by Nippon Aerosil Co., Ltd., trade name) 3 parts, methyl cellosolve acetate 200 parts, ethyl cellosolve 100 parts and dioxane 100 parts were weighed, prepared, and stirred at high speed. Thoroughly stir in a machine and filter through a 100-mesh wire mesh to reduce the bromine content in the resin component to 11.
A ~12% by weight adhesive solvent solution was prepared. Next, Kapton with a thickness of 25 μm (manufactured by DuPont,
Apply the above adhesive solution to a polyimide film (trade name) to a thickness of approximately 35 μm after drying,
It was dried at 120°C for 5 minutes and then at 150°C for 2 minutes.
Next, a UL standard V-0 Kapton base copper clad board (copper foil 35 μm) was placed on the shear side of the etched copper foil for evaluation, and a hot press was used to press at a temperature of 160 ± 2°C and a pressure of 40 kg. /cm 2 and a heating time of 20 minutes. The obtained coverlay coating was tested for peel strength, adhesion after heat deterioration, solder heat resistance, flame retardancy, solder resistance after humidification, and line insulation resistance.The results are shown in Table 2. Indicated. Example 3 Acrylic elastomer SG-80 (manufactured by Teikoku Kagaku Sangyo Co., Ltd., trade name) was mixed with methyl ethyl ketone/toluene.
300.3 parts of a 20% solution dissolved in a 1/1 mixed solvent,
Arontak S-1015 (manufactured by Toagosei Kagaku Co., Ltd., trade name) 9 parts, R-140 (mentioned above) 3.5 parts, polyvinyl formal resin Vinyretsu F of E (manufactured by Chitsuso Corporation, trade name) 2.0 parts, Maruzen Resin MB (manufactured by Chitsuso Corporation, trade name) issue) 27 copies,
Dicyandiamide 1 part, Epicure YPH-201
(manufactured by Yuka Ciel Epoxy Co., Ltd., trade name) 0.25 parts, H
-43M (listed above) 152.34 parts, methyl cellosolve 300
parts, 200 parts of dioxane and methyl ethyl ketone
289 parts of each were weighed, charged, thoroughly stirred with a high-speed stirrer, and filtered through a 100-mesh wire mesh to prepare an adhesive solution with a bromine content of 12 to 13% based on the resin component. Next, the adhesive solution was applied to Kapton (mentioned above) with a thickness of 25 μm so that it would have a thickness of about 35 μm after drying, and after drying at 120°C for 5 minutes and further at 150°C for 2 minutes, the adhesive solution was applied to UL standard V. -0 Kapton base copper clad board (copper foil 35μm) was placed on the shear side of the etched copper foil for evaluation, and heated using a hot press at a pressing temperature of 170±2℃ and a pressure of 40Kg/cm 2 . Lamination was performed for 45 minutes and coverlay coating was performed. The obtained coverlay coating was tested for peel strength, adhesion after heat deterioration, solder heat resistance, flame retardancy, solder resistance after humidification, line insulation resistance, and processability. Shown in the table. Comparative Example 2 In Example 2, Maruzen Resin MB (mentioned above)
An adhesive solution was prepared and laminated under the same conditions as in Example 2, except that 8.95 parts of phenol novolac resin TD-2093 (manufactured by Dainippon Ink & Chemicals, Inc., trade name) was substituted for 19 parts. The coverlay coating thus obtained was subjected to the same tests as in Example 2, and the results are shown in Table 2. Comparative Example 3 Except that 90 parts of H-43M (mentioned above) and 3 parts of Aerosil 200 (mentioned above) were not added in Example 2,
An adhesive solution was prepared and laminated under the same conditions as in Example 2. The coverlay coating thus obtained was tested in the same manner as in Example 2, and the results are shown in Table 2.
【表】【table】
【表】
の異常の有無を調べる
＊２：○良好 ×不良
［発明の効果］
以上説明したように、本発明のフレキシブル印
刷配線板用接着剤組成物は、接着性、耐熱劣化
性、難燃性、加湿後耐半田性、線間絶縁抵抗に優
れ、かつカバーレイ用とて用いる場合の加工性の
良い接着剤組成物であり、それらの特性バランス
がよいのでフレキシブル印刷配線板用として好適
のものである。Examine the presence or absence of abnormalities in [Table] *2: ○ Good × Bad [Effects of the invention] As explained above, the adhesive composition for flexible printed wiring boards of the present invention has excellent adhesive properties, heat deterioration resistance, and flame retardancy. It is an adhesive composition that has excellent properties such as solder resistance after humidification, and insulation resistance between lines, and has good processability when used for coverlays.With a good balance of these properties, it is suitable for use in flexible printed wiring boards. It is something.
Claims (1)
ロキシル基の群から選ばれた１種又は２種以上
の官能基を有するアクリルエラストマー、 (B) ポリパラビニルフエノール樹脂、 (C) エポキシ樹脂、 (D) ポリビニルホルマール樹脂、 (E) 硬化剤促進剤および (F) 無機充填剤 を必須成分とすることを特徴とするフレキシブル
印刷配線板用接着剤組成物。 ２ 接着剤組成物の樹脂成分［(A)＋(B)＋(C)＋(D)］
に対して、(A)アクリルエラストマーを30〜70重量
％、(D)ポリビニルホルマール樹脂を0.5〜5.0重量
％それぞれ含有する特許請求の範囲第１項記載の
フレキシブル印刷配線板用接着剤組成物。 ３ (B)フエノール樹脂のフエノール性水酸基当量
(b)と(C)エポキシ樹脂のエポキシ基当量(c)との当量
比［(b)／(c)］が0.5〜7.0の範囲内である特許請求
の範囲第１項又は第２項記載のフレキシブル印刷
配線板用接着剤組成物。 ４ 接着剤組成物の固形分に対して、(F)無機充填
剤を３〜65重量％含有する特許請求の範囲第１項
ないし第３項いずれか記載のフレキシブル印刷配
線板用接着剤組成物。 ５ 接着剤組成物の樹脂成分の臭素化率が８重量
％以上である特許請求の範囲第１項ないし第４項
いずれか記載のフレキシブル印刷配線板用接着剤
組成物。[Claims] 1 (A) an acrylic elastomer having one or more functional groups selected from the group of epoxy groups, carboxyl groups, and hydroxyl groups, (B) polyparavinylphenol resin, (C) An adhesive composition for a flexible printed wiring board, comprising an epoxy resin, (D) a polyvinyl formal resin, (E) a curing agent accelerator, and (F) an inorganic filler. 2 Resin component of adhesive composition [(A)+(B)+(C)+(D)]
The adhesive composition for a flexible printed wiring board according to claim 1, which contains (A) acrylic elastomer in an amount of 30 to 70% by weight, and (D) polyvinyl formal resin in an amount of 0.5 to 5.0% by weight. 3 (B) Phenolic hydroxyl group equivalent of phenolic resin
Claim 1 or 2, wherein the equivalent ratio [(b)/(c)] between (b) and the epoxy group equivalent (c) of the epoxy resin (C) is within the range of 0.5 to 7.0. Adhesive composition for flexible printed wiring boards. 4. The adhesive composition for a flexible printed wiring board according to any one of claims 1 to 3, which contains 3 to 65% by weight of (F) an inorganic filler based on the solid content of the adhesive composition. . 5. The adhesive composition for a flexible printed wiring board according to any one of claims 1 to 4, wherein the bromination rate of the resin component of the adhesive composition is 8% by weight or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60202536A JPS6262880A (en) | 1985-09-14 | 1985-09-14 | Adhesive composition for flexible printed wiring board |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60202536A JPS6262880A (en) | 1985-09-14 | 1985-09-14 | Adhesive composition for flexible printed wiring board |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6262880A JPS6262880A (en) | 1987-03-19 |
| JPH0552873B2 true JPH0552873B2 (en) | 1993-08-06 |
Family
ID=16459123
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60202536A Granted JPS6262880A (en) | 1985-09-14 | 1985-09-14 | Adhesive composition for flexible printed wiring board |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6262880A (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6429417A (en) * | 1987-07-24 | 1989-01-31 | Toshiba Corp | Epoxy resin composition |
| JPH0750819B2 (en) * | 1988-08-09 | 1995-05-31 | 信越化学工業株式会社 | Flame-retardant flexible printed circuit board |
| JPH08319466A (en) * | 1995-03-20 | 1996-12-03 | Fujitsu Ltd | Adhesive, semiconductor device, and its production |
| EP1268643A4 (en) * | 2000-03-28 | 2003-07-23 | Parlex Corp | Screen printable flame retardant coating |
| JP4654336B2 (en) * | 2003-12-18 | 2011-03-16 | 日本ゼオン株式会社 | Thermally conductive pressure-sensitive adhesive composition, thermally conductive sheet-like molded article, and method for producing the same |
| JP5654900B2 (en) * | 2010-03-03 | 2015-01-14 | 大日本印刷株式会社 | Adhesive composition and method for producing curable pressure-sensitive adhesive sheet |
-
1985
- 1985-09-14 JP JP60202536A patent/JPS6262880A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6262880A (en) | 1987-03-19 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |