JP4439614B2 - Alkali-developable photocurable / thermosetting composition - Google Patents
Alkali-developable photocurable / thermosetting composition Download PDFInfo
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- JP4439614B2 JP4439614B2 JP13859899A JP13859899A JP4439614B2 JP 4439614 B2 JP4439614 B2 JP 4439614B2 JP 13859899 A JP13859899 A JP 13859899A JP 13859899 A JP13859899 A JP 13859899A JP 4439614 B2 JP4439614 B2 JP 4439614B2
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
- C08L63/10—Epoxy resins modified by unsaturated compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1488—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing phosphorus
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
- C08G59/4292—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof together with monocarboxylic acids
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
Description
【０００１】
【発明の属する技術分野】
本発明は、プリント配線板、特にビルドアップ工法等による多層プリント配線板の層間絶縁材やソルダーレジスト等として有用なアルカリ現像型の光硬化性・熱硬化性組成物に関する。
【０００２】
【従来の技術】
最近の半導体部品の急速な進歩により、電子機器は小型軽量化、高性能化、多機能化の傾向にあり、これらに追従してプリント配線板の高密度化が進みつつある。例えば、導体回路の細線化、高多層化や、スルーバイアホール、ブラインドバイアホール等の小径化、さらには小型チップ部品の表面実装による高密度実装等が進みつつある。これらの高密度プリント配線板に対応して、多層プリント配線板の需要が増えてきており、このため、ビルドアップ工法等の新しい多層プリント配線板の製造方法が提唱されている。これらの用途で一様に必要とされる特性の１つに難燃性又は自己消火性がある。従来、難燃性又は自己消火性を付与するためには、ハロゲンを含有するエポキシ樹脂を熱硬化性成分として用いていた。
【０００３】
【発明が解決しようとする課題】
しかしながら、ハロゲン含有のエポキシ樹脂を使用した場合、廃棄後の多層プリント配線板の燃焼時にダイオキシン等の有害なガスを発生するということが最近問題となってきている。
そこで、本発明は、燃焼時にダイオキシン等の有害なガスが発生することのない、難燃性又は自己消火性を有するハロゲンフリーの光硬化性・熱硬化性組成物を提供することを目的としている。
【０００４】
【課題を解決するための手段】
前記目的を達成するために、本発明によれば、（Ａ）（ａ）１分子中に２個以上のエポキシ基を有する化合物のエポキシ基１当量に対して、（ｃ）下記一般式（１）で表わされる化合物を０．２〜０．８当量反応せしめ、次いでエポキシ残基に（ｂ）不飽和モノカルボン酸を反応せしめた後、（ｄ）飽和又は不飽和多塩基酸無水物を反応せしめて得られる、酸価が５０〜１５０ｍｇＫＯＨ／ｇの樹脂化合物、（Ｂ）光重合開始剤、（Ｃ）１分子中に２個以上のエポキシ基を有する化合物、（Ｄ）反応性及び／又は非反応性希釈剤、及び（Ｅ）メラミン、アセトグアナミン、ベンゾグアナミン、尿素及びジシアンジアミドから選ばれるいずれか少なくとも１種の窒素含有化合物を含むことを特徴とする難燃性又は自己消火性を有するアルカリ現像型の光硬化性・熱硬化性組成物が提供される。
【化２】
好適な態様においては、前記樹脂化合物（Ａ）の合成に用いられる１分子中に２個以上のエポキシ基を有する化合物（ａ）としては、フェノール又はクレゾールノボラック型エポキシ樹脂が用いられる。
前記一般式（１）で表わされる化合物（ｃ）の量は、前記１分子中に２個以上のエポキシ基を有する化合物（ａ）のエポキシ基１当量に対して、０．２〜０．８当量である。０．２当量未満では、難燃性の効果が小さくなり好ましくない。一方、０．８当量を越えた場合、不飽和モノカルボン酸の含有率が小さくなり、光硬化膜の耐アルカリ現像性が得られにくくなるため好ましくない。
【０００６】
また、前記樹脂化合物（Ａ）の酸価は５０〜１５０ｍｇＫＯＨ／ｇである。酸価が５０ｍｇＫＯＨ／ｇ未満では、アルカリ現像性が得られにくくなり好ましくない。一方、酸価が１５０ｍｇＫＯＨ／ｇより大きい場合、耐現像性が得られにくくなり好ましくない。
さらに他の好適な態様においては、前記樹脂化合物（Ａ）の合成に用いられる前記一般式（１）で表わされる化合物（ｃ）としては、ジフェニルホスフィン酸が用いられる。
【０００７】
【発明の実施の形態】
本発明に係る光硬化性・熱硬化性組成物は、（Ａ）（ａ）１分子中に２個以上のエポキシ基を有する化合物のエポキシ基１当量に対して、（ｃ）下記一般式（１）で表わされる化合物を０．２〜０．８当量反応せしめ、次いでエポキシ残基に（ｂ）不飽和モノカルボン酸を反応せしめた後、（ｄ）飽和又は不飽和多塩基酸無水物を反応せしめて得られる、酸価が５０〜１５０ｍｇＫＯＨ／ｇの樹脂化合物、（Ｂ）光重合開始剤、（Ｃ）１分子中に２個以上のエポキシ基を有する化合物、（Ｄ）反応性及び／又は非反応性希釈剤、及び（Ｅ）メラミン、アセトグアナミン、ベンゾグアナミン、尿素及びジシアンジアミドから選ばれるいずれか少なくとも１種の窒素含有化合物を含有することを特徴としている。すなわち、本発明の特徴は、難燃性又は自己消火性に効果のある下記一般式（１）のリン化合物を、カルボキシル基含有感光性樹脂化合物（上記（ａ）成分、（ｂ）成分及び（ｄ）成分の反応生成物）に導入した樹脂化合物（Ａ）を用いていることにある。その結果、ハロゲンフリーでも難燃性又は自己消火性に優れた光硬化性・熱硬化性組成物を構成することができる。
【化３】
前記樹脂化合物（Ａ）の合成に用いられる１分子中に２個以上のエポキシ基を有する化合物（ａ）としては、公知慣用の各種エポキシ樹脂、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、ビスフェノールＳ型エポキシ樹脂、水添ビスフェノールＡ型エポキシ樹脂、ビフェノール型エポキシ樹脂、ビキシレノール型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂、ビフェニル型エポキシ樹脂、ビスフェノールＡのノボラック型エポキシ樹脂などのグリシジルエーテル化合物、テレフタル酸ジグリシジルエステル、ヘキサヒドロフタル酸ジグリシジルエステル、ダイマー酸ジグリシジルエステルなどのグリシジルエステル化合物、トリグリシジルイソシアヌレート、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラグリシジルメタキシレンジアミン、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラグリシジルビスアミノメチルシクロヘキサン、Ｎ，Ｎ−ジグリシジルアニリンなどのグリシジルアミン化合物などが単独で又は２種以上を組み合わせて用いられるが、より好ましいものとしては高感度化やリンの導入率の調整が容易なフェノール又はクレゾールノボラック型エポキシ樹脂が挙げられる。
【０００９】
前記樹脂化合物（Ａ）の合成に用いられる不飽和モノカルボン酸（ｂ）としては、（メタ）アクリル酸、ヒドロキシル基含有の（メタ）アクリレートに多塩基酸無水物を付加したモノ（２−アクリロイルオキシエチル）コハク酸、モノ（２−アクリロイルオキシエチル）フタル酸、モノ（２−アクリロイルオキシエチル）ヘキサヒドロフタル酸、モノ（２−アクリロイルオキシプロピル）コハク酸、モノ（２−アクリロイルオキシプロピル）フタル酸、モノ（２−アクリロイルオキシプロピル）ヘキサヒドロフタル酸、モノ（２−メタクリロイルオキシエチル）コハク酸、モノ（２−メタクリロイルオキシエチル）フタル酸、モノ（２−メタクリロイルオキシエチル）ヘキサヒドロフタル酸、モノ（２−メタクリロイルオキシプロピル）コハク酸、モノ（２−メタクリロイルオキシプロピル）フタル酸、モノ（２−メタクリロイルオキシプロピル）ヘキサヒドロフタル酸などがあり、単独で又は２種以上を組み合わせて用いられる。なお、本明細書中において、（メタ）アクリル酸とはアクリル酸、メタクリル酸及びこれらの混合物を総称する用語であり、他の類似の表現についても同様である。
【００１０】
前記樹脂化合物（Ａ）の合成に用いられる前記一般式（１）で表わされる化合物（ｃ）としては、ジメチルホスフィン酸、ジブチルホスフィン酸、ジフェニルホスフィン酸などのホスフィン酸誘導体などが用いられるが、より好ましいものとしては、毒性が無く、安定性が良好なジフェニルホスフィン酸が用いられる。
【００１１】
前記樹脂化合物（Ａ）の合成に用いられる飽和又は不飽和多塩基酸無水物（ｄ）としては、フタル酸、テトラヒドロフタル酸、ヘキサヒドロフタル酸、コハク酸、トリメリット酸、ピロメリット酸等の無水物があり、これらの中でもテトラヒドロフタル酸、ヘキサヒドロフタル酸及びコハク酸の無水物が、硬化塗膜の特性の点から特に好ましい。これら飽和又は不飽和多塩基酸無水物（ｄ）は、単独で又は２種以上を組み合わせて用いることができる。
【００１２】
前記光重合開始剤（Ｂ）としては、公知慣用の各種光重合開始剤、例えば、ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル等のベンゾインとベンゾインアルキルエーテル類；アセトフェノン、２，２−ジメトキシ−２−フェニルアセトフェノン、２，２−ジエトキシ−２−フェニルアセトフェノン、１，１−ジクロロアセトフェノン等のアセトフェノン類；２−メチル−１−［４−（メチルチオ）フェニル］−２−モルホリノアミノプロパノン−１、２−ベンジル−２−ジメチルアミノ−１−（４−モルホリノフェニル）−ブタノン−１等のアミノアセトフェノン類；２−メチルアントラキノン、２−エチルアントラキノン、２−ターシャリーブチルアントラキノン、１−クロロアントラキノン等のアントラキノン類；２，４−ジメチルチオキサントン、２，４−ジエチルチオキサントン、２−クロロチオキサントン、２，４−ジイソプロピルチオキサントン等のチオキサントン類；アセトフェノンジメチルケタール、ベンジルジメチルケタール等のケタール類；ベンゾフェノン等のベンゾフェノン類；又はキサントン類などがある。これら公知慣用の光重合開始剤は、単独で又は２種以上を組み合わせて用いることができ、また、第３級アミン類のような公知慣用の光増感剤を単独で又は２種以上組み合わせて併用することができる。
これらの光重合開始剤の配合割合（光増感剤を併用する場合にはこれらの合計量）は、前記樹脂化合物（Ａ）１００重量部当り１〜３０重量部、好ましくは５〜２５重量部が適当である。光重合開始剤の使用量が、上記範囲より少ない場合、組成物の光硬化性が悪くなり、一方、多い場合は、光重合開始剤自身の吸収により厚膜での光硬化性が劣るので好ましくない。
【００１３】
前記化合物（Ｃ）としては、前記樹脂化合物（Ａ）の合成に用いるエポキシ化合物（ａ）と同様な公知慣用の各種エポキシ樹脂を用いることができる。
エポキシ化合物（Ｃ）の具体例としては、例えば、日本化薬（株）製ＥＢＰＳ−２００、旭電化工業（株）製ＥＰＸ−３０、大日本インキ化学工業（株）製エピクロンＥＸＡ−１５１４等のビスフェノールＳ型エポキシ樹脂；日本油脂（株）製ブレンマーＤＧＴ等のジグリシジルフタレート樹脂；日産化学（株）製ＴＥＰＩＣシリーズ、チバ・ガイギー社製アラルダイトＰＴ８１０等の複素環式エポキシ樹脂；油化シェルエポキシ（株）製ＹＸ−４０００等のビキシレノール型エポキシ樹脂；油化シェルエポキシ（株）製ＹＬ−６０５６等のビフェノール型エポキシ樹脂；東都化成（株）製ＺＸ−１０６３等のテトラグリシジルキシレノイルエタン樹脂；などの希釈剤に難溶性のエポキシ樹脂、
油化シェルエポキシ（株）製エピコート１００９、１０３１、大日本インキ化学工業（株）製エピクロンＮ−３０５０、Ｎ−７０５０、Ｎ−９０５０、旭化成工業（株）製ＡＥＲ−６６４、ＡＥＲ−６６７、ＡＥＲ−６６９、東都化成（株）製ＹＤ−０１２、ＹＤ−０１４、ＹＤ−０１７、ＹＤ−０２０、ＹＤ−００２、チバ・ガイギー社製ＸＡＣ−５００５、ＧＴ−７００４、６４８４Ｔ、６０９９、ダウ・ケミカル社製ＤＥＲ−６４２Ｕ、ＤＥＲ−６７３ＭＦ、旭電化工業（株）製ＥＰ−５４００、ＥＰ−５９００等のビスフェノールＡ型エポキシ樹脂；東都化成（株）製ＳＴ−２００４、ＳＴ−２００７等の水添ビスフェノールＡ型エポキシ樹脂；東都化成（株）製、ＹＤＦ−２００４、ＹＤＦ−２００７等のビスフェノールＦ型エポキシ樹脂；日本化薬（株）製ＥＰＰＮ−２０１、ＥＯＣＮ−１０３、ＥＯＣＮ−１０２０、ＥＯＣＮ−１０２５、旭化成工業（株）製ＥＣＮ−２７８、ＥＣＮ−２９２、ＥＣＮ−２９９、チバ・ガイギー社製ＥＣＮ−１２７３、ＥＣＮ−１２９９、東都化成（株）製ＹＤＣＮ−２２０Ｌ、ＹＤＣＮ−２２０ＨＨ、ＹＤＣＮ−７０２、ＹＤＣＮ−７０４、ＹＤＰＮ−６０１、ＹＤＰＮ−６０２、大日本インキ化学工業（株）製エピクロンＮ−６７３、Ｎ−６８０、Ｎ−６９５、Ｎ−７７０、Ｎ−７７５等のノボラック型エポキシ樹脂；旭電化工業（株）製ＥＰＸ−８００１、ＥＰＸ−８００２、ＥＰＰＸ−８０６０、ＥＰＰＸ−８０６１、大日本インキ化学工業（株）製エピクロンＮ−８８０等のビスフェノールＡのノボラック型エポキシ樹脂；旭電化工業（株）製ＥＰＸ−４９−６０、ＥＰＸ−４９−３０等のキレート型エポキシ樹脂；東都化成（株）製ＹＤＧ−４１４等のグリオキザール型エポキシ樹脂；東都化成（株）製ＹＨ−１４０２、ＳＴ−１１０、油化シェルエポキシ（株）製ＹＬ−９３１、ＹＬ−９３３等のアミノ基含有エポキシ樹脂；大日本インキ化学工業（株）製エピクロンＴＳＲ−６０１、旭電化工業（株）製ＥＰＸ−８４−２、ＥＰＸ−４０６１等のゴム変性エポキシ樹脂：山陽国策パルプ（株）製ＤＣＥ−４００等のジシクロペンタジエンフェノリック型エポキシ樹脂；旭電化工業（株）製Ｘ−１３５９等のシリコーン変性エポキシ樹脂；ダイセル化学工業（株）製プラクセルＧ−４０２、Ｇ−７１０等のε−カプロラクトン変性エポキシ樹脂；などの希釈剤に可溶性のエポキシ樹脂、などが挙げられる。
【００１４】
これらのエポキシ樹脂は、単独で又は２種以上を組み合わせて用いることができるが、特に、組成物中に微粒状で分散させることが好ましく、そのためには常温で固形もしくは半固形であることが好ましく、また混練時に前記樹脂化合物（Ａ）及び使用する希釈剤（Ｄ）に溶解しないもの、及び／又は感光性及び現像性に悪影響を及ぼさない範囲の溶解性のものがよい。つまり、希釈剤に難溶性の微粒状のエポキシ樹脂、あるいは難溶性のエポキシ樹脂と可溶性のエポキシ樹脂を組み合わせて用いることが好ましい。このとき、希釈剤に可溶なエポキシ樹脂の配合量は、熱硬化性成分としての全エポキシ化合物のエポキシ当量の５０モル％未満の割合であることが好ましい。希釈剤に可溶なエポキシ樹脂の配合割合が５０モル％以上（希釈剤に難溶性のエポキシ樹脂の配合割合が５０モル％未満）になると、仮乾燥後の指触乾燥性や現像ライフが低下するので好ましくないからである。また、希釈剤に可溶なエポキシ樹脂を多量に併用する場合には、プリント配線板への塗布前に多少増粘し易くなるので、前記樹脂化合物（Ａ）を主成分とする主剤とエポキシ化合物（Ｃ）を主成分とする硬化剤の二液形態に組成し、使用に際して両者を混合して用いるのが望ましい。
【００１５】
また、上記エポキシ化合物（Ｃ）の使用量の好適な範囲は、前記樹脂化合物（Ａ）のカルボキシル基１当量に対して、前記化合物（Ｃ）のエポキシ基が０．６〜２．０当量、さらに好ましくは１．０〜１．６当量となる割合である。エポキシ基が２．０当量を越える配合量では、アルカリ水溶液による塗膜の未露光部分の現像性、塗膜特性が低下するので好ましくない。一方、０．６当量未満では硬化塗膜の架橋密度が低下し、耐熱性等の必要な特性が得られないので好ましくない。
【００１６】
前記反応性及び／又は非反応性希釈剤（Ｄ）として用いられる反応性希釈剤の代表的なものとしては、２−ヒドロキシエチルアクリレート、２−ヒドロキシブチルアクリレートなどのヒドロキシアルキルアクリレート類；エチレングリコール、メトキシテトラエチレングリコール、ポリエチレングリコール、プロピレングリコールなどのグリコールのモノ又はジアクリレート類；Ｎ，Ｎ−ジメチルアクリルアミド、Ｎ−メチロールアクリルアミドなどのアクリルアミド類；Ｎ，Ｎ−ジメチルアミノエチルアクリレートなどのアミノアルキルアクリレート類；ヘキサジオール、トリメチロールプロパン、ペンタエリスリトール、ジペンタエリスリトール、トリス−ヒドロキシエチルイソシアヌレートなどの多価アルコール又はこれらのエチレンオキサイドの付加物もしくはプロピレンオキサイドの付加物の多価アクリレート類；フェノキシアクリレート、ビスフェノールＡジアクリレート、及びこれらのフェノール類のエチレンオキサイド付加物などのアクリレート類；グリセリンジグリシジルエーテル、トリメチロールプロパントリグリシジルエーテル、トリグリシジルイソシアヌレートなどのグリシジルエーテルのアクリレート類；及びメラミンアクリレート；及び／又は上記アクリレート類に対応するメタクリレート類などがある。上記のような反応性希釈剤は、単独で又は２種以上を組み合わせて用いることができる。反応性希釈剤の使用量の好適な範囲は、前記樹脂化合物（Ａ）１００重量部当り０〜３０重量部である。反応性希釈剤の配合割合が上記範囲を越えた場合、塗膜の指触乾燥性が低下するため好ましくない。
【００１７】
一方、前記反応性及び／又は非反応性希釈剤（Ｄ）として用いられる非反応性希釈剤の代表的なものとしては、エチルメチルケトン、シクロヘキサノン等のケトン類；トルエン、キシレン、テトラメチルベンゼン等の芳香族炭化水素類；セロソルブ、メチルセロソルブ、ブチルセロソルブ、カルビトール、メチルカルビトール、ブチルカルビトール、プロピレングリコールモノメチルエーテル、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールジエチルエーテル、トリプロピレングリコールモノメチルエーテル等のグリコールエーテル類；酢酸エチル、酢酸ブチル、乳酸ブチル、セロソルブアセテート、ブチルセロソルブアセテート、カルビトールアセテート、ブチルカルビトールアセテート、プロピレングリコールモノメチルエーテルアセテート、ジプロピレングリコールモノメチルエーテルアセテート、炭酸プロピレン等のエステル類；オクタン、デカン等の脂肪族炭化水素類；石油エーテル、石油ナフサ、ソルベントナフサ等の石油系溶剤などの公知慣用の有機溶剤がある。上記のような非反応性希釈剤は、単独で又は２種以上を組み合わせて用いることができる。非反応性希釈剤の使用量の好適な範囲は、塗布方法により異なるが、前記樹脂化合物（Ａ）１００重量部当り２０〜３００重量部、好ましくは３０〜２００重量部である。
【００１８】
本発明の光硬化性・熱硬化性組成物は、難燃性又は自己消火性を向上させるために、公知慣用の難燃剤を併用することができる。例えば、メラミン−リン酸塩；リン酸エステル系化合物；ポリリン酸塩系化合物；赤リン；水酸化アルミニウム、水酸化マグネシウム、ホウ酸亜鉛、ジルコニウム系化合物、モリブデン系化合物などの無機難燃剤を併用することができる。また、本発明の樹脂化合物（Ａ）のようなリン含有化合物は、メラミン、アセトグアナミン、ベンゾグアナミン、尿素、ジシアンジアミドなどの窒素含有化合物（Ｅ）と併用することにより、難燃性又は自己消火性を向上することができる。さらに、難燃性を有する熱硬化性樹脂であるメラミン樹脂、ベンゾグアナミン樹脂、尿素樹脂、シリコーン樹脂、ホスファゼン樹脂などを併用することもできる。これらの難燃剤や難燃性樹脂は、塗膜特性を低下させない範囲で使用することができる。
【００１９】
また、本発明の光硬化性・熱硬化性組成物は、塗膜の密着性、硬度等の特性を上げる目的で、硫酸バリウム、タルク、シリカ、酸化アルミニウム、水酸化アルミニウムなどの公知慣用の無機充填剤が使用できる。これらの無機充填剤の配合割合は前記樹脂化合物（Ａ）１００重量部当り、１００重量部以下が適当であり、好ましくは５０重量部以下である。上記範囲より多い場合、塗膜の強度の低下、感度低下などを生じるので好ましくない。さらに、必要に応じて、公知慣用の着色顔料、着色染料、熱重合禁止剤、増粘剤、消泡剤、レベリング剤、カップリング剤、難燃助剤等が使用できる。また、感度アップの目的で、必要に応じて、フェノチアジン系、アントラセン系、コロネン系、ベンズアントラセン系、ペリレン系、ピレン系、メロシアニン系、ケトクマリン系、チオキサントン系の増感色素が配合できる。さらに必要に応じて、潜在性の硬化触媒として、イミダゾール塩類や三フッ化ホウ素錯体、有機金属塩等を添加することができる。さらに、プリント配線板の回路、即ち銅の酸化防止の目的で、アデニン、ビニルトリアジン、ジシアンジアミド、オルソトリルビグアニド、メラミン等の化合物、又はこれらの塩を添加することができる。これらの化合物の配合割合は、前記樹脂化合物（Ａ）１００重量部当り２０重量部以下であり、これらを添加することにより、硬化塗膜の耐薬品性や銅箔との接着性が向上する。
【００２０】
本発明の光硬化性・熱硬化性組成物は、回路形成されたプリント配線板にスクリーン印刷法、カーテンコート法、スプレーコート法、ロールコート法等の方法により塗布し、例えば６０〜１００℃の温度で組成物中に含まれる有機溶剤を揮発乾燥（仮乾燥）させることにより、指触乾燥性に優れ、現像ライフの長い塗膜を形成できる。その後、パターンを形成したフォトマスクを通して選択的に活性光線により露光し、未露光部を希アルカリ水溶液により現像してレジストパターンを形成でき、さらに、例えば１４０〜１８０℃の温度に加熱して熱硬化させることにより、密着性、硬度、はんだ耐熱性、耐薬品性、耐溶剤性、電気絶縁性、耐電蝕性に優れた絶縁塗膜が形成される。
【００２１】
上記希アルカリ水溶液としては、水酸化カリウム、水酸化ナトリウム、炭酸ナトリウム、炭酸カリウム、リン酸ナトリウム、ケイ酸ナトリウム、アンモニア、アミン類などの希アルカリ水溶液が使用できる。
また、光硬化させるための照射光源としては、低圧水銀灯、中圧水銀灯、高圧水銀灯、超高圧水銀灯、キセノンランプ又はメタルハライドランプなどが適当である。その他、レーザー光線なども露光用活性光線として利用できる。
【００２２】
【実施例】
以下に合成例、実施例及び比較例を示して本発明を具体的に説明するが、本発明は下記実施例に限定されるものではない。なお、以下において「部」及び「％」とあるのは、特に断りのない限り全て重量基準である。
【００２３】
合成例１
クレゾールノボラック型エポキシ樹脂（エピクロンＮ−６８０、大日本インキ化学工業（株）製、エポキシ当量＝２１０）２１０部を撹拌機及び還流冷却器の付いた四つ口フラスコに入れ、カルビトールアセテート３０４部を加え、加熱溶解した。次に、反応触媒としてトリフェニルホスフィン２．０部及びジフェニルホスフィン酸１０９部を加え、９０〜１００℃で８時間反応させた。さらに、重合禁止剤としてヒドロキノン０．１部を加えた後、アクリル酸３６部を徐々に滴下し、１６時間反応させた。この反応物を８０〜９０℃まで冷却し、テトラヒドロフタル酸無水物１０１部を加え、８時間反応させ、冷却後、取り出した。
このようにして得られた感光性樹脂は、リンを３．４％含み、不揮発分が６０％、固形物の酸価が８２ｍｇＫＯＨ／ｇであった。以下、この反応溶液をＡワニスと称す。
【００２４】
比較合成例１
クレゾールノボラック型エポキシ樹脂（エピクロンＮ−６９５、大日本インキ化学工業（株）製、エポキシ当量＝２２０）２２０部を撹拌機及び還流冷却器の付いた四つ口フラスコに入れ、カルビトールアセテート２１４部を加え、加熱溶解した。次に、重合禁止剤としてハイドロキノン０．１部と、反応触媒としてトリフェニルホスフィン２．０部を加えた。この混合物を９５〜１０５℃に加熱し、アクリル酸７２部を徐々に滴下し、１６時間反応させた。この反応物を、８０〜９０℃まで冷却し、テトラヒドロフタル酸無水物１０６部を加え、８時間反応させ、冷却後、取り出した。
このようにして得られたエチレン性不飽和結合及びカルボキシル基を併せ持つ感光性樹脂は、不揮発分６５％、固形物の酸価１００ｍｇＫＯＨ／ｇであった。以下、この反応溶液をＢワニスと称す。
【００２５】
比較例１
前記合成例１で得られたＡワニスを用いた以下の配合成分（光硬化性組成物と熱硬化性組成物）を、それぞれ３本ロールミルで混練し、光硬化性組成物と熱硬化性組成物を得た。この光硬化性組成物６０部と熱硬化性組成物１６．５部を混合して光硬化性・熱硬化性組成物を得た。
光硬化性組成物
Ａワニス ３０部
イルガキュアー ９０７ ３部
（チバ・スペシャルティ・ケミカルズ（株）製の光重合開始剤）
ＫＳ−６６ ０．５部
（信越化学工業（株）製のシリコーン系消泡剤）
フタロシアニンブルー ０．２部
シリカ ２１部
タルク ３．３部
ジプロピレングリコールモノメチルエーテル ２部
合計 ６０部
熱硬化性組成物
トリグリシジルイソシアヌレート ８．５部
ジペンタエリスリトールヘキサアクリレート ８部
合計 １６．５部
【００２６】
実施例１
前記合成例１で得られたＡワニスを用いた以下の配合成分（光硬化性組成物と熱硬化性組成物）を、それぞれ３本ロールミルで混練し、光硬化性組成物と熱硬化性組成物を得た。この光硬化性組成物６０部と熱硬化性組成物１８部を混合して光硬化性・熱硬化性組成物を得た。
光硬化性組成物
Ａワニス ３０部
イルガキュアー ９０７ ３部
ＫＳ−６６ ０．５部
フタロシアニンブルー ０．２部
シリカ ２１部
タルク ３．３部
ジプロピレングリコールモノメチルエーテル ２部
合計 ６０部
熱硬化性組成物
トリグリシジルイソシアヌレート ８．５部
ジペンタエリスリトールヘキサアクリレート ８部
メラミン １．５部
合計 １８部
【００２７】
比較例２
前記合成例２で得られたＢワニスを用いた以下の配合成分（光硬化性組成物と熱硬化性組成物）を、それぞれ３本ロールミルで混練し、光硬化性組成物と熱硬化性組成物を得た。この光硬化性組成物６０部と熱硬化性組成物１６．５部を混合して光硬化性・熱硬化性組成物を得た。
光硬化性組成物
Ｂワニス ３０部
イルガキュアー ９０７ ３部
ＫＳ−６６ ０．５部
フタロシアニンブルー ０．２部
シリカ ２１部
タルク ３．３部
ジプロピレングリコールモノメチルエーテル ２部
合計 ６０部
熱硬化性組成物
トリグリシジルイソシアヌレート ８．５部
ジペンタエリスリトールヘキサアクリレート ８部
合計 １６．５部
【００２８】
比較例３
前記合成例２で得られたＢワニスを用いた以下の配合成分（光硬化性組成物と熱硬化性組成物）を、それぞれ３本ロールミルで混練し、光硬化性組成物と熱硬化性組成物を得た。この光硬化性組成物６０部と熱硬化性組成物１８部を混合して光硬化性・熱硬化性組成物を得た。
光硬化性組成物
Ｂワニス ３０部
イルガキュアー ９０７ ３部
ＫＳ−６６ ０．５部
フタロシアニンブルー ０．２部
シリカ ２１部
タルク ３．３部
ジプロピレングリコールモノメチルエーテル ２部
合計 ６０部
熱硬化性組成物
トリグリシジルイソシアヌレート ８．５部
ジペンタエリスリトールヘキサアクリレート ８部
メラミン １．５部
合計 １８部
【００２９】
比較例４
前記合成例２で得られたＢワニスを用いた以下の配合成分（光硬化性組成物と熱硬化性組成物）を、それぞれ３本ロールミルで混練し、光硬化性組成物と熱硬化性組成物を得た。この光硬化性組成物６０部と熱硬化性組成物４０部を混合して光硬化性・熱硬化性組成物を得た。
光硬化性組成物
Ｂワニス ３０部
イルガキュアー ９０７ ３部
ＫＳ−６６ ０．５部
フタロシアニンブルー ０．２部
シリカ ２１部
タルク ３．３部
ジプロピレングリコールモノメチルエーテル ２部
合計 ６０部
熱硬化性組成物
臭素化ノボラック型エポキシ樹脂
（エポキシ当量２８３、臭素含有量３５．５％） ３２部
ジペンタエリスリトールヘキサアクリレート ８部
合計 ４０部
【００３０】
比較例５
前記合成例２で得られたＢワニスを用いた以下の配合成分（光硬化性組成物と熱硬化性組成物）を、それぞれ３本ロールミルで混練し、光硬化性組成物と熱硬化性組成物を得た。この光硬化性組成物６０部と熱硬化性組成物４２部を混合して光硬化性・熱硬化性組成物を得た。
光硬化性組成物
Ｂワニス ３０部
イルガキュアー ９０７ ３部
ＫＳ−６６ ０．５部
フタロシアニンブルー ０．２部
シリカ ２１部
タルク ３．３部
ジプロピレングリコールモノメチルエーテル ２部
合計 ６０部
熱硬化性組成物
臭素化ノボラック型エポキシ樹脂
（エポキシ当量２８３、臭素含有量３５．５％） ３２部
ジペンタエリスリトールヘキサアクリレート ８部
メラミン ２部
合計 ４２部
【００３１】
性能評価：
前記各実施例及び比較例で得られた光硬化性・熱硬化性組成物を、基板上に全面塗布し、８０℃で２０分乾燥後、フォトマスクを介して露光を行い、アルカリ水溶液で現像した。この基板を１５０℃で６０分熱硬化し、評価基板を作製した。
【００３２】
（１）はんだ耐熱性
ロジン系フラックスを塗布した基板を、予め２６０℃に設定したはんだ槽に３０秒間浸漬し、プロピレングリコールモノメチエーテルアセテートでフラックスを洗浄した後、目視によるレジスト層の膨れ・剥がれ・変色について評価した。判定基準は以下のとおりである。
○ ：全く変化が認められないもの
△ ：ほんの僅か変化したもの
× ：レジスト層に膨れ、剥がれがあるもの
【００３３】
（２） 絶縁特性
ＩＰＣ Ｂ−２５のクシ型電極Ｂクーポンを用い、上記の条件で評価基板を作
製し、このクシ型電極にＤＣ５００Ｖのバイアスを印加し、絶縁抵抗値を測定した。
【００３４】
（３） 自己消火性
前記各実施例及び比較例で得られた光硬化性・熱硬化性組成物を、基板上に全面塗布し、８０℃で１５分乾燥した後、裏面にも全面塗布し、８０℃で２０分乾燥し、両面露光を行い、アルカリ水溶液で現像した。この基板を１５０℃で６０分熱硬化し、硬化塗膜の厚さが約８０μｍの評価基板を作製した。この基板を長さ１２５ｍｍ、幅１３ｍｍに切断し、下からガスバーナーの炎を接触させ、１０秒間保持した後、炎を遠ざけ、その後試料が燃焼していた時間を測定した。
得られた結果を表１に示す。
【表１】
【発明の効果】
以上のように、本発明の光硬化性・熱硬化性組成物をプリント配線板のソルダーレジストやビルドアップ工法等による多層プリント配線板の層間絶縁材として用いることにより、自己消火性があり、また燃焼時に有毒なガスが発生しない硬化物を得ることができる。しかも、プリント配線板上に本発明の光硬化性・熱硬化性組成物からなる塗膜を形成すると、露光後、アルカリ現像が可能となり、また、露光硬化部は自己消火性に優れたソルダーレジストを形成することができる。さらに、プリント配線板関係の永久保護レジスト、感光性接着剤、塗料、プラスチックレリーフ、プラスチックのハードコート剤、オフセット印刷板としてのＰＳ版、スクリーン印刷用の感光液及びレジストインキ等に用いることができ、幅広い分野で使用することができる。[0001]
BACKGROUND OF THE INVENTION
INDUSTRIAL APPLICABILITY The present invention is useful as an interlayer insulating material or a solder resist for a printed wiring board, particularly a multilayer printed wiring board by a buildup method or the like.Alkaline development typeThe present invention relates to a photocurable / thermosetting composition.
[0002]
[Prior art]
Due to recent rapid advances in semiconductor components, electronic devices are becoming smaller, lighter, higher performance, and multifunctional, and the printed wiring board is becoming increasingly dense following these trends. For example, conductor circuits have been made thinner, higher in number, smaller diameters such as through via holes and blind via holes, and high-density mounting by surface mounting of small chip components. Corresponding to these high-density printed wiring boards, the demand for multilayer printed wiring boards is increasing, and for this reason, a new multilayer printed wiring board manufacturing method such as a build-up method has been proposed. One property that is uniformly required in these applications is flame retardant or self-extinguishing. Conventionally, an epoxy resin containing a halogen has been used as a thermosetting component in order to impart flame retardancy or self-extinguishing properties.
[0003]
[Problems to be solved by the invention]
However, when a halogen-containing epoxy resin is used, it has recently become a problem that harmful gases such as dioxins are generated when the multilayer printed wiring board after disposal is burned.
Then, this invention aims at providing the halogen-free photocurable and thermosetting composition which has a flame retardance or self-extinguishing property, and does not generate | occur | produce harmful gas, such as a dioxin, at the time of combustion. .
[0004]
[Means for Solving the Problems]
In order to achieve the above object, according to the present invention, (A) (a) a compound having two or more epoxy groups in one molecule(C) 0.2 to 0.8 equivalents of the compound represented by the following general formula (1) is reacted with 1 equivalent of the epoxy group of(B) Unsaturated monocarboxylic acidTheAfter reaction, (d) obtained by reacting with saturated or unsaturated polybasic acid anhydrideAn acid value of 50 to 150 mg KOH / gResin compound, (B) photopolymerization initiator, (C) compound having two or more epoxy groups in one molecule, (D) reactive and / or non-reactive diluent, and (E) melamine, acetoguanamine And a flame-retardant or self-extinguishing alkali-curable photocurable / thermosetting composition comprising at least one nitrogen-containing compound selected from benzoguanamine, urea and dicyandiamide The
[Chemical 2]
In a preferred embodiment, phenol or a cresol novolac type epoxy resin is used as the compound (a) having two or more epoxy groups in one molecule used for the synthesis of the resin compound (A).
in frontThe amount of the compound (c) represented by the general formula (1) is 0.2 to 0.8 with respect to 1 equivalent of the epoxy group of the compound (a) having two or more epoxy groups in one molecule. EquivalentTheIf it is less than 0.2 equivalent, the effect of flame retardancy becomes small, which is not preferable. On the other hand, when it exceeds 0.8 equivalent, the content of unsaturated monocarboxylic acid is decreased, and it is difficult to obtain alkali developability of the photocured film, which is not preferable.
[0006]
Also,in frontThe acid value of the resin compound (A) is 50 to 150 mgKOH / g.TheWhen the acid value is less than 50 mgKOH / g, it is difficult to obtain alkali developability, which is not preferable. On the other hand, when the acid value is larger than 150 mgKOH / g, it is difficult to obtain development resistance, which is not preferable.
In still another preferred embodiment, diphenylphosphinic acid is used as the compound (c) represented by the general formula (1) used for the synthesis of the resin compound (A).
[0007]
DETAILED DESCRIPTION OF THE INVENTION
The photocurable / thermosetting composition according to the present invention comprises (A) (a) a compound having two or more epoxy groups in one molecule.(C) 0.2 to 0.8 equivalents of the compound represented by the following general formula (1) is reacted with 1 equivalent of the epoxy group of(B) Unsaturated monocarboxylic acidTheAfter reaction, (d) obtained by reacting with saturated or unsaturated polybasic acid anhydrideAn acid value of 50 to 150 mg KOH / gResin compound, (B) photopolymerization initiator, (C) compound having two or more epoxy groups in one molecule, (D) reactive and / or non-reactive diluent, and (E) melamine, acetoguanamine And at least one nitrogen-containing compound selected from benzoguanamine, urea and dicyandiamide. That is, the feature of the present invention is that a phosphorus compound represented by the following general formula (1) effective for flame retardancy or self-extinguishing properties is converted into a carboxyl group-containing photosensitive resin compound (the components (a), (b) and ( d) The resin compound (A) introduced into the reaction product of component) is used. As a result, a photocurable / thermosetting composition excellent in flame retardancy or self-extinguishing properties even without halogen can be constituted.
[Chemical Formula 3]
As the compound (a) having two or more epoxy groups in one molecule used for the synthesis of the resin compound (A), various known and usual epoxy resins such as bisphenol A type epoxy resins, bisphenol F type epoxy resins, Bisphenol S type epoxy resin, hydrogenated bisphenol A type epoxy resin, biphenol type epoxy resin, bixylenol type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene type epoxy resin, biphenyl type epoxy resin, bisphenol Glycidyl ether compounds such as A novolak epoxy resin, glycidyl ester compounds such as terephthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, dimer acid diglycidyl ester Glycidylamine compounds such as triglycidyl isocyanurate, N, N, N ′, N′-tetraglycidylmetaxylenediamine, N, N, N ′, N′-tetraglycidylbisaminomethylcyclohexane, N, N-diglycidylaniline Are used alone or in combination of two or more. More preferable examples include phenols or cresol novolac type epoxy resins which can easily increase the sensitivity and adjust the introduction rate of phosphorus.
[0009]
The unsaturated monocarboxylic acid (b) used for the synthesis of the resin compound (A) is mono (2-acryloyl) obtained by adding a polybasic acid anhydride to (meth) acrylic acid or hydroxyl group-containing (meth) acrylate. Oxyethyl) succinic acid, mono (2-acryloyloxyethyl) phthalic acid, mono (2-acryloyloxyethyl) hexahydrophthalic acid, mono (2-acryloyloxypropyl) succinic acid, mono (2-acryloyloxypropyl) phthalate Acid, mono (2-acryloyloxypropyl) hexahydrophthalic acid, mono (2-methacryloyloxyethyl) succinic acid, mono (2-methacryloyloxyethyl) phthalic acid, mono (2-methacryloyloxyethyl) hexahydrophthalic acid, Mono (2-methacryloyloxypropyl) koha Acid, mono (2-methacryloyloxypropyl) phthalate, include mono (2-methacryloyloxypropyl) hexahydrophthalic acid, used alone or in combination of two or more. In the present specification, (meth) acrylic acid is a generic term for acrylic acid, methacrylic acid and mixtures thereof, and the same applies to other similar expressions.
[0010]
As the compound (c) represented by the general formula (1) used for the synthesis of the resin compound (A), phosphinic acid derivatives such as dimethylphosphinic acid, dibutylphosphinic acid, and diphenylphosphinic acid are used. As a preferable one, diphenylphosphinic acid having no toxicity and good stability is used.
[0011]
Examples of the saturated or unsaturated polybasic acid anhydride (d) used for the synthesis of the resin compound (A) include phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, succinic acid, trimellitic acid, and pyromellitic acid. There are anhydrides, and among these, the anhydrides of tetrahydrophthalic acid, hexahydrophthalic acid and succinic acid are particularly preferred from the viewpoint of the properties of the cured coating film. These saturated or unsaturated polybasic acid anhydrides (d) can be used alone or in combination of two or more.
[0012]
Examples of the photopolymerization initiator (B) include various known photopolymerization initiators such as benzoin and benzoin alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether; acetophenone, 2,2- Acetophenones such as dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone; 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinoaminopropanone Aminoacetophenones such as -1,2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1; 2-methylanthraquinone, 2-ethylanthraquinone, 2-tertiarybutylanthraquinone, 1-chloroanthone Anthraquinones such as laquinone; thioxanthones such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone; ketals such as acetophenone dimethyl ketal and benzyldimethyl ketal; benzophenone Benzophenones; or xanthones. These known and commonly used photopolymerization initiators can be used alone or in combination of two or more, and known and commonly used photosensitizers such as tertiary amines can be used alone or in combination of two or more. Can be used together.
The blending ratio of these photopolymerization initiators (the total amount in the case of using a photosensitizer in combination) is 1 to 30 parts by weight, preferably 5 to 25 parts by weight per 100 parts by weight of the resin compound (A). Is appropriate. When the amount of the photopolymerization initiator used is less than the above range, the photocurability of the composition is deteriorated. Absent.
[0013]
As said compound (C), various well-known and usual epoxy resins similar to the epoxy compound (a) used for the synthesis | combination of the said resin compound (A) can be used.
Specific examples of the epoxy compound (C) include, for example, EBPS-200 manufactured by Nippon Kayaku Co., Ltd., EPX-30 manufactured by Asahi Denka Kogyo Co., Ltd., Epicron EXA-1514 manufactured by Dainippon Ink & Chemicals, Inc. Bisphenol S type epoxy resin; Diglycidyl phthalate resin such as Bremer DGT manufactured by Nippon Oil & Fats Co., Ltd .; heterocyclic epoxy resin such as TEPIC series manufactured by Nissan Chemical Co., Ltd., Araldite PT810 manufactured by Ciba-Geigy Co., Ltd .; Bixylenol type epoxy resin such as YX-4000 manufactured by Co., Ltd .; Biphenol type epoxy resin such as YL-6056 manufactured by Yuka Shell Epoxy Co., Ltd .; Tetraglycidyl xylenoyl ethane resin such as ZX-1063 manufactured by Tohto Kasei Co., Ltd. A poorly soluble epoxy resin in a diluent such as;
Epicoat 1009, 1031 manufactured by Yuka Shell Epoxy Co., Ltd., Epicron N-3050, N-7050, N-9050 manufactured by Dainippon Ink & Chemicals, Inc. AER-664, AER-667, AER manufactured by Asahi Kasei Kogyo Co., Ltd. -669, YD-012, YD-014, YD-017, YD-020, YD-002, Ciba-Geigy XAC-5005, GT-7004, 6484T, 6099, Dow Chemical DER-642U, DER-673MF manufactured by Asahi Denka Kogyo Co., Ltd. EP-5400, EP-5900 and other bisphenol A type epoxy resins; Toto Kasei Co., Ltd. ST-2004, hydrogenated bisphenol A such as ST-2007 Type epoxy resin; manufactured by Tohto Kasei Co., Ltd., YDF-2004, YDF-2007 and other bisphenol F type epoxy Shikasei; Nippon Kayaku Co., Ltd. EPPN-201, EOCN-103, EOCN-1020, EOCN-1025, Asahi Kasei Kogyo Co., Ltd. ECN-278, ECN-292, ECN-299, Ciba-Geigy ECN -1273, ECN-1299, YDCN-220L, YDCN-220HH, YDCN-702, YDCN-704, YDPN-601, YDPN-602, manufactured by Toto Kasei Co., Ltd., Epicron N-673, manufactured by Dainippon Ink & Chemicals, Inc. Novolak type epoxy resins such as N-680, N-695, N-770, N-775; EPX-8001, EPX-8002, EPPX-8060, EPPX-8061 manufactured by Asahi Denka Kogyo Co., Ltd., Dainippon Ink and Chemicals, Inc. Novolak epoxy resin of bisphenol A such as Epicron N-880 manufactured by Kogyo Co., Ltd. Chelate type epoxy resins such as EPX-49-60 and EPX-49-30 manufactured by Asahi Denka Kogyo Co., Ltd .; Glyoxal type epoxy resins such as YDG-414 manufactured by Tohto Kasei Co., Ltd .; YH-1402 manufactured by Tohto Kasei Co., Ltd. ST-110, YL-931, YL-933, YL-933, and other amino group-containing epoxy resins; Epicron TSR-601, Dainippon Ink & Chemicals Co., Ltd., EPX, Asahi Denka Kogyo Co., Ltd. -84-2, EPX-4061 rubber-modified epoxy resins: Sanyo Kokusaku Pulp Co., Ltd. DCE-400 and other dicyclopentadiene phenolic epoxy resins; Asahi Denka Kogyo Co., Ltd. X-1359 and other silicone-modified epoxies Diluent such as resin; ε-caprolactone-modified epoxy resin such as Plaxel G-402, G-710 manufactured by Daicel Chemical Industries, Ltd. Soluble epoxy resins, and the like.
[0014]
These epoxy resins can be used alone or in combination of two or more, but are preferably dispersed finely in the composition, and for that purpose it is preferably solid or semi-solid at normal temperature. In addition, those that do not dissolve in the resin compound (A) and the diluent (D) to be used at the time of kneading and / or those in the range that does not adversely affect the photosensitivity and developability are preferable. That is, it is preferable to use a slightly soluble epoxy resin hardly soluble in the diluent, or a combination of a hardly soluble epoxy resin and a soluble epoxy resin. At this time, it is preferable that the compounding quantity of the epoxy resin soluble in a diluent is a ratio of less than 50 mol% of the epoxy equivalent of all the epoxy compounds as a thermosetting component. If the blending ratio of the epoxy resin soluble in the diluent is 50 mol% or more (the blending ratio of the epoxy resin that is hardly soluble in the diluent is less than 50 mol%), the touch drying property after temporary drying and the development life are lowered. This is because it is not preferable. In addition, when a large amount of an epoxy resin soluble in the diluent is used in combination, it becomes easier to thicken slightly before application to the printed wiring board. Therefore, the main component and the epoxy compound containing the resin compound (A) as a main component It is desirable to use a two-component composition of a curing agent containing (C) as a main component, and to use a mixture of both.
[0015]
Moreover, the suitable range of the usage-amount of the said epoxy compound (C) is the epoxy group of the said compound (C) 0.6-2.0 equivalent with respect to 1 equivalent of carboxyl groups of the said resin compound (A), More preferably, the ratio is 1.0 to 1.6 equivalents. If the amount of the epoxy group exceeds 2.0 equivalents, the developability of the unexposed portion of the coating film and the coating film properties with the aqueous alkali solution are not preferable. On the other hand, if it is less than 0.6 equivalent, the crosslink density of the cured coating film is lowered, and necessary properties such as heat resistance cannot be obtained, which is not preferable.
[0016]
Representative reactive diluents used as the reactive and / or non-reactive diluent (D) include hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxybutyl acrylate; ethylene glycol, Mono- or diacrylates of glycols such as methoxytetraethylene glycol, polyethylene glycol and propylene glycol; acrylamides such as N, N-dimethylacrylamide and N-methylolacrylamide; aminoalkyl acrylates such as N, N-dimethylaminoethyl acrylate Polyhydric alcohols such as hexadiol, trimethylolpropane, pentaerythritol, dipentaerythritol, tris-hydroxyethyl isocyanurate or their ethylene Multivalent acrylates of adducts of xoxide or propylene oxide; acrylates such as phenoxy acrylate, bisphenol A diacrylate, and ethylene oxide adducts of these phenols; glycerin diglycidyl ether, trimethylolpropane triglycidyl ether Acrylates of glycidyl ethers such as triglycidyl isocyanurate; and melamine acrylates; and / or methacrylates corresponding to the above acrylates. The reactive diluents as described above can be used alone or in combination of two or more. A preferable range of the reactive diluent is 0 to 30 parts by weight per 100 parts by weight of the resin compound (A). When the mixing ratio of the reactive diluent exceeds the above range, it is not preferable because the dryness to touch of the coating film is lowered.
[0017]
On the other hand, typical non-reactive diluents used as the reactive and / or non-reactive diluent (D) include ketones such as ethyl methyl ketone and cyclohexanone; toluene, xylene, tetramethylbenzene and the like. Aromatic hydrocarbons: glycols such as cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, tripropylene glycol monomethyl ether Ethers: ethyl acetate, butyl acetate, butyl lactate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate, propylene glycol Known organic solvents such as esters such as methyl ether acetate, dipropylene glycol monomethyl ether acetate and propylene carbonate; aliphatic hydrocarbons such as octane and decane; petroleum solvents such as petroleum ether, petroleum naphtha and solvent naphtha is there. The non-reactive diluents as described above can be used alone or in combination of two or more. Although the suitable range of the usage-amount of a non-reactive diluent changes with coating methods, it is 20-300 weight part per 100 weight part of said resin compound (A), Preferably it is 30-200 weight part.
[0018]
In order to improve the flame retardancy or self-extinguishing properties, the photocurable / thermosetting composition of the present invention can be used in combination with a known and commonly used flame retardant. For example, melamine-phosphate; phosphate ester compound; polyphosphate compound; red phosphorus; combined with inorganic flame retardant such as aluminum hydroxide, magnesium hydroxide, zinc borate, zirconium compound, molybdenum compound be able to. Further, the phosphorus-containing compound such as the resin compound (A) of the present invention is a nitrogen-containing compound such as melamine, acetoguanamine, benzoguanamine, urea or dicyandiamide.(E)By using together, flame retardancy or self-extinguishing properties can be improved. Furthermore, a melamine resin, a benzoguanamine resin, a urea resin, a silicone resin, a phosphazene resin, or the like which is a thermosetting resin having flame retardancy can be used in combination. These flame retardants and flame retardant resins can be used as long as the coating film properties are not deteriorated.
[0019]
The photocurable / thermosetting composition of the present invention is a known and commonly used inorganic material such as barium sulfate, talc, silica, aluminum oxide, aluminum hydroxide for the purpose of improving the properties such as adhesion and hardness of the coating film. Fillers can be used. The blending ratio of these inorganic fillers is suitably 100 parts by weight or less, preferably 50 parts by weight or less, per 100 parts by weight of the resin compound (A). When the amount is more than the above range, it is not preferable because the strength of the coating film is lowered and the sensitivity is lowered. Furthermore, if necessary, known and commonly used color pigments, coloring dyes, thermal polymerization inhibitors, thickeners, antifoaming agents, leveling agents, coupling agents, flame retardant aids, and the like can be used. For the purpose of increasing sensitivity, phenothiazine-based, anthracene-based, coronene-based, benzanthracene-based, perylene-based, pyrene-based, merocyanine-based, ketocoumarin-based, and thioxanthone-based sensitizing dyes can be blended as necessary. Further, if necessary, imidazole salts, boron trifluoride complexes, organometallic salts, and the like can be added as latent curing catalysts. Furthermore, adenine, vinyltriazine, dicyandiamide, orthotolyl biguanide, melamine, or a salt thereof, or a salt thereof can be added for the purpose of preventing the oxidation of copper of the printed wiring board, that is, copper. The compounding ratio of these compounds is 20 parts by weight or less per 100 parts by weight of the resin compound (A), and by adding them, the chemical resistance of the cured coating film and the adhesion to the copper foil are improved.
[0020]
The photocurable / thermosetting composition of the present invention is applied to a printed wiring board on which a circuit is formed by a method such as a screen printing method, a curtain coating method, a spray coating method, or a roll coating method. By evaporating and drying (temporarily drying) the organic solvent contained in the composition at a temperature, it is possible to form a coating film having excellent touch drying properties and a long development life. Then, it can be selectively exposed with actinic rays through a photomask on which a pattern has been formed, and a resist pattern can be formed by developing an unexposed portion with a dilute aqueous alkali solution. As a result, an insulating coating film excellent in adhesion, hardness, solder heat resistance, chemical resistance, solvent resistance, electrical insulation and corrosion resistance is formed.
[0021]
As the dilute alkaline aqueous solution, dilute alkaline aqueous solutions such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, amines and the like can be used.
As the irradiation light source for photocuring, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a xenon lamp, a metal halide lamp, or the like is appropriate. In addition, a laser beam or the like can be used as an actinic ray for exposure.
[0022]
【Example】
Hereinafter, the present invention will be described in detail with reference to synthesis examples, examples and comparative examples, but the present invention is not limited to the following examples. In the following, “parts” and “%” are all based on weight unless otherwise specified.
[0023]
Synthesis example 1
210 parts of cresol novolac type epoxy resin (Epicron N-680, manufactured by Dainippon Ink & Chemicals, Inc., epoxy equivalent = 210) was placed in a four-necked flask equipped with a stirrer and reflux condenser, and 304 parts of carbitol acetate. Was added and dissolved by heating. Next, 2.0 parts of triphenylphosphine and 109 parts of diphenylphosphinic acid were added as reaction catalysts and reacted at 90-100 ° C. for 8 hours. Furthermore, after adding 0.1 part of hydroquinone as a polymerization inhibitor, 36 parts of acrylic acid was gradually added dropwise and reacted for 16 hours. The reaction product was cooled to 80 to 90 ° C., 101 parts of tetrahydrophthalic anhydride was added and reacted for 8 hours. After cooling, the reaction product was taken out.
The photosensitive resin thus obtained contained 3.4% of phosphorus, had a nonvolatile content of 60%, and had a solid acid value of 82 mgKOH / g. Hereinafter, this reaction solution is referred to as A varnish.
[0024]
Comparative Synthesis Example 1
Cresole novolak type epoxy resin (Epiclon N-695, Dainippon Ink & Chemicals, Epoxy equivalent = 220) 220 parts was placed in a four-necked flask equipped with a stirrer and reflux condenser, and 214 parts of carbitol acetate. Was added and dissolved by heating. Next, 0.1 part of hydroquinone as a polymerization inhibitor and 2.0 parts of triphenylphosphine as a reaction catalyst were added. This mixture was heated to 95 to 105 ° C., and 72 parts of acrylic acid was gradually added dropwise to react for 16 hours. The reaction product was cooled to 80 to 90 ° C., 106 parts of tetrahydrophthalic anhydride was added and reacted for 8 hours. After cooling, the reaction product was taken out.
The photosensitive resin having both an ethylenically unsaturated bond and a carboxyl group thus obtained had a nonvolatile content of 65% and a solid acid value of 100 mgKOH / g. Hereinafter, this reaction solution is referred to as B varnish.
[0025]
Comparative Example 1
The following blending components (photocurable composition and thermosetting composition) using the A varnish obtained in Synthesis Example 1 were kneaded with a three-roll mill, respectively, and the photocurable composition and the thermosetting composition were mixed. I got a thing. 60 parts of this photocurable composition and 16.5 parts of thermosetting composition were mixed to obtain a photocurable / thermosetting composition.
Photocurable composition
A varnish 30 parts
Irgacure 907 3 parts
(Photopolymerization initiator manufactured by Ciba Specialty Chemicals Co., Ltd.)
KS-66 0.5 part
(Shin-Etsu Chemical Co., Ltd. silicone-based antifoaming agent)
Phthalocyanine blue 0.2 parts
Silica 21 parts
Talc 3.3 parts
Dipropylene glycol monomethyl ether 2 parts
60 copies in total
Thermosetting composition
8.5 parts of triglycidyl isocyanurate
Dipentaerythritol hexaacrylate 8 parts
16.5 copies in total
[0026]
Example1
The following blending components (photocurable composition and thermosetting composition) using the A varnish obtained in Synthesis Example 1 were kneaded with a three-roll mill, respectively, and the photocurable composition and the thermosetting composition were mixed. I got a thing. 60 parts of this photocurable composition and 18 parts of a thermosetting composition were mixed to obtain a photocurable / thermosetting composition.
Photocurable composition
A varnish 30 parts
Irgacure 907 3 parts
KS-66 0.5 part
Phthalocyanine blue 0.2 parts
Silica 21 parts
Talc 3.3 parts
Dipropylene glycol monomethyl ether 2 parts
60 copies in total
Thermosetting composition
8.5 parts of triglycidyl isocyanurate
Dipentaerythritol hexaacrylate 8 parts
Melamine 1.5 parts
18 copies in total
[0027]
Comparative example2
The following blending components (photocurable composition and thermosetting composition) using the B varnish obtained in Synthesis Example 2 were kneaded with a three-roll mill, respectively, and the photocurable composition and the thermosetting composition were mixed. I got a thing. 60 parts of this photocurable composition and 16.5 parts of thermosetting composition were mixed to obtain a photocurable / thermosetting composition.
Photocurable composition
B varnish 30 parts
Irgacure 907 3 parts
KS-66 0.5 part
Phthalocyanine blue 0.2 parts
Silica 21 parts
Talc 3.3 parts
Dipropylene glycol monomethyl ether 2 parts
60 copies in total
Thermosetting composition
8.5 parts of triglycidyl isocyanurate
Dipentaerythritol hexaacrylate 8 parts
16.5 copies in total
[0028]
Comparative example3
The following blending components (photocurable composition and thermosetting composition) using the B varnish obtained in Synthesis Example 2 were kneaded with a three-roll mill, respectively, and the photocurable composition and the thermosetting composition were mixed. I got a thing. 60 parts of this photocurable composition and 18 parts of a thermosetting composition were mixed to obtain a photocurable / thermosetting composition.
Photocurable composition
B varnish 30 parts
Irgacure 907 3 parts
KS-66 0.5 part
Phthalocyanine blue 0.2 parts
Silica 21 parts
Talc 3.3 parts
Dipropylene glycol monomethyl ether 2 parts
60 copies in total
Thermosetting composition
8.5 parts of triglycidyl isocyanurate
Dipentaerythritol hexaacrylate 8 parts
Melamine 1.5 parts
18 copies in total
[0029]
Comparative example4
The following blending components (photocurable composition and thermosetting composition) using the B varnish obtained in Synthesis Example 2 were kneaded with a three-roll mill, respectively, and the photocurable composition and the thermosetting composition were mixed. I got a thing. 60 parts of the photocurable composition and 40 parts of the thermosetting composition were mixed to obtain a photocurable / thermosetting composition.
Photocurable composition
B varnish 30 parts
Irgacure 907 3 parts
KS-66 0.5 part
Phthalocyanine blue 0.2 parts
Silica 21 parts
Talc 3.3 parts
Dipropylene glycol monomethyl ether 2 parts
60 copies in total
Thermosetting composition
Brominated novolac epoxy resin
(Epoxy equivalent 283, bromine content 35.5%) 32 parts
Dipentaerythritol hexaacrylate 8 parts
40 copies in total
[0030]
Comparative example5
The following blending components (photocurable composition and thermosetting composition) using the B varnish obtained in Synthesis Example 2 were kneaded with a three-roll mill, respectively, and the photocurable composition and the thermosetting composition were mixed. I got a thing. 60 parts of this photocurable composition and 42 parts of thermosetting composition were mixed to obtain a photocurable / thermosetting composition.
Photocurable composition
B varnish 30 parts
Irgacure 907 3 parts
KS-66 0.5 part
Phthalocyanine blue 0.2 parts
Silica 21 parts
Talc 3.3 parts
Dipropylene glycol monomethyl ether 2 parts
60 copies in total
Thermosetting composition
Brominated novolac epoxy resin
(Epoxy equivalent 283, bromine content 35.5%) 32 parts
Dipentaerythritol hexaacrylate 8 parts
2 parts of melamine
42 copies in total
[0031]
Performance evaluation:
The photocurable / thermosetting compositions obtained in the above Examples and Comparative Examples were applied on the entire surface of the substrate, dried at 80 ° C. for 20 minutes, exposed through a photomask, and developed with an aqueous alkali solution. did. This substrate was thermally cured at 150 ° C. for 60 minutes to produce an evaluation substrate.
[0032]
(1) Solder heat resistance
The substrate coated with the rosin flux was dipped in a solder bath set at 260 ° C. for 30 seconds, washed with propylene glycol monomethyl ether acetate, and then visually evaluated for swelling, peeling and discoloration of the resist layer. The judgment criteria are as follows.
○: No change at all
△: Slightly changed
X: Resist layer swelled and peeled
[0033]
(2) Insulation characteristics
Using an IPC B-25 comb-type electrode B coupon, an evaluation board was made under the above conditions.
A bias of DC500V was applied to this comb-shaped electrode, and the insulation resistance value was measured.
[0034]
(3) Self-extinguishing properties
The photocurable / thermosetting composition obtained in each of the above Examples and Comparative Examples was applied to the entire surface of the substrate, dried at 80 ° C. for 15 minutes, and then applied to the entire back surface, and then at 80 ° C. for 20 minutes. It dried, performed double-sided exposure, and developed with aqueous alkali solution. This substrate was thermally cured at 150 ° C. for 60 minutes to produce an evaluation substrate having a cured coating thickness of about 80 μm. This substrate was cut into a length of 125 mm and a width of 13 mm, and a flame of a gas burner was contacted from below, held for 10 seconds, then moved away from the flame, and then the time during which the sample was burned was measured.
The obtained results are shown in Table 1.
[Table 1]
【The invention's effect】
As described above, by using the photocurable / thermosetting composition of the present invention as an interlayer insulating material of a multilayer printed wiring board by a solder resist of a printed wiring board or a build-up method, self-extinguishing is provided. A cured product in which no toxic gas is generated during combustion can be obtained. Moreover, when a coating film made of the photocurable / thermosetting composition of the present invention is formed on a printed wiring board, alkali development is possible after exposure, and the exposed cured part is a solder resist with excellent self-extinguishing properties. Can be formed. Furthermore, it can be used for permanent protection resists related to printed wiring boards, photosensitive adhesives, paints, plastic reliefs, hard coating agents for plastics, PS plates as offset printing plates, photosensitive liquids and resist inks for screen printing, etc. Can be used in a wide range of fields.
Claims (3)
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13859899A JP4439614B2 (en) | 1999-05-19 | 1999-05-19 | Alkali-developable photocurable / thermosetting composition |
| PCT/JP2000/003143 WO2000071597A1 (en) | 1999-05-19 | 2000-05-16 | Photocuring and thermosetting composition |
| TW89109471A TW527371B (en) | 1999-05-19 | 2000-05-17 | Photocurable and thermosetting composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13859899A JP4439614B2 (en) | 1999-05-19 | 1999-05-19 | Alkali-developable photocurable / thermosetting composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2000327742A JP2000327742A (en) | 2000-11-28 |
| JP4439614B2 true JP4439614B2 (en) | 2010-03-24 |
Family
ID=15225844
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13859899A Expired - Lifetime JP4439614B2 (en) | 1999-05-19 | 1999-05-19 | Alkali-developable photocurable / thermosetting composition |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP4439614B2 (en) |
| TW (1) | TW527371B (en) |
| WO (1) | WO2000071597A1 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4523703B2 (en) * | 2000-06-22 | 2010-08-11 | 昭和高分子株式会社 | Photosensitive flame retardant resin composition |
| JP4534313B2 (en) * | 2000-06-23 | 2010-09-01 | 日立化成工業株式会社 | Photosensitive resin composition, photosensitive element using the same, method for producing resist pattern, resist pattern and resist pattern laminated substrate |
| JP2002265567A (en) * | 2001-03-06 | 2002-09-18 | Showa Highpolymer Co Ltd | Photosensitive flame-retardant resin and its composition |
| JP4878597B2 (en) * | 2005-04-13 | 2012-02-15 | 株式会社タムラ製作所 | Photosensitive resin composition, printed wiring board, and semiconductor package substrate |
| TW200710570A (en) * | 2005-05-31 | 2007-03-16 | Taiyo Ink Mfg Co Ltd | Composition for forming adhesive pattern, multilayer structure obtained by using same, and method for producing such multilayer structure |
| JP5563256B2 (en) * | 2009-08-18 | 2014-07-30 | 京セラケミカル株式会社 | Photosensitive resin composition, and photosensitive film and photosensitive resist using the same |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3190251B2 (en) * | 1995-06-06 | 2001-07-23 | 太陽インキ製造株式会社 | Photocurable and thermosetting resin composition for alkali-developed flexible printed wiring boards |
| WO1997012925A1 (en) * | 1995-09-29 | 1997-04-10 | Toshiba Chemical Corporation | Halogen-free flame-retardant epoxy resin composition, and prepreg and laminate containing the same |
| DE19613063C2 (en) * | 1996-04-01 | 1998-09-17 | Clariant Gmbh | Phosphorus modified epoxy resins and a process for their preparation |
| DE19613067C2 (en) * | 1996-04-01 | 1998-12-03 | Clariant Gmbh | Phosphorus-modified epoxy resin mixtures of epoxy resins, phosphorus-containing compounds and a hardener, a process for their preparation and their use |
| DE19613064C2 (en) * | 1996-04-01 | 1998-12-17 | Clariant Gmbh | Phosphorus-modified epoxy resin mixtures of epoxy resins, phosphorus-containing compounds and a hardener, process for their preparation and their use |
-
1999
- 1999-05-19 JP JP13859899A patent/JP4439614B2/en not_active Expired - Lifetime
-
2000
- 2000-05-16 WO PCT/JP2000/003143 patent/WO2000071597A1/en active Application Filing
- 2000-05-17 TW TW89109471A patent/TW527371B/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| TW527371B (en) | 2003-04-11 |
| WO2000071597A1 (en) | 2000-11-30 |
| JP2000327742A (en) | 2000-11-28 |
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