JP2004359890A - Photocurable resin composition, photosensitive thermosetting resin composition and its cured product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a photocurable resin composition which forms an excellent film, and a photosensitive thermosetting resin composition containing the same. <P>SOLUTION: The photocurable resin composition is a mixture composed of (A) a photocurable compound obtained by reacting (a) an epoxy compound having at least three epoxy groups in the molecule with a monobasic acid selected from (b) an unsaturated group-containing monocarboxylic acid or a mixture of (b) the unsaturated group-containing monocarboxylic acid and (c) a saturated active hydrogen compound, followed by further reacting the reaction product with (d) a polybasic acid anhydride; (B) an epoxy-based saturated polycarboxylic acid compound obtained by reacting (e) an epoxy compound having at least two epoxy groups in the molecule with (c) the saturated active hydrogen compound, followed by further reacting the reaction product with (d) the polybasic acid anhydride; and/or (C) an acrylic saturated carboxylic acid compound obtained by polymerizing (f) a polymerizable monomer comprising (meth)acrylic acid as an essential component. The photosensitive thermosetting resin composition comprises the photocurable resin composition as an essential component. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

（式中、Ｍは―Ｈ又は

を表し、Ｍの少なくとも一つは

であり、Ｘ，Ｙは同じ又は異なる二価の芳香族基、ｍは１〜２０を表す。）
一般式（２）
【化４】

（式中、Ｒは―Ｈ又はＣＨ_３、ｎは１〜２０を表す。）
【００１２】
（２）飽和活性水素化合物（ｃ）が、モノカルボン酸、モノフェノール、２級のモノアミンからなる群より選ばれる少なくとも一種類以上の飽和活性水素化合物であることを特徴とする上記（１）記載の光硬化性樹脂組成物。
【００１３】
（３）上記光硬化性化合物（Ａ）とエポキシ系飽和ポリカルボン酸化合物（Ｂ）及び／又はアクリル系飽和ポリカルボン酸化合物（Ｃ）との混合物が、４０〜１６０ｍｇＫＯＨ／ｇの範囲の酸価を有することを特徴とする上記（１）又は（２）記載の光硬化性樹脂組成物。
【００１４】
（４）上記（１）〜（３）のいずれかに記載の光硬化性樹脂組成物と、１分子中に２個以上のエポキシ基を有するエポキシ化合物（Ｄ）、光重合開始剤（Ｅ）、希釈剤（Ｆ）を必須成分として含有することを特徴とする感光性熱硬化性樹脂組成物。
【００１５】
（５）１分子中に２個以上のエポキシ基を有するエポキシ化合物（Ｄ）のエポキシ基の当量が、光硬化性樹脂組成物中のカルボキシル基１当量に対して０．１〜１．５当量の範囲で配合されることを特徴とする上記（４）記載の感光性熱硬化性樹脂組成物。
【００１６】
（６）光重合開始剤（Ｅ）が、光硬化性樹脂組成物中の光硬化性化合物（Ａ）１００重量部に対して０．１〜３０重量部の範囲内で配合されることを特徴とする上記（４）又は（５）記載の感光性熱硬化性樹脂組成物。
【００１７】
（７）希釈剤（Ｆ）が、有機溶剤及び／又は（メタ）アクリル酸エステルであり、光硬化性樹脂組成物１００重量部に対して１〜３００重量部の範囲で配合されることを特徴とする上記（４）〜（６）のいずれかに記載の感光性熱硬化性樹脂組成物。
【００１８】
（８）上記（４）〜（７）のいずれかに記載の感光性熱硬化性樹脂組成物を硬化させて得られる硬化物。
を要旨とするものである。
【００１９】
【発明の実施の形態】
本発明について以下に詳細を説明する。
まず、本明細書中、（メタ）アクリル酸とは、アクリル酸、メタクリル酸又はこれらの混合物を、（メタ）アクリル酸エステルとは、アクリル酸エステル、メタクリル酸エステル、又はこれらの混合物を意味する。
【００２０】
本発明の第１の発明は、下記一般式（１）及び／又は（２）で示される１分子中に３個以上のエポキシ基を有するエポキシ化合物（ａ）と、不飽和基含有モノカルボン酸（ｂ）又は不飽和基含有モノカルボン酸（ｂ）と飽和活性水素化合物（ｃ）との混合物から選ばれる一塩基酸を反応させて得られる反応生成物に、さらに多塩基酸無水物（ｄ）を反応させて得られる光硬化性化合物（Ａ）と、１分子中に２個以上のエポキシを有するエポキシ化合物（ｅ）と、飽和活性水素化合物（ｃ）を反応させて得られる反応生成物に、さらに多塩基酸無水物（ｄ）を反応させて得られるエポキシ系飽和ポリカルボン酸化合物（Ｂ）及び／又は（メタ）アクリル酸を必須成分として含有する重合性モノマー（ｆ）を重合させて得られるアクリル系飽和ポリカルボン酸化合物（Ｃ）との混合物からなり、該混合物の二重結合当量が６００〜４０００ｇ／ｅｑ．の範囲である光硬化性樹脂組成物に関し、第２の発明は、該光硬化性樹脂組成物と、１分子中に２個以上のエポキシ基を有するエポキシ化合物（Ｄ）、光重合開始剤（Ｅ）、希釈剤（Ｆ）を必須成分として含有する感光性熱硬化性樹脂組成物に関する。
一般式（１）
【化５】

（式中、Ｍは―Ｈ又は

を表し、Ｍの少なくとも一つは

であり、Ｘ，Ｙは同じ又は異なる二価の芳香族基、ｍは１〜２０を表す。）
一般式（２）
【化６】

（式中、Ｒは―Ｈ又はＣＨ_３、ｎは１〜２０を表す。）
【００２１】
上記一般式（１）におけるＸ，Ｙは同じ又は異なる下記（ｇ）〜（ｍ）の二価の芳香族基を表し、例えば、下記の（ｇ），（ｈ）においてＲ_１，Ｒ_２，Ｒ_３，Ｒ_４は、水素原子、又は炭素数１〜４のアルキル基、又はハロゲン原子であり、ｐ，ｑ，ｒ，ｓはＲ_１，Ｒ_２，Ｒ_３，Ｒ_４がアルキル基のときは１〜４であり、ハロゲン原子のときは１又は２である。（ｉ），（ｊ）及び（ｍ）はにおいてＲ_５，Ｒ_６，Ｒ_７，Ｒ_８は、水素原子又は炭素数１〜１０のアルキル基であり、ｔ，ｘ，ｙは１〜４、ｚは１〜４である。また、（ｈ）におけるＡは、アルキレン、シクロアルキレン、ハロゲン、シクロキル又はアリール置換アルキレン、Ｓ、Ｓ＝Ｏ又はＯ＝Ｓ＝Ｏである。
【化７】

【化８】

【化９】

【化１０】

【化１１】

【化１２】

【化１３】

【００２２】
まず、本発明における光硬化性樹脂組成物について説明する。
本発明における光硬化性樹脂組成物は、下記の光硬化性化合物（Ａ）と、エポキシ系飽和ポリカルボン酸化合物（Ｂ）及び／又はアクリル系飽和ポリカルボン酸化合物（Ｃ）よりなる。該光硬化性化合物（Ａ）は、感光性の二重結合とカルボキシル基を有し、紫外線照射による光硬化工程で共存する光重合開始剤の存在でラジカル重合して硬化物となる。この時に紫外線が照射されない部分は、分子中のカルボキシル基の存在でアルカリ現像工程において除去される。また、硬化物中のカルボキシル基は、熱硬化工程においてエポキシ化合物（Ｄ）と反応して強固な結合を形成する作用を有する。また、エポキシ系飽和ポリカルボン酸化合物（Ｂ）及び／又はアクリル系飽和ポリカルボン酸化合物（Ｃ）は、カルボキシル基のみを有し、上記アルカリ現像工程を容易にする作用を有し、また硬化物中のカルボキシル基は、熱硬化工程においてエポキシ化合物（Ｄ）と反応して強固な結合を形成する作用を有する。
【００２３】
このような光硬化性樹脂組成物を構成する光硬化性化合物（Ａ）は、上記一般式（１）及び／又は（２）で示される１分子中に３個以上のエポキシ基を有するエポキシ化合物（ａ）と、不飽和基含有モノカルボン酸（ｂ）又は不飽和基含有モノカルボン酸（ｂ）と飽和活性水素化合物（ｃ）との混合物から選ばれる一塩基酸を公知の触媒、重合禁止剤を存在させて、不活性ガス気流中又は空気の存在下、６０〜１５０℃で反応させて得られる生成物における分子中のアルコール性水酸基に、さらに多塩基酸無水物（ｄ）を３０〜１５０℃で反応させることにより製造することができる。
【００２４】
また、光硬化性樹脂組成物を構成するエポキシ系飽和ポリカルボン酸化合物（Ｂ）は、１分子中に２個以上のエポキシ基を有するエポキシ化合物（ｅ）と、飽和活性水素化合物（ｃ）を公知の触媒を存在させて、不活性ガス気流中又は空気の存在下、６０〜２００℃で反応させて得られる生成物における分子中のアルコール性水酸基に、さらに多塩基酸無水物（ｄ）を３０〜２００℃で反応させることにより製造することができる。
【００２５】
さらに、光硬化性樹脂組成物を構成するアクリル系飽和ポリカルボン酸化合物（Ｃ）は、（メタ）アクリル酸を必須成分とする下記の重合性モノマー（ｆ）を公知の有機過酸化物の存在下、不活性ガス気流中又は空気の存在下、６０〜１５０℃でラジカル重合させることにより製造することができる。
【００２６】
上記一般式（１）に示される１分子中に３個以上のエポキシ基を有するエポキシ化合物（ａ）は、上記（ｇ）〜（ｍ）の二価の芳香族基における２個のフェノール性水酸基を有するフェノール類を、単独又は２種以上を組み合わせて、公知の方法によりエピクロルヒドリンにてエポキシ化するか、もしくは、上記（ｇ）〜（ｍ）の二価の芳香族基における２個のエポキシ基を有するエポキシ化合物と、上記（ｇ）〜（ｍ）の二価の芳香族基における２個のフェノール性水酸基を有するフェノール類を単独又は２種以上を組み合わせて公知の方法により製造したエポキシ化合物を用い、分子中における２級のアルコール性水酸基を公知の方法によりエピクロルヒドリンにてさらにエポキシ化することにより製造することできる。
【００２７】
また、上記一般式（２）で示される１分子中に３個以上のエポキシ基を有するエポキシ化合物（ａ）は、フェノール、クレゾールをホルムアルデヒドで付加縮合させて得られる１分子中に３個以上のフェノール性水酸基を有するフェノールノボラック化合物、クレゾールノボラック化合物を公知の方法によりエピクロルヒドリンにてエポキシ化することにより製造することができる。
【００２８】
上記一般式（１）のエポキシ化合物の製造に使用される１分子中に２個のエポキシ基を有するエポキシ化合物、及び一般式（２）における１分子中に３個以上のエポキシ基を有するフェノールノボラック型エポキシ化合物、クレゾールノボラック型エポキシ化合物は、市販のエポキシ化合物を使用することもできる。
市販のエポキシ化合物としては、例えば、ジャパンエポキシレジン社製の商品名「エピコート８２８」、「エピコート８３４」、「エピコート１００１」、「エピコート１００４」、大日本インキ化学工業社製の商品名「エピクロン８４０」、「エピクロン８５０」、「エピクロン１０５０」、「エピクロン２０５５」、東都化成社製の商品名「エポトートＹＤ−０１１」、「エポトートＹＤ−０１３」、「エポトートＹＤ−１２７」、「エポトート１２８」、ダウケミカル社製の商品名「Ｄ．Ｅ．Ｒ．３１７」、「Ｄ．Ｅ．Ｒ．３３１」、「Ｄ．Ｅ．Ｒ．６６１」、「Ｄ．Ｅ．Ｒ．６６４」、旭化成工業社製の商品名「アラルダイト２５０」、「アラルダイト２６０」、「アラルダイト２６００」、住友化学工業社製の商品名「スミエポキシＥＳＡ−０１１」、「スミエポキシＥＳＡ−０１４」、「スミエポキシＥＬＡ−１１５」、「スミエポキシＥＬＡ−１２８」等のビスフェノールＡ型エポキシ化合物、大日本インキ化学工業社製の商品名「エピクロン８３０Ｓ」、ジャパンエポキシレジン社製の商品名「エピコート８０７」、東都化成社製の商品名「エポトートＹＤＦ−１７０」、「エポトートＹＤＦ−１７５」、「エポトートＹＤＦ−２００４」、旭化成工業社製の「アラルダイトＸＰＹ３０６」等のビスフェノールＦ型エポキシ化合物、日本化薬社製の商品名「ＥＢＰＳ−２００」、旭電化工業社製の商品名「ＥＰＸ−３０」、大日本インキ化学工業社製の商品名「エピクロンＥＸＡ１５１４」等のビスフェノールＳ型エポキシ化合物、大阪ガス社製の商品名「ＢＰＦＧ」等のビスフェノールフルオレン型エポキシ化合物、ジャパンエポキシレジン社製の商品名「ＹＬ−６０５６」、「ＹＬ−６０２１」、「ＹＸ−４０００」、「ＹＸ−４００Ｈ」等のビキシレノール型、或いはビフェニル型エポキシ化合物、又はそれらの混合物、東都化成社製の商品名「エポトートＳＴ−２００４」、「ＳＴ−２００７」、「ＳＴ−３０００」等の水添ビスフェノールＡ型エポキシ化合物、ジャパンエポキシレジン社製の商品名「エピコート１５２」、「エピコート１５４」、ダウケミカル社製の商品名「Ｄ．Ｅ．Ｎ．４３１」、「Ｄ．Ｅ．Ｎ．４３８」、大日本インキ化学工業社製の商品名「エピクロンＮ−６９０」、「エピクロンＮ−６９５」、「エピクロンＮ−７３０」、「エピクロンＮ−７７０」、「エピクロンＮ−８６５」、東都化成社製の商品名「エポトートＹＤＣＮ−７０１」、「エポトートＹＤＣＮ−７０４」、旭化成工業社製の商品名「アラルダイトＥＣＮ１２３５」、「アラルダイトＥＣＮ１２７３」、「アラルダイトＥＣＮ１２９９」、「アラルダイトＸＰＹ３０７」、日本化薬社製の商品名「ＥＰＰＮ−２０１」、「ＥＯＣＮ−１０２５」、「ＥＯＣＮ−１０２０」、「ＥＯＣＮ−１０４Ｓ」、「ＲＥ−３０６」、住友化学工業社製の商品名「スミエポキシＥＳＣＮ−１９５Ｘ」、「ＥＳＣＮ−２２０」等のノボラック型エポキシ化合物、ジャパンエポキシレジン社製の商品名「エピコート１５７Ｓ」等のビスフェノールＡ型ノボラックエポキシ化合物、ジャパンエポキシレジン社製の商品名「エピコートＹＬ９０３」、大日本インキ化学工業社製の商品名「エピクロン１５２」、「エピクロン１６５」、東都化成社製の商品名「エポトートＹＤＢ−４００」、「エポトートＹＤＢ−５００」、ダウケミカル社製の商品名「Ｄ．Ｅ．Ｒ．５４２」、旭化成工業社製の商品名「アラルダイト８０１１」、住友化学工業社製の商品名「スミエポキシＥＳＢ−４００」、「スミエポキシＥＳＢ−７００」等の臭素化エポキシ化合物、新日鉄化学社製の商品名「ＥＳＮ−１９０」、「ＥＳＮ−３６０」、大日本インキ化学工業社製の商品名「ＨＰ−４０３２」、「ＥＸＡ−４７５０」、「ＥＸＡ−４７００」等のナフタレン骨格を有するエポキシ化合物、大日本インキ化学工業社製の商品名「ＨＰ−７２００」、「ＨＰ−７２００Ｈ」等のジシクロペンダジエン骨格を有するエポキシ化合物、ジャパンエポキシレジン社製の商品名「ＹＬ−９３３」、日本化薬社製の商品名「ＥＰＰＮ−５０１」、「ＥＰＰＮ−５０２」等のトリスヒドロキシフェニルメタン型エポキシ化合物、日産化学社製の商品名「ＴＥＰＩＣ」、三菱ガス化学社製の商品名「ＴＧＩ」等の複素環式エポキシ化合物、ジャパンエポキシレジン社製の商品名「エピコート６０４」、東都化成社製の商品名「エポトートＹＨ−４３４」、旭化成工業社製の商品名「アラルダイトＭＹ７２０」、住友化学工業社製の商品名「スミエポキシＥＬＭ−１２０」等のグリシジルアミン型エポキシ化合物、ダイセル化学工業社製の商品名「セロキサイド２０１１」、旭化成工業社製の商品名「アラルダイトＣＹ１７５」、「アラルダイトＣＹ１７９」、新日本理化社製の商品名「ＨＢＥ−１００」等の脂環式エポキシ化合物等が挙げられるが、これらに限定されるものではない。これらエポキシ化合物は単独、又は２種以上を組み合わせて使用することができる。
【００２９】
また、上記１分子中に２個以上のエポキシ基を有するエポキシ化合物（ｅ）は、上記（ｇ）〜（ｍ）の二価の芳香族基における２個のフェノール性水酸基を有するフェノール類、又は１分子中に２個のカルボキシル基を有するカルボン酸類、又は１分子中に２個のアルコール性水酸基を有するアルコール類を、単独又は２種以上を組み合わせて、公知の方法によりエピクロルヒドリンにてエポキシ化するか、もしくは、これらのエポキシ化合物と、上記（ｇ）〜（ｍ）の二価の芳香族基における２個のフェノール性水酸基を有するフェノール類、又は１分子中に２個のカルボキシル基を有するカルボン酸類を単独又は２種以上を組み合わせて公知の方法により製造することができる。これらのエポキシ化合物は、分子中における２級のアルコール性水酸基を公知の方法によりエピクロルヒドリンにてさらにエポキシ化することにより製造することもできる。さらに、上記一般式（２）に示される１分子中に３個以上のエポキシ基を有するエポキシ化合物も使用することができる。
【００３０】
上記１分子中に２個のカルボキシル基を有するカルボン酸類は、特に限定されないが、例えば、シュウ酸、マロン酸、コハク酸、グルタル酸、アジピン酸、セパシン酸、１，４−シクロヘキシルジカルボン酸、フタル酸、イソフタル酸、テレフタル酸、テトラヒドロフタル酸等が挙げられる。これらは単独或いは２種以上を組み合わせて使用することができる。
【００３１】
上記、１分子中に２個のアルコール性水酸基を有するアルコール類は、特に限定されないが、例えば、エチレングリコール、プロピレングリコール、ネオペンチルグリコール、１，３−ブタンジオール、１，４−ブタンジオール、ジエチレングリコール、ジプロピレングリコール、１，５−ペンタンジオール、１，６−ヘキサンジオール、ポリエチレングリコール、ポリプロピレングリコール、ビスフェノールＡのエチレンオキサイド付加物、ビスフェノールＡのプロピレンオキサイド付加物、水添ビスフェノールＡ等が挙げられる。これらは単独或いは２種以上を組み合わせて用いることができる。
【００３２】
上記不飽和基含有モノカルボン酸（ｂ）は、ラジカル重合性を示すモノカルボン酸であり、例えば、アクリル酸、メタクリル酸、２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、４−ヒドロキシブチル（メタ）アクリレート、トリメチロールプロパンジ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、（メタ）アクリル酸カプロラクトン付加物など水酸基含有（メタ）アクリル酸エステルの二塩基酸無水物付加物等が挙げられる。ここで特に好ましいのはアクリル酸、メタクリル酸である。これら不飽和基含有モノカルボン酸は単独又は２種以上を組み合わせて使用することができる。
【００３３】
上記飽和活性水素化合物（ｃ）は、ラジカル重合性を示さない飽和モノカルボン酸類、飽和モノフェノール類、飽和２級モノアミン類であり、例えば、ギ酸、酢酸、プロピオン酸、ｎ−酪酸、イソ酪酸、吉草酸、イソ吉草酸、ピバリン酸、パルミチン酸、ステアリン酸、シクロヘキサンカルボン酸等の脂肪族モノカルボン酸類、安息香酸、ｐ−ブチル安息香酸、ｐ−アセチルオキシ安息香酸、フェノキシ酢酸、フェノキシプロピオン酸、ｐ−フェノキシ安息香酸、２，６−ジメトキシ安息香酸、１−ナフタレンカルボン酸等の芳香族モノカルボン酸類、並びにグリコール酸、乳酸、グリセリン酸やジオールと二塩基酸無水物等の水酸基含有モノカルボン酸類、フェノール、クレゾール、キシレノール、ｐ−エチルフェノール、２−メトキシフェノール、２−エトキシフェノール、ｐ−ｔ−ブチルフェノール、ｐ−ｔ−オクチルフェノール、フェニルフェノール、フェノキシフェノール、ヒドロキシプロピオフェノン、チモール、ｐ−ヒドロシキフェニル酢酸メチルエステル、４−（１−メチルエチル）フェノール、ナフトール、クロロフェノール、トリクロロフェノール、ブロモフェノール、ニトロフェノール、ジニトロフェノール、トリニトロフェノール等のモノフェノール類、エチルメチルアミン、Ｎ−ベンジルエタノールアミン等の２級モノアミン類が挙げられるが、これに限定されるものではない。これらは単独又は２種以上を組み合わせて使用することができる。
【００３４】
上記光硬化性化合物（Ａ）における不飽和基含有モノカルボン酸（ｂ）、又は不飽和基含有モノカルボン酸（ｂ）と飽和活性水素化合物（ｃ）との混合物から選ばれる一塩基酸の混合比は、不飽和基含有モノカルボン酸（ｂ）：飽和活性水素化合物（ｃ）＝１００：０〜１：９９（重量比）の範囲で混合される。飽和活性水素化合物（ｃ）の混合量は０重量％であっても問題ないが、形成される皮膜の可撓性や、硬化後の反りを十分に小さくするためには、飽和活性水素化合物（ｃ）を５〜５０重量％の範囲で混合することが好ましい。一方、不飽和基含有モノカルボン酸（ｂ）が１重量％未満の場合は、形成される皮膜の光硬化性が低下し、レジストパターンを形成できないため好ましくない。
【００３５】
上記光硬化性化合物（Ａ）における不飽和基含有モノカルボン酸（ｂ）、又は不飽和基含有モノカルボン酸（ｂ）と上記飽和活性水素化合物（ｃ）との混合物から選ばれる一塩基酸は、カルボキシル基及び／又はフェノール性水酸基及び／又はアミノ基の合計が、１分子中に３個以上のエポキシ基を有するエポキシ化合物（ａ）のエポキシ基１当量に対し、０．８〜１．５当量、好ましくは１．０〜１．２当量の範囲で配合される。０．８当量未満の場合は、反応中にゲル化を起こし好ましくない。一方、１．５当量を超える場合は、未反応の不飽和基含有モノカルボン酸（ｂ）、又は不飽和基含有モノカルボン酸（ｂ）と飽和活性水素化合物（ｃ）との混合物から選ばれる一塩基酸が製品中に残存するため好ましくない。
【００３６】
上記光硬化性化合物（Ａ）における一般式（１）及び／又は（２）で示される１分子中に３個以上のエポキシ基を有するエポキシ化合物（ａ）のエポキシ基と不飽和基含有モノカルボン酸（ｂ）、又は不飽和基含有モノカルボン酸（ｂ）と飽和活性水素化合物（ｃ）との混合物から選ばれる一塩基酸のカルボキシル基及び／又はフェノール性水酸基及び／又はアミノ基の反応は、上記の配合で、さらに、製造中に下記の重合禁止剤の酸化によるゲル化等のない良好な反応生成物を得るために、１分子中に３個以上のエポキシ基を有するエポキシ化合物（ａ）と、不飽和基含有モノカルボン酸（ｂ）、又は不飽和基含有モノカルボン酸（ｂ）と飽和活性水素化合物（ｃ）との混合物から選ばれる一塩基酸を仕込み、下記の希釈剤の存在下又は非存在下で、反応温度６０〜１５０℃、好ましくは８０〜１３０℃に加熱して、好ましくは空気の存在下、反応時間は０．５〜３０時間の範囲内で反応させる。反応温度が６０℃より低い場合は、長時間反応が必要となり不経済であり好ましくない。一方、１５０℃より高い場合は、反応中にゲル化を起こし好ましくない。
【００３７】
上記光硬化性化合物（Ａ）における一般式（１）及び／又は（２）で示される１分子中に３個以上のエポキシ基を有するエポキシ化合物（ａ）のエポキシ基と、不飽和基含有モノカルボン酸（ｂ）、又は不飽和基含有モノカルボン酸（ｂ）と飽和活性水素化合物（ｃ）との混合物から選ばれる一塩基酸のカルボキシル基及び／又はフェノール性水酸基及び／又はアミノ基との反応は、反応を円滑に進めるために公知の触媒を用いることが好ましい。このような触媒としては、例えば、トリエチルアミン、ジメチルベンジルアミン等の３級アミン或いは４級塩、イミダゾール、２−メチルイミダゾール等のイミダゾール誘導体、トリフェニルホスフィン、等の有機燐化合物、等を挙げることができる。これら触媒の使用量は、上記一般式（１）及び／又は（２）で示される１分子中に３個以上のエポキシ基を有するエポキシ化合物（ａ）と、不飽和基含有モノカルボン酸（ｂ）、又は不飽和含有モノカルボン酸（ｂ）と飽和活性水素化合物（ｃ）との混合物から選ばれる一塩基酸の合計１００重量部に対して０．０１〜１０重量部、好ましくは０．０５〜５重量部の範囲で使用することができる。０．０１重量部未満の場合は、長時間反応が必要となり不経済であり好ましくない。一方、１０重量部を超える場合は、反応が早すぎるため、温度コントロールが難しく、発熱が高い場合はゲル化を起こす場合もありいずれも好ましくない。
【００３８】
上記光硬化性化合物（Ａ）における一般式（１）及び／又は（２）で示される１分子中に３個以上のエポキシ基を有するエポキシ化合物（ａ）と、不飽和基含有モノカルボン酸（ｂ）、又は不飽和基含有モノカルボン酸（ｂ）と飽和活性水素化合物（ｃ）との混合物から選ばれる一塩基酸のカルボキシル基及び／又はフェノール性水酸基及び／又はアミノ基との反応は、製造中の安定性と反応生成物の貯蔵安定性を確保するため、公知の重合禁止剤が使用される。このような重合禁止剤としては、例えば、ハイドロキノン、モノメチルエーテルハイドロキノン、トルハイドロキノン、ジ−ｔｅｒｔ−ブチル−４−メチルフェノール、トリメチルハイドロキノン、フェノチアジン、ｔｅｒｔ−ブチルカテコール等を挙げることができる。これらの使用量は、上記一般式（１）及び／又は（２）で示される１分子中に３個以上のエポキシ基を有するエポキシ化合物（ａ）、不飽和基含有モノカルボン酸（ｂ）、又は不飽和基含有モノカルボン酸（ｂ）と飽和活性水素化合物（ｃ）との混合物から選ばれる一塩基酸の合計１００重量部に対して、０．０００１〜１重量部の範囲で、好ましくは０．００１〜０．２重量部の範囲で使用することができる。０．０００１重量部未満の場合は、重合禁止効果が小さく、反応途中でゲル化を起こし、目的とする化合物が得られない場合や、反応生成物の貯蔵安定性が極端に悪くなるので好ましくない。１重量部を超える場合は、樹脂組成物の硬化反応を阻害し、未硬化の硬化物が得られ、各特性の要求性能を満足しないので好ましくない。
【００３９】
また、上記エポキシ系飽和ポリカルボン酸化合物（Ｂ）における飽和活性水素化合物（ｃ）は、カルボキシル基及び／又はフェノール性水酸基及び／又はアミノ基の合計が、上記１分子中に２個以上のエポキシ基を有するエポキシ化合物（ｅ）のエポキシ基１当量に対し、０．８〜１．５当量、好ましくは１．０〜１．２当量の範囲で配合される。０．８当量未満の場合は、未反応のエポキシ基が多量に残存し、下記の多塩基酸無水物（ｃ）との反応において高分子化するため好ましくない。一方、１．２当量を超える場合は、未反応の飽和活性水素化合物が製品中に残存するためいずれも好ましくない。
【００４０】
上記エポキシ系飽和ポリカルボン酸化合物（Ｂ）における１分子中に２個以上のエポキシ基を有するエポキシ化合物（ｅ）のエポキシ基と、飽和活性水素化合物（ｃ）のカルボキシル基及び／又はフェノール性水酸基及び／又はアミノ基との反応は、上記の配合で、１分子中に２個以上のエポキシ基を有するエポキシ化合物（ｅ）と、飽和活性水素化合物（ｃ）を仕込み、下記の希釈剤の存在下又は非存在下で、反応温度６０〜２００℃、好ましくは８０〜１５０℃に加熱して、好ましくは不活性気体の存在下、反応時間は０．５〜３０時間の範囲内で反応させる。反応温度が６０℃より低い場合は、長時間反応が必要となり不経済であり好ましくない。一方、２００℃より高い場合は、反応が早すぎるため発熱量が多く、温度をコントロールすることが困難となるため好ましくない。
【００４１】
上記エポキシ系飽和ポリカルボン酸化合物（Ｂ）における１分子中に２個以上のエポキシ基を有するエポキシ化合物（ｅ）のエポキシ基と、飽和活性水素化合物（ｃ）のカルボキシル基及び／又はフェノール性水酸基及び／又はアミノ基との反応は、反応を円滑に進めるために公知の触媒を用いることが好ましい。このような触媒としては、例えば、トリエチルアミン、ジメチルベンジルアミン等の３級アミン或いは４級塩、イミダゾール、２−メチルイミダゾール、等のイミダゾール誘導体、トリフェニルホスフィン等の有機燐化合物、等を挙げることができる。これら触媒の使用量は、上記１分子中に２個以上のエポキシ基を有するエポキシ化合物（ｅ）と、飽和活性水素化合物（ｃ）の合計１００重量部に対して、０．０１〜１０重量部、好ましくは０．０５〜５重量部の範囲で使用することができる。０．０１重量部未満の場合は、長時間反応が必要となり不経済であり好ましくない。一方、１０重量部を超える場合は、反応が早すぎるため発熱量が多く、温度コントロールが困難となるため好ましくない。
【００４２】
本発明の光硬化性樹脂組成物を構成する光硬化性化合物（Ａ）は、上記一般式（１）及び／又は（２）で示される１分子中に３個以上のエポキシ基を有するエポキシ化合物（ａ）と、不飽和基含有モノカルボン酸（ｂ）、又は不飽和基含有モノカルボン酸（ｂ）と飽和活性水素化合物（ｃ）との混合物から選ばれる一塩基酸とを反応させて得られる生成物の分子中における２級のアルコール性水酸基、及び、エポキシ系飽和ポリカルボン酸化合物（Ｂ）は、上記１分子中に２個以上のエポキシ基を有するエポキシ化合物（ｅ）と、飽和活性水素化合物（ｃ）を反応させて得られる生成物の分子中における２級のアルコール性水酸基に、さらに下記の多塩基酸無水物（ｄ）を反応させ、分子中にカルボキシル基を導入する。
【００４３】
多塩基酸無水物（ｄ）としては、例えば、無水マレイン酸、無水コハク酸、無水イタコン酸、オクテニル無水コハク酸、ペンタドデセニル無水コハク酸、無水フタル酸、テトラヒドロ無水フタル酸、メチルテトラヒドロ無水フタル酸、ヘキサヒドロ無水フタル酸、メチルヘキサヒドロ無水フタル酸、無水ナジック酸、３，６−エンドメチレンテトラヒドロ無水フタル酸、テトラブロモ無水フタル酸、無水トリメリット酸、ビフェニルテトラカルボン酸二無水物、ジフェニルエーテルテトラカルボン酸二無水物、ブタンテトラカルボン酸二無水物、無水ピロメリット酸、無水ベンゾフェノンテトラカルボン酸等が挙げられる。これら多塩基酸無水物（ｄ）は単独又は２種以上を組み合わせて用いることができる。
多塩基酸無水物（ｄ）の使用量は、光硬化性化合物（Ａ）と下記のエポキシ系飽和ポリカルボン酸化合物（Ｂ）の混合物が、４０〜１６０ｍｇＫＯＨ／ｇ、好ましくは６０〜１３０ｍｇＫＯＨ／ｇの範囲内にある酸価を有していれば良く、この範囲を満足するに足る量が使用されるが、光硬化性化合物（Ａ）とエポキシ系飽和ポリカルボン酸化合物（Ｂ）の各々が上記範囲内の酸価を有していることが好ましい。光硬化性化合物（Ａ）とエポキシ系飽和ポリカルボン酸化合物（Ｂ）の酸価が４０ｍｇＫＯＨ／ｇよりも低いときは、アルカリ水溶液に対する溶解性が悪くなり、形成した皮膜の現像が困難になる。一方、１６０ｍｇＫＯＨ／ｇよりも高くなると、露光の条件によらず露光部の表面まで現像されてしまい好ましくない。
【００４４】
次に、本発明の光硬化性樹脂組成物を構成するアクリル系飽和ポリカルボン酸化合物（Ｃ）について説明する。
上記アクリル系飽和ポリカルボン酸化合物（Ｃ）は、（メタ）アクリル酸を必須成分として含有する下記の重合性モノマー（ｆ）を、公知の方法、例えば溶液重合法、乳化重合法、懸濁重合法、等により重合させることにより製造することができる。
最も好適な方法は溶液重合法であり、具体的には、反応釜に溶剤を入れ、攪拌しながら（メタ）アクリル酸を必須成分とする下記の重合性モノマー（ｆ）と重合開始剤を予め混合した液を一定速度で滴下、又は、下記重合性モノマーと重合性開始剤を各々一定速度で同時に滴下することにより重合を行うことができる。
【００４５】
上記重合性モノマー（ｆ）とは、（メタ）アクリル酸を必須成分として含有するラジカル重合性を示す（メタ）アクリル酸エステル類及び／又はビニルモノマー類であり、例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、イソプロピル（メタ）アクリレート、ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｔｅｒｔ−ブチル（メタ）アクリレート、２−エチルへキシル（メタ）アクリレート、ラウリル（メタ）アクリレート、ステアリル（メタ）アクリレート等のアルキル（メタ）アクリレート、グリシジル（メタ）アクリレート等のエポキシ基含有（メタ）アクリレート、（メタ）アクリルアミド、Ｎ，Ｎ−ジメチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ−ジエチルアミノエチル（メタ）アクリレート等のアミノアルキル（メタ）アクリレート、２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、等のヒドロキシアルキル（メタ）アクリレート、スチレン、α−メチルスチレン、ビニルトルエン、ｐ−メチルスチレン等の芳香族重合性モノマー、酢酸ビニル等のビニルエステル、（メタ）アクリロニトリル等の重合性シアノ化合物、クロトン酸、マレイン酸、フマル酸、マレイン酸モノアルキルエステル等のカルボキシル基含有重合性モノマー等を挙げることができる。これらを単独或いは２種以上を組み合わせて使用することができる。
【００４６】
上記重合性モノマー（ｆ）の必須成分である（メタ）アクリル酸の使用量は、光硬化性化合物（Ａ）とエポキシ系飽和ポリカルボン酸化合物（Ｂ）及び／又はアクリル系飽和ポリカルボン酸化合物（Ｃ）の混合物が、４０〜１６０ｍｇＫＯＨ／ｇ、好ましくは、７０〜１３０ｍｇＫＯＨ／ｇの範囲内にある酸価を有していれば良く、この範囲を満足するに足る量が使用されるが、光硬化性化合物（Ａ）とエポキシ系飽和ポリカルボン酸化合物（Ｂ）及び／又はアクリル系飽和ポリカルボン酸化合物（Ｃ）の各々が上記範囲内の酸価を有していることが好ましい。アクリル系飽和ポリカルボン酸化合物（Ｃ）の酸価が４０ｍｇＫＯＨ／ｇよりも低いときは、アルカリ水溶液に対する溶解性が悪くなり、形成した皮膜の現像が困難になる。一方、１６０ｍｇＫＯＨ／ｇよりも高くなると、露光の条件によらず露光部の表面まで現像されてしまい好ましくない。
【００４７】
この場合に使用できる溶剤は、例えば、メチルエチルケトン、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、メチルセロソルブ、ブチルセロソルブ、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エチルエーテル、ジプロピレングリコールジエチルエーテル、トリエチレングリコールモノエ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、ブチルセロソルブアセテート、カルビトールアセテート、等のエステル類、エタノール、プロパノール、エチレングリコール、プロピレングリコール等のアルコール類、オクタン、デカン等の脂肪族炭化水素、石油エーテル、石油ナフサ、水添石油ナフサ、ソルベントナフサ等の石油系溶剤、等の有機溶剤を挙げることができ、これらは単独或いは２種以上を組み合わせて使用することができる。
【００４８】
また、重合開始剤としては、公知のラジカル重合触媒が使用でき、例えば、アゾビスイソブチロニトリル、過酸化ベンゾイル、クメンヒドロパーオキサイド、ｔｅｒｔ−ブチルパーオキシベンゾエート等が挙げられる。これらは単独或いは２種以上を組み合わせて使用できる。さらに、必要に応じて、ラウリルメルカプタン、２−メルカプトエタノール等の連鎖移動剤を使用することができる。
上記重合開始剤の使用量は、（メタ）アクリル酸を必須成分として含有する重合性モノマー（ｆ）の合計１００重量部に対して、０．１〜５重量％の範囲で使用することができる。０．１重量％未満の場合は、反応時間が長く不経済であり、反応によって得られる重合物の分子量が過大に高くなるため好ましくない。一方、５重量％以上の場合は、反応が早く、温度コントロールが困難になることや、反応によって得られる重合物が低分子量となるためいずれも好ましくない。
【００４９】
上記アクリル系飽和ポリカルボン酸化合物（Ｃ）の反応は、反応温度３０〜１８０℃の範囲、好ましくは６０〜１５０℃の範囲であり、不活性ガス又は空気の存在下、１〜１０時間加熱して行う。このような溶液重合法によって通常重量平均分子量が３，０００〜３００，０００、好ましくは８，０００〜２５０，０００の共重合物が得られる。
【００５０】
本発明における光硬化性樹脂組成物は、前記の光硬化性化合物（Ａ）と、エポキシ系飽和ポリカルボン酸化合物（Ｂ）及び／又はアクリル系飽和ポリカルボン酸化合物（Ｃ）の混合物からなる。光硬化性化合物（Ａ）と、エポキシ系飽和ポリカルボン酸化合物（Ｂ）及び／又はアクリル系飽和ポリカルボン酸化合物（Ｃ）の混合割合は、混合物が６００〜４０００ｇ／ｅｑ．の二重結合当量を有する範囲が好ましく、さらに形成される皮膜に十分な可撓性を与え、反りが十分に小さく、はんだ耐熱性に優れた硬化皮膜を得るためには、１０００〜２０００ｇ／ｅｑ．の二重結合当量を有する範囲であることがより好ましい。二重結合当量が６００ｇ／ｅｑ．より低いときは、はんだ耐熱性に優れた硬化皮膜が得られるが、その硬化皮膜は脆く、さらに大きな反りを生じるため好ましくない。一方、二重結合当量が４０００ｇ／ｅｑ．より高いときは、光硬化性が低下し、皮膜にレジストパターンを形成できないため好ましくない。
【００５１】
次に、本発明の感光性熱硬化性樹脂組成物（以下、単に「樹脂組成物」ということがある）中における１分子中に２個以上のエポキシ基を有するエポキシ化合物（Ｄ）について詳細に説明する。
１分子中に２個以上のエポキシ基を有するエポキシ化合物（Ｄ）は、例えば、ジャパンエポキシレジン社製の商品名「エピコート８２８」、「エピコート８３４」、「エピコート１００１」、「エピコート１００４」、大日本インキ化学工業社製の商品名「エピクロン８４０」、「エピクロン８５０」、「エピクロン１０５０」、「エピクロン２０５５」、東都化成社製の商品名「エポトートＹＤ−０１１」、「エポトートＹＤ−０１３」、「エポトートＹＤ−１２７」、「エポトート１２８」、ダウケミカル社製の商品名「Ｄ．Ｅ．Ｒ．３１７」、「Ｄ．Ｅ．Ｒ．３３１」、「Ｄ．Ｅ．Ｒ．６６１」、「Ｄ．Ｅ．Ｒ．６６４」、旭化成工業社製の商品名「アラルダイト２５０」、「アラルダイト２６０」、「アラルダイト２６００」、住友化学工業社製の商品名「スミエポキシＥＳＡ−０１１」、「スミエポキシＥＳＡ−０１４」、「スミエポキシＥＬＡ−１１５」、「スミエポキシＥＬＡ−１２８」等のビスフェノールＡ型エポキシ化合物、大日本インキ化学工業社製の商品名「エピクロン８３０Ｓ」、ジャパンエポキシレジン社製の商品名「エピコート８０７」、東都化成社製の商品名「エポトートＹＤＦ−１７０」、「エポトートＹＤＦ−１７５」、「エポトートＹＤＦ−２００４」、旭化成工業社製の「アラルダイトＸＰＹ３０６」等のビスフェノールＦ型エポキシ化合物、日本化薬社製の商品名「ＥＢＰＳ−２００」、旭電化工業社製の商品名「ＥＰＸ−３０」、大日本インキ化学工業社製の商品名「エピクロンＥＸＡ１５１４」等のビスフェノールＳ型エポキシ化合物、大阪ガス社製の商品名「ＢＰＦＧ」等のビスフェノールフルオレン型エポキシ化合物、ジャパンエポキシレジン社製の商品名「ＹＬ−６０５６」、「ＹＬ−６０２１」、「ＹＸ−４０００」、「ＹＸ−４００Ｈ」等のビキシレノール型、或いはビフェニル型エポキシ化合物、又はそれらの混合物、東都化成社製の商品名「エポトートＳＴ−２００４」、「ＳＴ−２００７」、「ＳＴ−３０００」等の水添ビスフェノールＡ型エポキシ化合物、ジャパンエポキシレジン社製の商品名「エピコート１５２」、「エピコート１５４」、ダウケミカル社製の商品名「Ｄ．Ｅ．Ｎ．４３１」、「Ｄ．Ｅ．Ｎ．４３８」、大日本インキ化学工業社製の商品名「エピクロンＮ−６９０」、「エピクロンＮ−６９５」、「エピクロンＮ−７３０」、「エピクロンＮ−７７０」、「エピクロンＮ−８６５」、東都化成社製の商品名「エポトートＹＤＣＮ−７０１」、「エポトートＹＤＣＮ−７０４」、旭化成工業社製の商品名「アラルダイトＥＣＮ１２３５」、「アラルダイトＥＣＮ１２７３」、「アラルダイトＥＣＮ１２９９」、「アラルダイトＸＰＹ３０７」、日本化薬社製の商品名「ＥＰＰＮ−２０１」、「ＥＯＣＮ−１０２５」、「ＥＯＣＮ−１０２０」、「ＥＯＣＮ−１０４Ｓ」、「ＲＥ−３０６」、住友化学工業社製の商品名「スミエポキシＥＳＣＮ−１９５Ｘ」、「ＥＳＣＮ−２２０」等のノボラック型エポキシ化合物、ジャパンエポキシレジン社製の商品名「エピコート１５７Ｓ」等のビスフェノールＡ型ノボラックエポキシ化合物、ジャパンエポキシレジン社製の商品名「エピコートＹＬ９０３」、大日本インキ化学工業社製の商品名「エピクロン１５２」、「エピクロン１６５」、東都化成社製の商品名「エポトートＹＤＢ−４００」、「エポトートＹＤＢ−５００」、ダウケミカル社製の商品名「Ｄ．Ｅ．Ｒ．５４２」、旭化成工業社製の商品名「アラルダイト８０１１」、住友化学工業社製の商品名「スミエポキシＥＳＢ−４００」、「スミエポキシＥＳＢ−７００」等の臭素化エポキシ化合物、新日鉄化学社製の商品名「ＥＳＮ−１９０」、「ＥＳＮ−３６０」、大日本インキ化学工業社製の商品名「ＨＰ−４０３２」、「ＥＸＡ−４７５０」、「ＥＸＡ−４７００」等のナフタレン骨格を有するエポキシ化合物、大日本インキ化学工業社製の商品名「ＨＰ−７２００」、「ＨＰ−７２００Ｈ」等のジシクロペンダジエン骨格を有するエポキシ化合物、ジャパンエポキシレジン社製の商品名「ＹＬ−９３３」、日本化薬社製の商品名「ＥＰＰＮ−５０１」、「ＥＰＰＮ−５０２」等のトリスヒドロキシフェニルメタン型エポキシ化合物、日産化学社製の商品名「ＴＥＰＩＣ」、三菱ガス化学社製の商品名「ＴＧＩ」等の複素環式エポキシ化合物、ジャパンエポキシレジン社製の商品名「エピコート６０４」、東都化成社製の商品名「エポトートＹＨ−４３４」、旭化成工業社製の商品名「アラルダイトＭＹ７２０」、住友化学工業社製の商品名「スミエポキシＥＬＭ−１２０」等のグリシジルアミン型エポキシ化合物、ダイセル化学工業社製の商品名「セロキサイド２０１１」、旭化成工業社製の商品名「アラルダイトＣＹ１７５」、「アラルダイトＣＹ１７９」、新日本理化社製の商品名「ＨＢＥ−１００」等の脂環式エポキシ化合物等が挙げられるが、これらに限定されるものではない。これらエポキシ化合物は単独、又は２種以上を組み合わせて使用することができる。
【００５２】
上記１分子中に２個以上のエポキシ基を有するエポキシ化合物（Ｄ）は、レジストパターン形成後、熱硬化させることによりソルダーレジストの密着性、耐熱性、等の特性を向上させる。その配合量は、光硬化性化合物（Ａ）と、エポキシ系飽和ポリカルボン酸化合物（Ｂ）及び／又はアクリル系飽和ポリカルボン酸化合物（Ｃ）の混合物からなる光硬化性樹脂組成物が有するカルボキシル基１当量に対して、エポキシ基が０．１〜１．５当量、好ましくは０．５〜１．３当量の範囲内で配合される。０．１当量未満の場合は、硬化皮膜の吸湿性が高くなり電気絶縁性が低下する。一方、１．５当量を超えると、光硬化性やアルカリ現像性が低下し、レジストパターンの形成が困難になるためいずれも好ましくない。
【００５３】
次に、本発明の樹脂組成物における光重合開始剤（Ｅ）について詳細に説明する。本発明で用いる光重合開始剤（Ｅ）は、樹脂組成物を光（紫外線）硬化させる際に紫外線照射によりラジカルを発生し、ラジカル重合により硬化させる作用を有する。
【００５４】
このような光重合開始剤（Ｅ）としては公知のものを使用することができ、好ましい光重合開始剤（Ｅ）としては、例えば、ベンゾイン、ベンジル、ベンゾインメチルエーテル、ベンゾインイソプロピルエーテル等のベンゾイン類及びベンゾインアルキルエーテル類、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、１−ヒドロキシシクロヘキシルフェニルケトン、２−メチル−１−［４−（メチルチオ）フェニル］−２−モルフォリノ−プロパン−１−オン、２−ベンジル−２−ジメチルアミノ−１−（４−モルフォリノフェニル）−ブタノン−１、Ｎ，Ｎ−ジメチルアミノアセトフェノン等のアエトフェノン類、２−メチルアントラキノン、２−エチルアントラキノン、２−アミノ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、メチルベンゾフェノン、４，４’−ジクロロベンゾフェノン、４，４’−ビスジエチルアミノベンゾフェノン等のベンゾフェノン類、及びキサントン類等が挙げられ、これらは単独或いは２種以上を組み合わせて使用することができる。
【００５５】
さらに、このような光重合開始剤（Ｅ）は、エチル−４−ジメチルアミノベンゾエート、２−（ジメチルアミノ）エチルベンゾエート等の安息香酸エステル類、或いはトリエチルアミン、トリエタノールアミン等の三級アミン類のような公知の光増感剤を単独或いは２種以上を組み合わせて使用することができる。
光重合開始剤（Ｅ）の使用量は、光硬化性化合物（Ａ）と、エポキシ系飽和ポリカルボン酸化合物（Ｂ）及び／又はアクリル系飽和ポリカルボン酸化合物（Ｃ）からなる光硬化性樹脂組成物１００重量部に対して、０．１〜３０重量部の範囲で使用することが好ましく、さらに１〜２０重量部の範囲で使用することが好ましい。０．１重量部未満の場合は、紫外線照射により重合が進まず、形成される皮膜は未硬化になり現像性が悪くなるため好ましくない。一方、３０重量部を超える場合は、硬化皮膜の耐熱性、機械的特性が低下するためいずれも好ましくない。
【００５６】
次に、本発明の樹脂組成物における希釈剤（Ｆ）について詳細に説明する。
本発明で使用する希釈剤（Ｆ）は、上記光硬化性化合物（Ａ）と、エポキシ系飽和ポリカルボン酸化合物（Ｂ）及び／又はアクリル系飽和ポリカルボン酸化合物（Ｃ）を溶解し、インキとして適切な作業粘度を確保する作用と反応性を有するものはラジカル重合する際にネットワーク中に取り込まれ、光硬化性、耐熱性の向上、等に作用を有する。
【００５７】
このような希釈剤（Ｆ）としては、例えば、メチルエチルケトン、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、メチルセロソルブ、ブチルセロソルブ、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エチルエーテル、ジプロピレングリコールジエチルエーテル、トリエチレングリコールモノエ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、ブチルセロソルブアセテート、カルビトールアセテート等のエステル類、エタノール、プロパノール、エチレングリコール、プロピレングリコール等のアルコール類、オクタン、デカン等の脂肪族炭化水素、石油エーテル、石油ナフサ、水添石油ナフサ、ソルベントナフサ等の石油系溶剤等の有機溶剤を挙げることができ、これらに限定されるものではない。これらは単独或いは２種以上を組み合わせて使用することができる。
【００５８】
また、希釈剤（Ｆ）は、上記有機溶剤の一部又は全量を、光硬化性を有する（メタ）アクリル酸エステル類に置き換えて使用することができる。このような（メタ）アクリル酸エステル類としては、例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、イソプロピル（メタ）アクリレート、ブチル（メタ）アクリレート、ｉ−ブチル（メタ）アクリレート、ｔ−ブチル（メタ）アクリレート、２−エチルへキシル（メタ）アクリレート、ラウリル（メタ）アクリレート、ステアリル（メタ）アクリレート等のアルキル（メタ）アクリレート、グリシジル（メタ）アクリレート等のエポキシ基含有（メタ）アクリレート、（メタ）アクリルアミド、Ｎ，Ｎ−ジメチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ−ジエチルアミノエチル（メタ）アクリレート等のアミノアルキル（メタ）アクリレート、２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート等のヒドロキシアルキル（メタ）アクリレート、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等のグリコールのモノ又はジ（メタ）アクリレート類、Ｎ，Ｎ−ジメチル（メタ）アクリルアミド類、Ｎ，Ｎ−ジメチルアミノエチル（メタ）アクリレート等のアミノアルキル（メタ）アクリレート類、ヘキサンジオール、トリメチロールプロパン、ペンタエリスリトール、ジトリメチロールプロパン、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ヌレート等の多価アルコール、又は、これらのエチレンオキサイド、もしくはプロピレンオキサイド付加物の多価（メタ）アクリレート類、フェノキシエチル（メタ）アクリレート、ビスフェノールＡのポリエトキシジ（メタ）アクリレート等のフェノール類のエチレンオキサイド或いはプロピレンオキサイド付加物の（メタ）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等のグリシジルエーテルの（メタ）アクリレート類、ε−カプロラクトン変性トリス（アクリロキシエチル）イソシアヌレート等のε−カプロラクトン変性（メタ）アクリレート類、及びメラミン（メタ）アクリレート等を挙げることができ、これらに限定されるものではない。これらは単独或いは２種以上を組み合わせて使用することができる。
【００５９】
上記希釈剤（Ｆ）の使用量は、光硬化性化合物（Ａ）とエポキシ系飽和ポリカルボン酸化合物（Ｂ）及び／又はアクリル系飽和ポリカルボン酸化合物（Ｃ）との混合物１００重量部に対して１〜３００重量部の範囲で配合される。また、上記希釈剤（Ｆ）において、（メタ）アクリル酸エステル類を使用する場合は、その使用量は、上記光硬化性化合物（Ａ）と、エポキシ系飽和ポリカルボン酸化合物（Ｂ）及び／又はアクリル系飽和ポリカルボン酸化合物（Ｃ）の混合からなる光硬化性樹脂組成物１００重量部に対して、３〜５０重量部の範囲で、好ましくは５〜１５重量部の範囲で使用することが好ましい。３重量部未満の場合は、光硬化性付与の効果は十分ではなく、５０重量部を超える場合は、乾燥皮膜の指触乾燥性が低下するため好ましくない。
【００６０】
本発明の樹脂組成物は、熱硬化工程における前記光硬化性化合物（Ａ）と、エポキシ系飽和ポリカルボン酸化合物（Ｂ）及び／又はアクリル系飽和ポリカルボン酸化合物（Ｃ）の混合物からなる光硬化性樹脂組成物のカルボキシル基と、１分子中に２個以上のエポキシ基を有するエポキシ化合物（Ｄ）との反応を促進させる目的で、硬化促進剤を添加することができる。硬化促進剤としては、例えば、イミダゾール、２−メチルイミダゾール、２−エチルイミダゾール、２−エチル−４−メチルイミダゾール、２−フェニルイミダゾール、４−フェニルイミダゾール、１−シアノエチル−２−フェニルイミダゾール、１−（２−シアノエチル）−２−エチル−４−メチルイミダゾール等のイミダゾール誘導体、グアナミン、アセトグアナミン、ベンゾグアナミン等のグアナミン類、ジシアンジアミド、ベンジルジメチルアミン、４−（ジメチルアミノ）−Ｎ，Ｎ−ジメチルベンジルアミン、４−メチル−Ｎ，Ｎ−ジメチルベンジルアミン、メラミン等のアミン化合物などが挙げられる。これらは単独或いは２種以上を組み合わせて使用することができる。
【００６１】
このような硬化促進剤の使用量は、上記光硬化性化合物（Ａ）と、エポキシ系飽和ポリカルボン酸化合物（Ｂ）及び／又はアクリル系飽和ポリカルボン酸化合物（Ｃ）の混合から成る光硬化性樹脂組成物１００重量部に対して、０．１〜１０重量部の範囲で、好ましくは０．５〜２重量部の範囲で使用することができる。０．１重量部未満の場合は、１分子中に２個以上のエポキシ基を有するエポキシ化合物（Ｄ）の硬化反応を促進する効果が小さくなり、また、１０重量部を超える場合は、樹脂組成物のライフが短くなりいずれも好ましくない。
【００６２】
本発明の樹脂組成物には、プリント配線板との密着性を向上させることを目的に無機充填剤を添加することができる。例えば、タルク、シリカ、硫酸バリウム、チタン酸バリウム、酸化珪素、酸化アルミニウム、炭酸カルシウム、水酸化アルミニウム等の無機充填剤を配合することができる。これら無機充填剤は、樹脂組成物１００重量部に対して最大１５０重量部の範囲で添加することができる。１５０重量部を超えると硬化性に悪影響を及ぼし、硬化皮膜の物性が低下する。
【００６３】
本発明の樹脂組成物には、以上の成分の他に通常の樹脂組成物に添加されている種々の着色剤、レベリング剤及び消泡剤などを添加することができる。
【００６４】
本発明の樹脂組成物は、以上述べた配合成分をロールミル、サンドミル等により均一に混合して得ることができる。また、本発明の樹脂組成物のプリント配線板上への塗布は、通常スクリーン印刷法、静電塗装法、ロールコーター法、カーテンコーター法等で行われる。塗布後は、６０〜９０℃の範囲で１０〜６０分間乾燥し、紫外線等の活性エネルギー線を照射後、０．１〜５重量％の炭酸ナトリウム水溶液などの希アルカリ水溶液で未露光部分を除去し現像する。最後に皮膜を完全に硬化させるために熱風乾燥機又は遠赤外線などを用いて熱処理（１００〜１８０℃で５〜６０分間）することにより上記１分子中に２個以上のエポキシ基を有するエポキシ化合物（Ｄ）の硬化反応に加えて光硬化性化合物（Ａ）及び希釈剤（Ｆ）の（メタ）アクリル酸エステル類の重合が促進され、密着性、耐熱性、機械特性の優れた硬化皮膜を得ることができる。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、さらに必要に応じて、光硬化性化合物（Ａ）及び希釈剤（Ｆ）の（メタ）アクリル酸エステル類の重合を促進する目的で、光（紫外線）にて露光することもできる。
また、光（紫外線）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等が使用できる。
【００６５】
【実施例】
以下、本発明を実施例によりさらに具体的に説明する。本発明は、下記の実施例に限定されるものではない。本実施例において「部」は特に断らない限り重量部である。
【００６６】
（１）光硬化性化合物（Ａ）の合成原料となるエポキシ化合物の合成例
【００６７】
合成例１
ガス導入管、撹拌装置、冷却管、温度計、滴下装置を備えたフラスコに、ビスフェノールＡ型エポキシ化合物（旭化成工業社製の商品名「アラルダイト２６００」）７６３部とビスフェノールＦ２３７部を仕込み、フラスコ内を窒素で置換した後、撹拌下１００℃に加熱して溶解させた。次いで、撹拌下、トリフェニルホスフィンを０．５部仕込み、１５０〜１６０℃で１時間反応させ、エピクロルヒドリン２４５２部にて希釈した。次いで、撹拌下、４０℃に冷却保持し、９８重量％テトラブチルアンモニウムブロマイド１７部仕込み溶解させた。その後、撹拌下、４８重量％苛性ソーダ２６５部を１時間かけて連続的に滴下し、滴下後３時間反応させた。反応終了後、過剰のエピクロルヒドリンを減圧蒸留にて留去し、副生塩を含む反応生成物をメチルイソブチルケトン２０００部で希釈し、水５００部にて３回水洗した。次いで、メチルイソブチルケトンを減圧蒸留にて留去することにより、エポキシ当量２７３ｇ／ｅｑ．（これは、１分子あたり平均で５．０個のエポキシ基を有することを意味する。）、軟化点５９℃のビスフェノールＦ変性ビスフェノールＡ型多官能エポキシ化合物（ａ）を得た。
【００６８】
合成例２
合成例１と同様の装置を備えたフラスコに、前記一般式（２）におけるｎの値が２〜３であるクレゾールノボラック化合物７１４部、エピクロルヒドリン２７７５部を仕込み、フラスコ内を窒素で置換した後、撹拌下、４０℃に加熱して溶解させた。その後、撹拌下、温度を６８℃に昇温し、４８重量％苛性ソーダ４５０部を連続的に滴下しながら３．５時間反応させた。反応終了後、過剰のエピクロルヒドリンを減圧蒸留にて留去し、副生塩を含む反応生成物をメチルイソブチルケトン２０００部に溶解し、さらに１０重量％苛性ソーダを仕込み、８０〜８５℃で１．５時間反応させた。反応終了後、水５００部で３回水洗した。その後、メチルイソブチルケトンを減圧蒸留にて留去し、エポキシ当量２０８ｇ／ｅｑ．、軟化点８７℃のクレゾールノボラック型エポキシ化合物（ｂ）を得た。
【００６９】
（２）光硬化性化合物（Ａ）の合成例
【００７０】
合成例３
ガス導入管、撹拌装置、冷却管、温度計を備えたフラスコに、合成例１で得られたエポキシ化合物（ａ）３４６部を仕込み、撹拌下、１００〜１１０℃に加熱し溶解させた。その後、撹拌下、空気を吹き込みながら、アクリル酸９１部、モノメチルエーテルハイドロキノン０．４部、トリフェニルホスフィン１．３部を仕込み、１１０〜１２０℃で１０時間反応させた。次いで、撹拌下、カルビトールアセテート２８０部にて希釈した後、テトラヒドロ無水フタル酸１６３部を仕込み、１１０〜１２０℃でさらに８時間反応させ、ソルベントナフサ１２０部にて希釈し冷却することにより、酸価（不揮発分）１００ｍｇＫＯＨ／ｇ、不揮発分６０％、二重結合当量４７３ｇ／ｅｑ．の光硬化性化合物（Ａ−１）を得た。
【００７１】
合成例４
合成例３と同様の装置で、合成例１で得られたエポキシ化合物（ａ）を４３６部、アクリル酸を１１５部、モノメチルエーテルハイドロキノンを０．６部、トリフェニルホスフィンを１．７部、テトラヒドロ無水フタル酸を４９部に変更した以外は、合成例３と同様の配合及び操作を行い、酸価（不揮発分）３０ｍｇＫＯＨ／ｇ、不揮発分６０％、二重結合当量３７６ｇ／ｅｑ．の光硬化性化合物（Ａ−２）を得た。
【００７２】
合成例５
合成例３と同様の装置で、合成例１で得られたエポキシ化合物（ａ）３４６部を仕込み、撹拌下、１００〜１１０℃に加熱し溶解させた。その後、撹拌下、空気を吹き込みながら、アクリル酸７８部、プロピオン酸１４部、モノメチルエーテルハイドロキノン０．４部、トリフェニルホスフィン１．３部を仕込み１１０〜１２０℃で１０時間反応させた。次いで、撹拌下、カルビトールアセテート２８０部にて希釈した後、テトラヒドロ無水フタル酸１６３部を仕込み、１１０〜１２０℃でさらに８時間反応させ、ソルベントナフサ１２０部にて希釈し冷却することにより、酸価（不揮発分）１００ｍｇＫＯＨ／ｇ、不揮発分６０％、二重結合当量５５７ｇ／ｅｑ．の光硬化性化合物（Ａ−３）を得た。
【００７３】
合成例６
合成例３と同様の装置で、合成例２で得られたエポキシ化合物（ｂ）３４３部を仕込み、撹拌下、１００〜１１０℃に加熱し溶解させた。その後、撹拌下、空気を吹き込みながら、アクリル酸１１９部、モノメチルエーテルハイドロキノン０．５部、トリフェニルホスフィン１．４部を仕込み１１０〜１２０℃で１０時間反応させた。次いで、撹拌下、カルビトールアセテート２８０部にて希釈した後、テトラヒドロ無水フタル酸１３８部を仕込み、１１０〜１２０℃でさらに８時間反応させ、ソルベントナフサ１２０部にて希釈し冷却することにより、酸価（不揮発分）８５ｍｇＫＯＨ／ｇ、不揮発分６０％、二重結合当量３６４ｇ／ｅｑ．の光硬化性化合物（Ａ−４）を得た。
【００７４】
合成例７
合成例３と同様の装置で、合成例２で得られたエポキシ化合物（ｂ）３３０部を仕込み、撹拌下、１００〜１１０℃に加熱し溶解させた。その後、撹拌下、空気を吹き込みながら、アクリル酸８０部、クレゾール５１部、モノメチルエーテルハイドロキノン０．５部、トリフェニルホスフィン１．４部を仕込み１１０〜１２０℃で１０時間反応させた。次いで、撹拌下、カルビトールアセテート２８０部にて希釈した後、テトラヒドロ無水フタル酸１３８部を仕込み、１１０〜１２０℃でさらに８時間反応させ、ソルベントナフサ１２０部にて希釈し冷却することにより、酸価（不揮発分）８５ｍｇＫＯＨ／ｇ、不揮発分６０％、二重結合当量５４７ｇ／ｅｑ．の光硬化性化合物（Ａ−５）を得た。
【００７５】
（３）エポキシ系飽和ポリカルボン酸化合物（Ｂ）の合成例
【００７６】
合成例８
合成例３と同様の装置で、水添ビスフェノールＡ型エポキシ化合物（新日本理化社製の商品名「ＨＢＥ−１００」）３２６部と、アジピン酸６３部を仕込み、フラスコ内を窒素で置換した後、撹拌下１００℃に加熱して溶解させた。次いで、撹拌下、トリフェニルホスフィンを０．２部仕込み、１５０〜１６０℃で１時間反応させた。その後、１００℃まで冷却し、プロピオン酸４８部、トリフェニルホスフィン１．３部を仕込み、撹拌下、１３０〜１４０℃で５時間反応させた。次いで、撹拌下、カルビトールアセテート２８０部にて希釈した後、テトラヒドロ無水フタル酸１６３部を仕込み、１１０〜１２０℃にてさらに８時間反応させ、ソルベントナフサ１２０部にて希釈し冷却することにより、酸価（不揮発分）１００ｍｇＫＯＨ／ｇ、不揮発分６０％のエポキシ系飽和ポリカルボン酸化合物（Ｂ−１）を得た。
【００７７】
合成例９
合成例３と同様の装置で、合成例８で使用したと同様の水添ビスフェノールＡ型エポキシ化合物を４１１部、アジピン酸を８０部、プロピオン酸６１部、トリフェニルホスフィンを１．７部、テトラヒドロ無水フタル酸を４９部に変更した以外は、合成例８と同様の配合及び操作を行い、酸価（不揮発分）３０ｍｇＫＯＨ／ｇ、不揮発分６０％のエポキシ系飽和ポリカルボン酸化合物（Ｂ−２）を得た。
【００７８】
合成例１０
合成例３と同様の装置で、ビスフェノールＦ型エポキシ化合物（大日本化学工業社製の商品名「エピクロン８３０Ｓ」）２６６部、ビスフェノールＦ９８部を仕込み、フラスコ内を窒素で置換した後、撹拌下１００℃に加熱して溶解させた。次いで、撹拌下、トリフェニルホスフィンを０．２部仕込み、１５０〜１６０℃で１時間反応させた。その後、１００℃まで冷却し、ベンジルメチルアミン７３部を仕込み、撹拌下、１１０〜１２０℃で５時間反応させた。次いで、撹拌下、カルビトールアセテート２８０部にて希釈した後、テトラヒドロ無水フタル酸１６３部を仕込み、１１０〜１２０℃にてさらに８時間反応させ、ソルベントナフサ１２０部にて希釈し冷却することにより、酸価（不揮発分）１００ｍｇＫＯＨ／ｇ、不揮発分６０％のエポキシ系飽和ポリカルボン酸化合物（Ｂ−３）を得た。
【００７９】
（４）アクリル系飽和ポリカルボン酸化合物（Ｃ）の合成例
【００８０】
合成例１１
合成例１と同様の装置で、カルビトールアセテート２８０部を仕込み、窒素で置換した後、撹拌下、１３０〜１３５℃で、メチルメタクリレート１１８部、エチルアクリレート３９０部、メタクリル酸９２部、ジ−ｔ−ブチルパーオキサイド３．６部の混合液を３時間かけて連続的に滴下して重合反応を行い、さらに１３０〜１３５℃で３時間反応させた。その後、ソルベントナフサ１２０部にて希釈し冷却することにより、酸価（不揮発分）１００ｍｇＫＯＨ／ｇ、不揮発分６０％のアクリル系飽和ポリカルボン酸化合物（Ｃ−１）を得た。
【００８１】
合成例１２
合成例１と同様の装置で、メチルメタクリレートを１３３部、エチルアクリレートを４３９部、メタクリル酸を２８部に変更した以外は合成例１１と同様の配合及び操作を行い、酸価（不揮発分）３０ｍｇＫＯＨ／ｇ、不揮発分６０％のアクリル系飽和ポリカルボン酸化合物（Ｃ−２）を得た。
【００８２】
合成例１３
合成例１と同様の装置で、メチルメタクリレートを９７部、エチルアクリレートを３１９部、メタクリル酸を１８４部に変更した以外は合成例１１と同様の配合及び操作を行い、酸価（不揮発分）２００ｍｇＫＯＨ／ｇ、不揮発分６０％のアクリル系飽和ポリカルボン酸化合物（Ｃ−３）を得た。
【００８３】
実施例１〜１４及び比較例１〜１４
上記合成例３〜７で得られた光硬化性化合物（Ａ）と、合成例８〜１０で得られたエポキシ系飽和ポリカルボン酸化合物（Ｂ）及び／又は合成例１１〜１３で得られたアクリル系飽和ポリカルボン酸化合物（Ｃ）を混合してなる光硬化性樹脂組成物ワニスを用いた表１，表２に示す配合からなる組成物を３本ロールミルで混練し、感光性熱硬化性樹脂組成物を得た。各組成物の物性を表３，表４に示す。
【００８４】
尚、表１，表２において、
１）「イルガキュア９０７」は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ン−１（チバ・スペシャリティー・ケミカルズ社製、光重合開始剤）。
２）「ＹＸ−４０００」はキシレンビフェニル型エポキシ化合物（ジャパンエポキシレジン社製）。
３）「ＢＹＫ−Ａ５５５」はアクリル系消泡剤（ＢＹＫビックケミー社製）。
４）「カルボキシル基」は、光硬化性樹脂組成物が有するカルボキシル基。
５）「エポキシ基」は、エポキシ化合物（Ｄ）が有するエポキシ基。
【００８５】
【表１】

【００８６】
【表２】

【００８７】
表３，表４における物性評価は下記に示す方法で行った。
【００８８】
（１）指触乾燥性
上記各実施例及び比較例の組成物を、銅箔基板上（厚さ１．６ｍｍ）にスクリーン印刷にて全面塗布し、熱風乾燥炉にて８０℃で３０分間乾燥し、室温まで放冷した後、塗膜の指触乾燥性を指で確認した。判定基準は以下の通りである。
○：タックがない。
×：タックがある。
【００８９】
（２）アルカリ現像性
上記各実施例及び比較例の組成物を、銅箔基板上（厚さ１．６ｍｍ）にスクリーン印刷にて全面塗布し、熱風乾燥炉にて８０℃で３０分間乾燥し、室温まで放冷した後、３０℃の１％炭酸ナトリウム水溶液をスプレー圧０．２ＭＰａの条件で６０秒間現像を行い、塗膜の現像残りの有無を目視で確認した。判定基準は以下の通りである。
○：完全に現像されている。
△：一部塗膜が残っている。
×：塗膜が完全に残っている。
【００９０】
（３）感度
上記各実施例及び比較例の組成物を、銅箔基板上（厚さ１．６ｍｍ）にスクリーン印刷にて全面塗布し、熱風乾燥炉にて８０℃で３０分間乾燥し、室温まで放冷した後、塗膜にステップタブレット（コダックＮｏ．２、全１４段）をのせ、露光量５００ｍＪ／ｃｍ^２の条件で露光し、３０℃の１％炭酸ナトリウム水溶液をスプレー圧０．２ＭＰａの条件で６０秒間現像を行い、残存塗膜の段数を目視で数えることにより評価した。
【００９１】
（４）密着性
上記各実施例及び比較例の組成物を、ポリイミドフィルム（厚さ５０μｍ）上にスクリーン印刷にて全面塗布し、熱風乾燥炉にて８０℃で３０分間乾燥し、室温まで放冷した後、露光量５００ｍＪ／ｃｍ^２の条件で露光し、熱風乾燥炉にて１５０℃で６０分間硬化させ、室温まで放冷した（膜厚２０μｍ）。その硬化塗膜の密着性をＪＩＳ Ｄ０２０２に従い、以下の基準で評価した。
○：碁盤目の数が完全に残るもの。
△：碁盤目の数が１００個未満、６０個以上残るもの。
×：碁盤目の数が６０個未満しか残らなかったもの。
【００９２】
（５）耐折れ性
上記各実施例及び比較例の組成物を、ポリイミドフィルム（厚さ２５μｍ）上にスクリーン印刷にて全面塗布し、熱風乾燥炉にて８０℃で３０分間乾燥し、室温まで放冷した後、露光量５００ｍＪ／ｃｍ^２の条件で露光し、熱風乾燥炉にて１５０℃で６０分間硬化させ、室温まで放冷した（膜厚２０μｍ）。その硬化塗膜の耐折れ性は、得られた硬化塗膜を１８０度折り曲げ、以下の基準で評価した。
○：硬化塗膜にクラックがないもの。
△：硬化塗膜に若干クラックがあるもの。
×：硬化塗膜に多数クラックがあるもの。
【００９３】
（６）反り性
上記各実施例及び比較例の組成物を、ポリイミドフィルム（厚さ２５μｍ）上にスクリーン印刷にて全面塗布し、熱風乾燥炉にて８０℃で３０分間乾燥し、室温まで放冷した後、露光量５００ｍＪ／ｃｍ^２の条件で露光し、熱風乾燥炉にて１５０℃で６０分間硬化させ、室温まで放冷した（膜厚２０μｍ）。その後、得られた硬化塗膜を５ｃｍ×５ｃｍの大きさに切りだし試験片とした。各組成物の硬化塗膜の反り性は、各試験片の四隅が反り上がった高さを定規にてはかり、その平均値を以下の基準で評価した。
◎：反り上がりが完全にないもの。
○：反り上がりが０ｍｍ以上１ｍｍ未満のもの。
△：反り上がりが１ｍｍ以上５ｍｍ未満のもの。
×：反り上がりが５ｍｍ以上のもの。
【００９４】
（７）はんだ耐熱性
上記各実施例及び比較例の組成物を、銅箔基板上（１．６ｍｍ）にスクリーン印刷にて全面塗布し、熱風乾燥炉にて８０℃で３０分間乾燥し、室温まで放冷した後、露光量５００ｍＪ／ｃｍ^２の条件で露光し、熱風乾燥炉にて１５０℃で６０分間硬化させ、室温まで放冷した（膜厚２０μｍ）。得られた硬化塗膜にロジン系フラックスを塗布し、２６０℃のはんだ槽に１０秒間浸漬し（２回）、塗膜の状態を以下の基準で評価した。
○：硬化塗膜にふくれ、剥がれ、変色がないもの。
△：硬化塗膜に若干ふくれ、剥がれ、変色があるもの。
×：硬化塗膜の大部分がふくれ、剥がれ、変色があるもの。
【００９５】
（８）ＰＣＴ（プレッシャー・クッカー・テスト）耐性
上記各実施例及び比較例の組成物を、銅箔基板上（１．６ｍｍ）にスクリーン印刷にて全面塗布し、熱風乾燥炉にて８０℃で３０分間乾燥し、室温まで放冷した後、露光量５００ｍＪ／ｃｍ^２の条件で露光し、熱風乾燥炉にて１５０℃で６０分間硬化させ、室温まで放冷した（膜厚２０μｍ）。ＰＣＴ耐性は、得られた硬化塗膜を１２１℃、１００％ＲＨの環境化に置き、５０時間後の塗膜の状態を以下の基準で評価した。
○：硬化塗膜にふくれ、剥がれ、変色がないもの。
△：硬化塗膜に若干のふくれ、剥がれ、変色があるもの。
×：硬化塗膜の大部分がふくれ、剥がれ、変色があるもの。
【００９６】
【表３】

【００９７】
【表４】

【００９８】
表３，表４の結果から明らかなように、本発明の感光性熱硬化性樹脂組成物は、塗膜の指触乾燥性、アルカリ現像性、感度にバランスがとれ、その硬化物は、十分な可撓性を有し、反りが無いかもしくは小さく、かつ基材のポリイミドフィルムとの密着性に優れ、はんだ耐熱性、ＰＣＴ耐性に優れた硬化物を与えることができる。これに対して、比較例の樹脂組成物は、指触乾燥性、アルカリ現像性、感度、基材との密着性にバランスが悪く、反りも大きいものであった。
【００９９】
【発明の効果】
以上のように、本発明の光硬化性樹脂組成物は、１分子中に３個以上のエポキシ基を有するエポキシ化合物から製造される光硬化性化合物と、エポキシ系飽和ポリカルボン酸化合物及び／又はアクリル系飽和ポリカルボン酸化合物の混合物よりなり、光硬化性化合物は光硬化性や耐熱性を保持する作用効果を有し、さらに官能基としてカルボキシル基のみを分子中に有するエポキシ系飽和ポリカルボン酸化合物及び／又はアクリル系飽和ポリカルボン酸化合物を混合することにより、反りの原因である熱硬化後の塗膜内の応力歪みを緩和する作用効果を有する。
【０１００】
また、このような光硬化性樹脂組成物を光硬化性成分として含有する本発明の感光性熱硬化性樹脂組成物は、指触乾燥性、光硬化性、アルカリ現像性のバランスに優れ、かつ十分な可撓性、耐熱性、密着性、ＰＣＴ耐性に高いレベルで優れた硬化物を与えるとともに、熱硬化後の反りがないため、プリント配線板の製造、及びソルダーレジストを施したプリント配線板と封止樹脂を用いたＢＧＡ（ボール・グリッド・アレイ）やＣＳＰ（チップ・スケール・パッケージ）等のＩＣパッケージの製造、特にポリイミドフィルム等の薄膜基材を用いるＣＯＦ（チップ・オン・フィルム）及び／又はフレキシブルプリント配線板への電子部品の装着を容易にする。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to the field of printed wiring boards and the manufacture of IC packages such as BGA (ball grid array) and CSP (chip scale package) using a printed wiring board subjected to solder resist and a sealing resin. Particularly, a photocurable resin composition and a photosensitive thermosetting resin composition useful for a liquid solder resist ink used for the production of a COF (chip-on-film) and / or a flexible printed wiring board, and a dry film type solder resist. More specifically, the alkali-developability required for a COF and / or flexible printed wiring board, adhesion to a substrate, bending resistance, bending resistance, flexibility without causing warpage of a film after thermosetting. Curable resin suitable for forming a flexible film with excellent heat resistance, plating resistance, PCT resistance, solder heat resistance, and electrical insulation Composition, and a photosensitive thermosetting resin composition containing a photocurable resin composition, and to a cured product thereof.
[0002]
[Prior art]
The current manufacturing of printed wiring boards involves the formation of solder (circuit) patterns after soldering, when soldering electronic components to the printed wiring boards to protect the unnecessary parts from solder adhesion. It has been practiced to coat a protective layer called a mask.
[0003]
Solder resist used in the production of COF and / or flexible printed wiring boards is to punch a polyimide film called a coverlay film with a mold that matches the resist pattern, and then attach it to the wiring board using an adhesive A type obtained by coating, a liquid UV-curable type, or a type in which a thermosetting type or a combined type of UV and heat solder resist ink is applied by a printing method such as screen printing, and further, a polyester film or the like as a support. There is a type in which a dry film resist containing no organic solvent is applied to a wiring board to obtain a coating by peeling off the support.
[0004]
However, the coverlay film has sufficient flexibility but requires a mold, so that the cost is high, and it is difficult to follow the copper foil, and it is not possible to form a highly accurate resist pattern. Further, there is a problem that the adhesive protrudes from the bonding surface. On the other hand, liquid solder resist inks and dry film resists can easily form inexpensive and high-precision resist patterns, but they do not provide sufficient flexibility or adhesion to substrates such as polyimide, Has a problem that warpage occurs due to large volume shrinkage due to curing of the solder resist and large heat shrinkage after thermal curing.
[0005]
Various attempts have been made to address such problems. For example, there is a resist ink composition containing an epoxy compound and a dibasic acid anhydride as essential components (for example, see Patent Literature 1). However, there is a problem that the adhesiveness to the polyimide deteriorates. Further, there is a reaction product obtained by reacting a polybasic acid anhydride with a reaction product of a bisphenol-type polyfunctional epoxy compound and an unsaturated group-containing monocarboxylic acid, and a resist ink containing an epoxy compound as an essential component. Reference 2) solves the problems of the flexibility of the film to be formed and the adhesion of the substrate to polyimide, but the alkali developability is insufficient and the formation of a resist pattern becomes difficult. Also, there is a problem that warpage after curing is large.
[0006]
Further, there is an acrylic polycarboxylic acid compound having a glass transition temperature of −60 to 40 ° C. and a resist ink containing an epoxy compound as an essential component (for example, see Patent Document 3). Although the problems of alkali developability and warpage after curing have been solved, there is a problem that heat resistance is low and it is not possible to cope with recent high-density mounting. Further, a reaction product obtained by reacting a polybasic acid anhydride with a reaction product of an epoxy compound selected from a bisphenol F type epoxy compound or a rubber-modified epoxy compound and a monocarboxylic acid having an unsaturated group, and an epoxy compound as an essential component Resist ink (see, for example, Patent Document 4), a reaction product obtained by reacting a reaction product of a bisphenol type epoxy compound with a monocarboxylic acid having an unsaturated group with a polybasic anhydride, and a novolak type epoxy compound. A reaction product obtained by reacting a polybasic anhydride with a reaction product with a saturated group-containing monocarboxylic acid, and a resist ink containing an epoxy compound as an essential component (for example, see Patent Document 5), and further having a specific structure Reaction formation by reacting polybasic anhydride with the reaction product of bisphenol type polyfunctional epoxy compound and unsaturated monocarboxylic acid And a resist ink containing an epoxy compound as an essential component (for example, see Patent Literature 6), but excellent in flexibility of a formed film, adhesion to a substrate of polyimide, alkali developability, and heat resistance. On the other hand, the problem of warpage after curing has not been solved, and there is a problem that the intended use is limited. Further, an epoxy compound having two or more epoxy groups in one molecule, a compound having two or more hydroxyl groups in one molecule and one reactive group other than a hydroxyl group reacting with the epoxy group, and an unsaturated group-containing monocarboxylic acid There is a reaction product obtained by reacting a polybasic acid anhydride with an acid reactant, and a resist ink containing polyalkylene glycol di (meth) acrylate and an epoxy compound having a specific structure as essential components (for example, see Patent Document 7). ) However, although the flexibility of the film and the adhesion of the substrate to polyimide are excellent and the warping after curing is small, the warping problem has not been completely solved yet, and COF (chip-on) (Film) and / or flexible printed wiring boards.
[0007]
As described above, when flexibility and warpage resistance are simultaneously imparted to the formed film, generally either the alkali developability or the heat resistance is greatly reduced, and further, the touch dryness after the solvent drying step is obtained. The balance of the basic properties of a solder resist ink used in the manufacture of flexible printed wiring boards, such as dryness to the touch, alkali developability, flexibility, and heat resistance, is achieved. It is extremely difficult to eliminate warpage after curing, and there is no satisfactory solution to date.
[0008]
[Patent Document 1]
JP-A-5-75032
[Patent Document 2]
JP-A-8-134390
[Patent Document 3]
JP-A-11-158252
[Patent Document 4]
JP-A-10-42540
[Patent Document 5]
JP 2000-109541 A
[Patent Document 6]
JP 2001-278947 A
[Patent Document 7]
JP 2002-40647 A
[0009]
[Problems to be solved by the invention]
Accordingly, an object of the present invention is to manufacture a printed wiring board, and an IC such as a BGA (ball grid array) or a CSP (chip scale package) using a printed wiring board subjected to a solder resist and a sealing resin. In the manufacture of packages, especially in the field of electronic materials such as liquid solder resist inks for COF (chip-on-film) and / or flexible printed wiring boards and dry film solder resists, alkali-developed films are obtained without causing warpage of the cured films. Photocurable resin composition suitable for forming a film having excellent heat resistance, adhesion to a substrate, bending resistance, bending resistance, flexibility, plating resistance, PCT resistance, soldering heat resistance, and electrical insulation. An object of the present invention is to provide a photosensitive thermosetting resin composition containing a photocurable resin composition.
[0010]
[Means for Solving the Problems]
The present inventors have conducted intensive studies to solve the above problems, and as a result, have found that a photocurable compound mixed with an epoxy-based saturated polycarboxylic acid compound and / or an acrylic-based saturated polycarboxylic acid compound is mixed. Photosensitive resin composition, a photosensitive thermosetting resin composition in which an epoxy compound, a photopolymerization initiator, and a diluent are blended as essential components in the photocurable resin composition, with the above-described conflicting performances in a well-balanced manner. Completion of the present invention, which has been found that it is possible to give a cured product having alkali developability, excellent adhesion to a substrate, and excellent heat resistance without causing warpage in a film after heat curing. I let it.
[0011]
That is, the present invention
(1) An epoxy compound (a) having three or more epoxy groups in one molecule represented by the following general formulas (1) and / or (2), and an unsaturated group-containing monocarboxylic acid (b) or unsaturated compound A reaction product obtained by reacting a monobasic acid selected from a mixture of a group-containing monocarboxylic acid (b) and a saturated active hydrogen compound (c) is further reacted with a polybasic anhydride (d). Reaction product obtained by reacting the photocurable compound (A) obtained, the epoxy compound (e) having two or more epoxy groups in one molecule, and the saturated active hydrogen compound (c) with a polybasic compound. An acrylic compound obtained by polymerizing a polymerizable monomer (f) containing an epoxy-based saturated polycarboxylic acid compound (B) and / or (meth) acrylic acid as an essential component obtained by reacting an acid anhydride (d). Saturated polycarboxylation It consists of a mixture of objects (C), double bond equivalent of the mixture is 600~4000g / eq. A photocurable resin composition characterized by the above range.
General formula (1)
Embedded image

(Where M is -H or

And at least one of M is

X and Y are the same or different divalent aromatic groups, and m represents 1 to 20. )
General formula (2)
Embedded image

(Wherein R is —H or CH ₃ , N represents 1 to 20. )
[0012]
(2) The above (1), wherein the saturated active hydrogen compound (c) is at least one or more saturated active hydrogen compounds selected from the group consisting of monocarboxylic acids, monophenols and secondary monoamines. Photocurable resin composition.
[0013]
(3) A mixture of the photocurable compound (A) and the epoxy-based saturated polycarboxylic acid compound (B) and / or the acrylic-based saturated polycarboxylic acid compound (C) has an acid value in the range of 40 to 160 mgKOH / g. The photocurable resin composition according to the above (1) or (2), comprising:
[0014]
(4) The photocurable resin composition according to any one of the above (1) to (3), an epoxy compound (D) having two or more epoxy groups in one molecule, and a photopolymerization initiator (E) A photosensitive thermosetting resin composition, comprising a diluent (F) as an essential component.
[0015]
(5) The equivalent of the epoxy group of the epoxy compound (D) having two or more epoxy groups in one molecule is 0.1 to 1.5 equivalent to 1 equivalent of the carboxyl group in the photocurable resin composition. The photosensitive thermosetting resin composition according to the above (4), which is blended in the range of (4).
[0016]
(6) The photopolymerization initiator (E) is blended in an amount of 0.1 to 30 parts by weight based on 100 parts by weight of the photocurable compound (A) in the photocurable resin composition. (4) or the photosensitive thermosetting resin composition according to (5).
[0017]
(7) The diluent (F) is an organic solvent and / or (meth) acrylic acid ester, and is mixed in a range of 1 to 300 parts by weight based on 100 parts by weight of the photocurable resin composition. The photosensitive thermosetting resin composition according to any one of the above (4) to (6).
[0018]
(8) A cured product obtained by curing the photosensitive thermosetting resin composition according to any one of (4) to (7).
It is the gist.
[0019]
BEST MODE FOR CARRYING OUT THE INVENTION
The present invention will be described in detail below.
First, in this specification, (meth) acrylic acid means acrylic acid, methacrylic acid or a mixture thereof, and (meth) acrylic ester means an acrylic ester, a methacrylic ester, or a mixture thereof. .
[0020]
The first invention of the present invention relates to an epoxy compound (a) having three or more epoxy groups in one molecule represented by the following general formulas (1) and / or (2), and an unsaturated group-containing monocarboxylic acid (B) or a reaction product obtained by reacting a monobasic acid selected from a mixture of an unsaturated group-containing monocarboxylic acid (b) and a saturated active hydrogen compound (c), and a polybasic acid anhydride (d ), A reaction product obtained by reacting an epoxy compound (e) having two or more epoxies in one molecule with a saturated active hydrogen compound (c) Is further polymerized with a polymerizable monomer (f) containing an epoxy-based saturated polycarboxylic acid compound (B) and / or (meth) acrylic acid as essential components obtained by reacting a polybasic acid anhydride (d). Acrylic saturated po Consist of a mixture of a carboxylic acid compound (C), double bond equivalent of the mixture is 600~4000g / eq. The second invention relates to a photo-curable resin composition having a range of (a) to (c), a photo-curable resin composition, an epoxy compound (D) having two or more epoxy groups in one molecule, and a photo-polymerization initiator ( E) and a photosensitive thermosetting resin composition containing a diluent (F) as an essential component.
General formula (1)
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(Where M is -H or

And at least one of M is

X and Y are the same or different divalent aromatic groups, and m represents 1 to 20. )
General formula (2)
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(Wherein R is —H or CH ₃ , N represents 1 to 20. )
[0021]
X and Y in the general formula (1) represent the same or different divalent aromatic groups of the following (g) to (m). For example, in the following (g) and (h), R ₁ , R ₂ , R ₃ , R ₄ Is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a halogen atom, and p, q, r, and s are R ₁ , R ₂ , R ₃ , R ₄ Is 1 to 4 when is an alkyl group, and 1 or 2 when is a halogen atom. (I), (j) and (m) are R ₅ , R ₆ , R ₇ , R ₈ Is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, t, x, y are 1 to 4, and z is 1 to 4. A in (h) is alkylene, cycloalkylene, halogen, cycloalkyl or aryl-substituted alkylene, S, S = O or O = S = O.
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[0022]
First, the photocurable resin composition of the present invention will be described.
The photocurable resin composition of the present invention comprises the following photocurable compound (A), and an epoxy-based saturated polycarboxylic acid compound (B) and / or an acrylic-based saturated polycarboxylic acid compound (C). The photocurable compound (A) has a photosensitive double bond and a carboxyl group, and becomes a cured product by radical polymerization in the presence of a photopolymerization initiator that coexists in the photocuring step by irradiation with ultraviolet light. At this time, a portion not irradiated with ultraviolet rays is removed in the alkali developing step due to the presence of a carboxyl group in the molecule. Further, the carboxyl group in the cured product has a function of reacting with the epoxy compound (D) in the heat curing step to form a strong bond. Further, the epoxy-based saturated polycarboxylic acid compound (B) and / or the acrylic-based saturated polycarboxylic acid compound (C) have only a carboxyl group, have an action of facilitating the alkali developing step, and have a cured product. The carboxyl group therein has an action of reacting with the epoxy compound (D) in the heat curing step to form a strong bond.
[0023]
The photocurable compound (A) constituting such a photocurable resin composition is an epoxy compound represented by the general formula (1) and / or (2) and having three or more epoxy groups in one molecule. (A) and a monobasic acid selected from an unsaturated group-containing monocarboxylic acid (b) or a mixture of an unsaturated group-containing monocarboxylic acid (b) and a saturated active hydrogen compound (c) by a known catalyst and polymerization inhibition The polybasic acid anhydride (d) is further added to the alcoholic hydroxyl group in the molecule of the product obtained by reacting at 60 to 150 ° C. in an inert gas stream or in the presence of air in the presence of It can be produced by reacting at 150 ° C.
[0024]
Further, the epoxy-based saturated polycarboxylic acid compound (B) constituting the photocurable resin composition includes an epoxy compound (e) having two or more epoxy groups in one molecule and a saturated active hydrogen compound (c). A polybasic acid anhydride (d) is further added to an alcoholic hydroxyl group in a molecule of a product obtained by reacting at 60 to 200 ° C. in an inert gas stream or in the presence of air in the presence of a known catalyst. It can be produced by reacting at 30 to 200 ° C.
[0025]
Further, the acrylic saturated polycarboxylic acid compound (C) constituting the photocurable resin composition is obtained by using the following polymerizable monomer (f) containing (meth) acrylic acid as an essential component in the presence of a known organic peroxide. It can be produced by radical polymerization at 60 to 150 ° C. in an inert gas stream or in the presence of air.
[0026]
The epoxy compound (a) having three or more epoxy groups in one molecule represented by the above general formula (1) is obtained by using two phenolic hydroxyl groups in the above divalent aromatic groups (g) to (m). Are epoxidized with epichlorohydrin by a known method alone or in combination of two or more phenols, or two epoxy groups in the above divalent aromatic groups (g) to (m) And an epoxy compound produced by a known method by combining the above-mentioned (g) to (m) phenols having two phenolic hydroxyl groups in the divalent aromatic group alone or in combination of two or more. It can be produced by further epoxidizing a secondary alcoholic hydroxyl group in the molecule with epichlorohydrin by a known method.
[0027]
Further, the epoxy compound (a) having three or more epoxy groups in one molecule represented by the above general formula (2) is obtained by subjecting phenol or cresol to addition condensation with formaldehyde to obtain three or more epoxy compounds in one molecule. It can be produced by epoxidizing a phenol novolak compound having a phenolic hydroxyl group or a cresol novolak compound with epichlorohydrin by a known method.
[0028]
An epoxy compound having two epoxy groups in one molecule and a phenol novolak having three or more epoxy groups in one molecule in the general formula (2) used for producing the epoxy compound of the general formula (1) A commercially available epoxy compound can also be used for the type epoxy compound and the cresol novolak type epoxy compound.
Examples of commercially available epoxy compounds include “Epicoat 828”, “Epicoat 834”, “Epicoat 1001”, and “Epicoat 1004” manufactured by Japan Epoxy Resin, and “Epiclon 840” manufactured by Dainippon Ink and Chemicals, Inc. "," Epiclon 850 "," Epiclon 1050 "," Epiclon 2055 ", trade names" Epototo YD-011 "," Epototo YD-013 "," Epototo YD-127 "," Epototo 128 ", manufactured by Toto Kasei Co., Ltd., Dow Chemical's trade names "D.E.R.317", "D.E.R.331", "D.E.R.661", "D.E.R.664", Asahi Kasei Corporation "Araldite 250", "Araldite 260", "Araldite 2600" manufactured by Sumitomo Chemical Co., Ltd. Bisphenol A type epoxy compounds such as "ESA-011", "Sumiepoxy ESA-014", "Sumiepoxy ELA-115", "Sumiepoxy ELA-128", trade name "Epiclon 830S" manufactured by Dainippon Ink and Chemicals, Japan Epoxy Resin's product name "Epicoat 807", Toto Kasei's product name "Epototo YDF-170", "Epototo YDF-175", "Epototo YDF-2004", Asahi Kasei's "Araldite XPY306", etc. Bisphenol F type epoxy compounds, such as "EBPS-200" manufactured by Nippon Kayaku Co., Ltd., "EPX-30" manufactured by Asahi Denka Kogyo, "Epiclon EXA1514" manufactured by Dainippon Ink and Chemicals, etc. Bisphenol S type epoxy compound, trade name "BPF" manufactured by Osaka Gas Co., Ltd. , Etc., and the product name "YL-6056", "YL-6021", "YX-4000", "YX-400H", etc., or the bixylenol type or biphenyl type epoxy manufactured by Japan Epoxy Resin Co., Ltd. Compounds or mixtures thereof, hydrogenated bisphenol A-type epoxy compounds such as "Epototo ST-2004", "ST-2007", "ST-3000" manufactured by Toto Kasei, trade names manufactured by Japan Epoxy Resin "Epicoat 152", "Epicoat 154", trade names "DEN431" and "DEN438" manufactured by Dow Chemical Company, and "Epiclon N" manufactured by Dainippon Ink and Chemicals, Inc. -690 "," Epiclon N-695 "," Epiclon N-730 "," Epiclon N-770 "," Epiclon N " -865 ", trade names" Epototo YDCN-701 "and" Epototo YDCN-704 "manufactured by Toto Kasei Co., Ltd.," Araldite ECN1235 "," Araldite ECN1273 "," Araldite ECN1299 ", and" Araldite XPY307 "manufactured by Asahi Kasei Corporation. , "Nippon Kayaku Co., Ltd. product name" EPPN-201 "," EOCN-1025 "," EOCN-1020 "," EOCN-104S "," RE-306 ", Sumitomo Chemical Co., Ltd. product name" Sumiepoxy Novolak-type epoxy compounds such as "ESCN-195X" and "ESCN-220", bisphenol A-type novolak epoxy compounds such as "Epicoat 157S" manufactured by Japan Epoxy Resin, and "Epicoat YL903" manufactured by Japan Epoxy Resin. , Dainippon Ink Industry Co., Ltd. under the trade name "Epichlone 152", "Epichlone 165", manufactured by Toto Kasei Co., Ltd. under the trade name "EPOTOHTO YDB-400", "EPOTOHTO YDB-500", Dow Chemical Co., Ltd. under the trade name "D. E. FIG. R. 542 ", a product name" Araldite 8011 "manufactured by Asahi Kasei Kogyo Co., Ltd., a brominated epoxy compound such as" Sumiepoxy ESB-400 "," Sumiepoxy ESB-700 "manufactured by Sumitomo Chemical Co., Ltd., a product name manufactured by Nippon Steel Chemical Co., Ltd. Epoxy compounds having a naphthalene skeleton such as "ESN-190", "ESN-360", trade names "HP-4032", "EXA-4750", and "EXA-4700" manufactured by Dainippon Ink and Chemicals, Dainippon Epoxy compounds having a dicyclopentadiene skeleton such as “HP-7200” and “HP-7200H” manufactured by Ink Chemical Industry Co., Ltd., “YL-933” manufactured by Japan Epoxy Resin, manufactured by Nippon Kayaku Co., Ltd. Trishydroxyphenylmethane type epoxy compounds such as "EPPN-501" and "EPPN-502", Nissan Chemical Heterocyclic epoxy compounds such as "TEPIC" manufactured by Mitsubishi Gas Chemical Company, "TGI" manufactured by Mitsubishi Gas Chemical Company, "Epicoat 604" manufactured by Japan Epoxy Resin, "Epototo YH" manufactured by Toto Kasei Glycidylamine-type epoxy compounds such as "-araldite MY720" manufactured by Asahi Kasei Kogyo Co., Ltd., "Sumiepoxy ELM-120" manufactured by Sumitomo Chemical Co., Ltd., and "Celoxide 2011" manufactured by Daicel Chemical Industries, Ltd. And alicyclic epoxy compounds such as "Araldite CY175" and "Araldite CY179" manufactured by Asahi Kasei Kogyo Co., Ltd., and "HBE-100" manufactured by Shin Nippon Rika Co., Ltd., and the like, but are not limited thereto. is not. These epoxy compounds can be used alone or in combination of two or more.
[0029]
The epoxy compound (e) having two or more epoxy groups in one molecule is a phenol having two phenolic hydroxyl groups in the divalent aromatic groups (g) to (m), or Epoxylation of carboxylic acids having two carboxyl groups in one molecule or alcohols having two alcoholic hydroxyl groups in one molecule with epichlorohydrin by a known method alone or in combination of two or more. Alternatively, these epoxy compounds may be combined with a phenol having two phenolic hydroxyl groups in the above divalent aromatic groups (g) to (m), or a carboxylic acid having two carboxyl groups in one molecule. The acids can be produced singly or in combination of two or more by a known method. These epoxy compounds can also be produced by further epoxidizing a secondary alcoholic hydroxyl group in the molecule with epichlorohydrin by a known method. Further, an epoxy compound represented by the general formula (2) and having three or more epoxy groups in one molecule can also be used.
[0030]
Although the carboxylic acids having two carboxyl groups in one molecule are not particularly limited, for example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, 1,4-cyclohexyldicarboxylic acid, phthalic acid Acids, isophthalic acid, terephthalic acid, tetrahydrophthalic acid and the like. These can be used alone or in combination of two or more.
[0031]
The alcohols having two alcoholic hydroxyl groups in one molecule are not particularly limited. Examples thereof include ethylene glycol, propylene glycol, neopentyl glycol, 1,3-butanediol, 1,4-butanediol, and diethylene glycol. , Dipropylene glycol, 1,5-pentanediol, 1,6-hexanediol, polyethylene glycol, polypropylene glycol, ethylene oxide adduct of bisphenol A, propylene oxide adduct of bisphenol A, hydrogenated bisphenol A, and the like. These can be used alone or in combination of two or more.
[0032]
The unsaturated group-containing monocarboxylic acid (b) is a monocarboxylic acid having radical polymerizability, such as acrylic acid, methacrylic acid, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, Hydroxyl group-containing (meth) acryl such as 4-hydroxybutyl (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and adduct of caprolactone (meth) acrylate And dibasic acid anhydride adducts of acid esters. Particularly preferred herein are acrylic acid and methacrylic acid. These unsaturated group-containing monocarboxylic acids can be used alone or in combination of two or more.
[0033]
The saturated active hydrogen compound (c) is a saturated monocarboxylic acid, a saturated monophenol, or a saturated secondary monoamine that does not exhibit radical polymerizability, and examples thereof include formic acid, acetic acid, propionic acid, n-butyric acid, isobutyric acid, Valeric acid, isovaleric acid, pivalic acid, palmitic acid, stearic acid, aliphatic monocarboxylic acids such as cyclohexanecarboxylic acid, benzoic acid, p-butylbenzoic acid, p-acetyloxybenzoic acid, phenoxyacetic acid, phenoxypropionic acid, Aromatic monocarboxylic acids such as p-phenoxybenzoic acid, 2,6-dimethoxybenzoic acid and 1-naphthalenecarboxylic acid, and hydroxyl-containing monocarboxylic acids such as glycolic acid, lactic acid, glyceric acid and diols and dibasic acid anhydrides , Phenol, cresol, xylenol, p-ethylphenol, 2-methoxyphenol Nol, 2-ethoxyphenol, pt-butylphenol, pt-octylphenol, phenylphenol, phenoxyphenol, hydroxypropiophenone, thymol, p-hydroxyphenylacetic acid methyl ester, 4- (1-methylethyl) phenol But monophenols such as naphthol, chlorophenol, trichlorophenol, bromophenol, nitrophenol, dinitrophenol and trinitrophenol, and secondary monoamines such as ethylmethylamine and N-benzylethanolamine, but are not limited thereto. It is not done. These can be used alone or in combination of two or more.
[0034]
Mixture of monobasic acid selected from the unsaturated group-containing monocarboxylic acid (b) or the mixture of unsaturated group-containing monocarboxylic acid (b) and saturated active hydrogen compound (c) in the photocurable compound (A) The ratio is mixed in the range of unsaturated group-containing monocarboxylic acid (b): saturated active hydrogen compound (c) = 100: 0 to 1:99 (weight ratio). Although the mixing amount of the saturated active hydrogen compound (c) may be 0% by weight, there is no problem. However, in order to sufficiently reduce the flexibility of the formed film and the warpage after curing, the saturated active hydrogen compound (c) is used. Preferably, c) is mixed in the range of 5 to 50% by weight. On the other hand, when the content of the unsaturated group-containing monocarboxylic acid (b) is less than 1% by weight, the photocurability of the film to be formed is reduced and a resist pattern cannot be formed, which is not preferable.
[0035]
The monobasic acid selected from the unsaturated group-containing monocarboxylic acid (b) or the mixture of the unsaturated group-containing monocarboxylic acid (b) and the saturated active hydrogen compound (c) in the photocurable compound (A) is , The total of carboxyl groups and / or phenolic hydroxyl groups and / or amino groups is 0.8 to 1.5 with respect to 1 equivalent of epoxy group of epoxy compound (a) having 3 or more epoxy groups in one molecule. Equivalent, preferably in the range of 1.0 to 1.2 equivalent. If the amount is less than 0.8 equivalent, gelation occurs during the reaction, which is not preferable. On the other hand, if it exceeds 1.5 equivalents, it is selected from unreacted unsaturated group-containing monocarboxylic acid (b) or a mixture of unsaturated group-containing monocarboxylic acid (b) and saturated active hydrogen compound (c). It is not preferable because monobasic acid remains in the product.
[0036]
The epoxy group and unsaturated group-containing monocarboxylic acid of the epoxy compound (a) having three or more epoxy groups in one molecule represented by the general formula (1) and / or (2) in the photocurable compound (A). The reaction of the carboxyl group and / or phenolic hydroxyl group and / or amino group of the monobasic acid selected from the mixture of the acid (b) or the unsaturated group-containing monocarboxylic acid (b) and the saturated active hydrogen compound (c) In order to obtain a good reaction product having no gelation due to oxidation of the following polymerization inhibitor during the production, the epoxy compound having three or more epoxy groups in one molecule (a ) And a monobasic acid selected from the group consisting of an unsaturated group-containing monocarboxylic acid (b) or a mixture of an unsaturated group-containing monocarboxylic acid (b) and a saturated active hydrogen compound (c). Presence or non In standing under a reaction temperature of 60 to 150 ° C., preferably heated to 80 to 130 ° C., preferably in the presence of air, the reaction time the reaction within the range of 0.5 to 30 hours. When the reaction temperature is lower than 60 ° C., a long-time reaction is required, which is uneconomical and not preferable. On the other hand, if the temperature is higher than 150 ° C., gelation occurs during the reaction, which is not preferable.
[0037]
The epoxy group of the epoxy compound (a) having three or more epoxy groups in one molecule represented by the general formula (1) and / or (2) in the photocurable compound (A), and an unsaturated group-containing monomer. With a carboxyl group and / or a phenolic hydroxyl group and / or an amino group of a monobasic acid selected from a mixture of a carboxylic acid (b) or an unsaturated group-containing monocarboxylic acid (b) and a saturated active hydrogen compound (c). In the reaction, it is preferable to use a known catalyst in order to smoothly carry out the reaction. Examples of such a catalyst include tertiary amines or quaternary salts such as triethylamine and dimethylbenzylamine, imidazole derivatives such as imidazole and 2-methylimidazole, and organic phosphorus compounds such as triphenylphosphine. it can. The amounts of these catalysts used are the epoxy compound (a) having three or more epoxy groups in one molecule represented by the general formula (1) and / or (2), and the unsaturated group-containing monocarboxylic acid (b) ), Or 0.01 to 10 parts by weight, preferably 0.05 to 100 parts by weight of a total of monobasic acids selected from a mixture of an unsaturated monocarboxylic acid (b) and a saturated active hydrogen compound (c). It can be used in the range of up to 5 parts by weight. If the amount is less than 0.01 part by weight, a long-time reaction is required, which is uneconomical and is not preferred. On the other hand, if it exceeds 10 parts by weight, the reaction is too fast, so that it is difficult to control the temperature. If the heat generation is high, gelation may occur, which is not preferable.
[0038]
An epoxy compound (a) having three or more epoxy groups in one molecule represented by the general formula (1) and / or (2) in the photocurable compound (A) and an unsaturated group-containing monocarboxylic acid ( b) or the reaction of a monobasic acid selected from a mixture of an unsaturated group-containing monocarboxylic acid (b) and a saturated active hydrogen compound (c) with a carboxyl group and / or a phenolic hydroxyl group and / or an amino group, Known polymerization inhibitors are used to ensure stability during production and storage stability of the reaction product. Examples of such a polymerization inhibitor include hydroquinone, monomethyl ether hydroquinone, toluhydroquinone, di-tert-butyl-4-methylphenol, trimethylhydroquinone, phenothiazine, tert-butylcatechol and the like. The amounts of these used are the epoxy compound (a) having three or more epoxy groups in one molecule represented by the general formulas (1) and / or (2), the unsaturated group-containing monocarboxylic acid (b), Alternatively, in the range of 0.0001 to 1 part by weight, preferably 100 parts by weight of a total of monobasic acids selected from a mixture of an unsaturated group-containing monocarboxylic acid (b) and a saturated active hydrogen compound (c). It can be used in the range of 0.001 to 0.2 parts by weight. When the amount is less than 0.0001 part by weight, the polymerization inhibiting effect is small, gelation occurs during the reaction, and the target compound cannot be obtained, or the storage stability of the reaction product is extremely deteriorated, which is not preferable. . When the amount exceeds 1 part by weight, the curing reaction of the resin composition is inhibited, and an uncured cured product is obtained, which does not satisfy the required performance of each property, which is not preferable.
[0039]
In addition, the saturated active hydrogen compound (c) in the epoxy-based saturated polycarboxylic acid compound (B) has a total of carboxyl groups and / or phenolic hydroxyl groups and / or amino groups of two or more epoxy groups in one molecule. It is compounded in the range of 0.8 to 1.5 equivalents, preferably 1.0 to 1.2 equivalents, per 1 equivalent of the epoxy group of the epoxy compound (e) having a group. When the amount is less than 0.8 equivalent, a large amount of unreacted epoxy groups remains, which is not preferable because it becomes a polymer in the reaction with the following polybasic acid anhydride (c). On the other hand, when the amount exceeds 1.2 equivalents, unreacted saturated active hydrogen compounds remain in the product, which is not preferable.
[0040]
The epoxy group of the epoxy compound (e) having two or more epoxy groups in one molecule in the epoxy-based saturated polycarboxylic acid compound (B) and the carboxyl group and / or phenolic hydroxyl group of the saturated active hydrogen compound (c) And / or the reaction with an amino group is carried out in the above-mentioned manner by charging an epoxy compound (e) having two or more epoxy groups in one molecule and a saturated active hydrogen compound (c) in the presence of the following diluent: The reaction is carried out at a reaction temperature of 60 to 200 ° C., preferably 80 to 150 ° C., in the presence or absence, preferably in the presence of an inert gas, for a reaction time in the range of 0.5 to 30 hours. When the reaction temperature is lower than 60 ° C., a long-time reaction is required, which is uneconomical and not preferable. On the other hand, when the temperature is higher than 200 ° C., the reaction is too fast and the amount of heat generated is large, and it becomes difficult to control the temperature, which is not preferable.
[0041]
The epoxy group of the epoxy compound (e) having two or more epoxy groups in one molecule in the epoxy-based saturated polycarboxylic acid compound (B) and the carboxyl group and / or phenolic hydroxyl group of the saturated active hydrogen compound (c) The reaction with the amino group and / or the amino group is preferably performed using a known catalyst in order to smoothly carry out the reaction. Examples of such a catalyst include tertiary amines or quaternary salts such as triethylamine and dimethylbenzylamine, imidazole derivatives such as imidazole and 2-methylimidazole, and organic phosphorus compounds such as triphenylphosphine. it can. These catalysts are used in an amount of 0.01 to 10 parts by weight based on a total of 100 parts by weight of the epoxy compound (e) having two or more epoxy groups in one molecule and the saturated active hydrogen compound (c). , Preferably in the range of 0.05 to 5 parts by weight. If the amount is less than 0.01 part by weight, a long-time reaction is required, which is uneconomical and is not preferred. On the other hand, when the amount exceeds 10 parts by weight, the reaction is too fast, and the calorific value is large, and the temperature control becomes difficult.
[0042]
The photocurable compound (A) constituting the photocurable resin composition of the present invention is an epoxy compound represented by the above general formula (1) and / or (2) and having three or more epoxy groups in one molecule. (A) and a monobasic acid selected from the group consisting of an unsaturated group-containing monocarboxylic acid (b) or a mixture of an unsaturated group-containing monocarboxylic acid (b) and a saturated active hydrogen compound (c). The secondary alcoholic hydroxyl group and the epoxy-based saturated polycarboxylic acid compound (B) in the molecule of the product to be obtained are the same as those of the epoxy compound (e) having two or more epoxy groups in one molecule and the saturation activity. The secondary alcoholic hydroxyl group in the molecule of the product obtained by reacting the hydrogen compound (c) is further reacted with the following polybasic acid anhydride (d) to introduce a carboxyl group into the molecule.
[0043]
Examples of the polybasic acid anhydride (d) include maleic anhydride, succinic anhydride, itaconic anhydride, octenyl succinic anhydride, pentadodecenyl succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, Hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, nadic anhydride, 3,6-endomethylenetetrahydrophthalic anhydride, tetrabromophthalic anhydride, trimellitic anhydride, biphenyltetracarboxylic dianhydride, diphenylethertetracarboxylic dianhydride Anhydride, butanetetracarboxylic dianhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride and the like can be mentioned. These polybasic acid anhydrides (d) can be used alone or in combination of two or more.
The amount of the polybasic acid anhydride (d) used is such that the mixture of the photocurable compound (A) and the following epoxy-based saturated polycarboxylic acid compound (B) is 40 to 160 mgKOH / g, preferably 60 to 130 mgKOH / g. It is sufficient that the photocurable compound (A) and the epoxy-based saturated polycarboxylic acid compound (B) each have an acid value in the range of It preferably has an acid value within the above range. When the acid values of the photocurable compound (A) and the epoxy-based saturated polycarboxylic acid compound (B) are lower than 40 mgKOH / g, the solubility in an alkaline aqueous solution becomes poor, and the development of the formed film becomes difficult. On the other hand, if it is higher than 160 mgKOH / g, the surface of the exposed portion is developed irrespective of the exposure conditions, which is not preferable.
[0044]
Next, the acrylic saturated polycarboxylic acid compound (C) constituting the photocurable resin composition of the present invention will be described.
The acrylic saturated polycarboxylic acid compound (C) is prepared by polymerizing the following polymerizable monomer (f) containing (meth) acrylic acid as an essential component by a known method such as a solution polymerization method, an emulsion polymerization method, and a suspension polymerization method. It can be produced by polymerizing by a legal method or the like.
The most preferred method is a solution polymerization method. Specifically, a solvent is charged into a reaction vessel, and the following polymerizable monomer (f) containing (meth) acrylic acid as an essential component and a polymerization initiator are added in advance while stirring. Polymerization can be carried out by dropping the mixed solution at a constant rate, or simultaneously dropping the following polymerizable monomer and polymerizable initiator at a constant rate.
[0045]
The polymerizable monomer (f) is a radically polymerizable (meth) acrylic acid ester and / or vinyl monomer containing (meth) acrylic acid as an essential component, for example, methyl (meth) acrylate, Ethyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl ( Alkyl (meth) acrylates such as meth) acrylates, epoxy group-containing (meth) acrylates such as glycidyl (meth) acrylate, (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl ( Meta) a Hydroxyalkyl (meth) acrylates such as aminoalkyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, styrene, α-methylstyrene, vinyltoluene, p-methyl Aromatic polymerizable monomers such as styrene, vinyl esters such as vinyl acetate, polymerizable cyano compounds such as (meth) acrylonitrile, and carboxyl group-containing polymerizable monomers such as crotonic acid, maleic acid, fumaric acid, and monoalkyl maleate. Can be mentioned. These can be used alone or in combination of two or more.
[0046]
The amount of (meth) acrylic acid, which is an essential component of the polymerizable monomer (f), depends on the amount of the photocurable compound (A), the saturated epoxy polycarboxylic acid compound (B), and / or the saturated acrylic polycarboxylic acid compound. It is sufficient that the mixture of (C) has an acid value in the range of 40 to 160 mgKOH / g, preferably 70 to 130 mgKOH / g, and an amount sufficient to satisfy this range is used. It is preferable that each of the photocurable compound (A) and the epoxy-based saturated polycarboxylic acid compound (B) and / or the acrylic-based saturated polycarboxylic acid compound (C) has an acid value within the above range. When the acid value of the acrylic saturated polycarboxylic acid compound (C) is lower than 40 mgKOH / g, the solubility in an aqueous alkali solution becomes poor, and development of the formed film becomes difficult. On the other hand, if it is higher than 160 mgKOH / g, the surface of the exposed portion is developed irrespective of the exposure conditions, which is not preferable.
[0047]
Solvents that can be used in this case include, for example, methyl ethyl ketone, ketones such as cyclohexanone, aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene, methyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, and propylene glycol monoethyl. Glycol ethers such as ether, dipropylene glycol diethyl ether and triethylene glycol monoethyl ether, esters such as ethyl acetate, butyl acetate, butyl cellosolve acetate, carbitol acetate, alcohols such as ethanol, propanol, ethylene glycol and propylene glycol Organic solvents such as petroleum solvents such as oils, petroleum ethers, petroleum naphtha, hydrogenated petroleum naphtha, solvent naphtha, etc. It can be mentioned, which can be used in combination singly or in combination.
[0048]
As the polymerization initiator, a known radical polymerization catalyst can be used, and examples thereof include azobisisobutyronitrile, benzoyl peroxide, cumene hydroperoxide, and tert-butyl peroxybenzoate. These can be used alone or in combination of two or more. Further, if necessary, a chain transfer agent such as lauryl mercaptan or 2-mercaptoethanol can be used.
The polymerization initiator can be used in an amount of 0.1 to 5% by weight based on 100 parts by weight of the polymerizable monomer (f) containing (meth) acrylic acid as an essential component. . If the amount is less than 0.1% by weight, the reaction time is long and uneconomical, and the molecular weight of the polymer obtained by the reaction is undesirably high. On the other hand, when the content is 5% by weight or more, the reaction is too fast and the temperature control becomes difficult, and the polymer obtained by the reaction has a low molecular weight.
[0049]
The reaction of the acrylic saturated polycarboxylic acid compound (C) is performed at a reaction temperature of 30 to 180 ° C, preferably 60 to 150 ° C, and heating for 1 to 10 hours in the presence of an inert gas or air. Do it. By such a solution polymerization method, a copolymer having a weight average molecular weight of usually 3,000 to 300,000, preferably 8,000 to 250,000 is obtained.
[0050]
The photocurable resin composition of the present invention comprises a mixture of the photocurable compound (A) and the epoxy-based saturated polycarboxylic acid compound (B) and / or the acrylic-based saturated polycarboxylic acid compound (C). The mixing ratio of the photocurable compound (A) and the epoxy-based saturated polycarboxylic acid compound (B) and / or the acrylic-based saturated polycarboxylic acid compound (C) is such that the mixture is 600 to 4000 g / eq. Is preferable. In order to provide a cured film having sufficient flexibility, sufficiently small warpage, and excellent solder heat resistance, a range of 1000 to 2000 g / eq. . Is more preferably within the range having a double bond equivalent weight of When the double bond equivalent is 600 g / eq. When the temperature is lower, a cured film having excellent solder heat resistance can be obtained, but the cured film is not preferable because the cured film is brittle and generates a larger warpage. On the other hand, when the double bond equivalent is 4000 g / eq. If it is higher, the photocurability is reduced, and a resist pattern cannot be formed on the film, which is not preferable.
[0051]
Next, the epoxy compound (D) having two or more epoxy groups in one molecule in the photosensitive thermosetting resin composition of the present invention (hereinafter sometimes simply referred to as “resin composition”) will be described in detail. explain.
Epoxy compounds (D) having two or more epoxy groups in one molecule include, for example, trade names “Epicoat 828”, “Epicoat 834”, “Epicoat 1001”, “Epicoat 1004”, and the like manufactured by Japan Epoxy Resin Co., Ltd. "Epiclon 840", "Epiclon 850", "Epiclon 1050", "Epiclon 2055" manufactured by Nippon Ink and Chemicals, "Epototo YD-011", "Epototo YD-013" manufactured by Toto Kasei Co., "Epotote YD-127", "Epotote 128", trade names "DER317", "DER331", "DER 661", "Dow Chemical Co., Ltd." DER 664 ”, trade names“ Araldite 250 ”,“ Araldite 260 ”,“ Araldite 2600 ”manufactured by Asahi Kasei Corporation, Sumitomo Bisphenol A type epoxy compounds such as Gumi Kogyo Co., Ltd. product name "Sumiepoxy ESA-011", "Sumiepoxy ESA-014", "Sumiepoxy ELA-115", "Sumiepoxy ELA-128", manufactured by Dainippon Ink & Chemicals, Inc. Product name "Epiclon 830S", product name "Epicoat 807" manufactured by Japan Epoxy Resin Co., Ltd., product name "Epototo YDF-170", "Epototo YDF-175", "Epototo YDF-2004" manufactured by Toto Kasei, Asahi Kasei Corporation Bisphenol F type epoxy compounds such as "Araldite XPY306" manufactured by Nippon Kayaku Co., Ltd .; product name "EBPS-200" manufactured by Nippon Kayaku Co., Ltd .; product name "EPX-30" manufactured by Asahi Denka Kogyo Co., Ltd .; Bisphenol S-type epoxy compound such as "Epiclon EXA1514" Bisphenol fluorene type epoxy compounds such as "BPFG" manufactured by Osaka Gas Co., Ltd .; "YL-6056", "YL-6021", "YX-4000", "YX-400H" manufactured by Japan Epoxy Resin Co., Ltd. And the like, or hydrogenated bisphenol A type epoxy such as "Epototo ST-2004", "ST-2007", and "ST-3000" manufactured by Toto Kasei Co., Ltd. Compounds “Epicoat 152” and “Epicoat 154” manufactured by Japan Epoxy Resin, “DEN431” and “DEN438” manufactured by Dow Chemical, Dainippon Ink. “Epiclon N-690”, “Epiclon N-695”, “Epiclon N-730”, “Epiclon N-690” Ron N-770 "," Epiclon N-865 ", trade names" Epototo YDCN-701 "and" Epototo YDCN-704 "manufactured by Toto Kasei Co., Ltd., and" Araldite ECN1235 "and" Araldite ECN1273 "manufactured by Asahi Kasei Corporation. , "Araldite ECN1299", "Araldite XPY307", trade names "EPPN-201", "EOCN-1025", "EOCN-1020", "EOCN-104S", "RE-306", manufactured by Nippon Kayaku Co., Ltd., Sumitomo Novolak epoxy compounds such as "Sumiepoxy ESCN-195X" and "ESCN-220" manufactured by Chemical Industry Co., Ltd. Bisphenol A type novolak epoxy compounds such as "Epicoat 157S" manufactured by Japan Epoxy Resin, and Japan Epoxy Resin Company name “Epico” YL903 ", trade names" Epiclon 152 "and" Epiclon 165 "manufactured by Dainippon Ink & Chemicals, Inc., trade names" Epototo YDB-400 "and" Epototo YDB-500 "manufactured by Toto Kasei Co., Ltd. Product name "D. E. FIG. R. 542 ", a product name" Araldite 8011 "manufactured by Asahi Kasei Kogyo Co., Ltd., a brominated epoxy compound such as" Sumiepoxy ESB-400 "," Sumiepoxy ESB-700 "manufactured by Sumitomo Chemical Co., Ltd., a product name manufactured by Nippon Steel Chemical Epoxy compounds having a naphthalene skeleton such as "ESN-190", "ESN-360", trade names "HP-4032", "EXA-4750", and "EXA-4700" manufactured by Dainippon Ink and Chemicals, Dainippon Epoxy compounds having a dicyclopentadiene skeleton such as “HP-7200” and “HP-7200H” manufactured by Ink Chemical Industry Co., Ltd., “YL-933” manufactured by Japan Epoxy Resin, manufactured by Nippon Kayaku Co., Ltd. Trishydroxyphenylmethane type epoxy compounds such as "EPPN-501" and "EPPN-502", Nissan Chemical Heterocyclic epoxy compounds such as "TEPIC" manufactured by Mitsubishi Gas Chemical Company, "TGI" manufactured by Mitsubishi Gas Chemical Company, "Epicoat 604" manufactured by Japan Epoxy Resin, "Epototo YH" manufactured by Toto Kasei Glycidylamine-type epoxy compounds such as “-araldite MY720” manufactured by Asahi Kasei Kogyo Co., Ltd., “Sumiepoxy ELM-120” manufactured by Sumitomo Chemical Co., Ltd., and “Celoxide 2011” manufactured by Daicel Chemical Industries, Ltd. And alicyclic epoxy compounds such as "Araldite CY175" and "Araldite CY179" manufactured by Asahi Kasei Kogyo Co., Ltd., and "HBE-100" manufactured by Shin Nippon Rika Co., Ltd., and the like, but are not limited thereto. is not. These epoxy compounds can be used alone or in combination of two or more.
[0052]
The epoxy compound (D) having two or more epoxy groups in one molecule improves properties such as adhesiveness and heat resistance of the solder resist by heat curing after forming a resist pattern. The compounding amount of the photocurable compound (A) and the carboxyl group of the photocurable resin composition composed of a mixture of the epoxy-based saturated polycarboxylic acid compound (B) and / or the acrylic-based saturated polycarboxylic acid compound (C) The epoxy group is blended in the range of 0.1 to 1.5 equivalents, preferably 0.5 to 1.3 equivalents, per 1 equivalent of the group. If the amount is less than 0.1 equivalent, the moisture absorption of the cured film is increased and the electrical insulation is reduced. On the other hand, when the amount exceeds 1.5 equivalents, the photocurability and the alkali developability are reduced, and it is difficult to form a resist pattern.
[0053]
Next, the photopolymerization initiator (E) in the resin composition of the present invention will be described in detail. The photopolymerization initiator (E) used in the present invention has a function of generating radicals by irradiating ultraviolet rays when curing the resin composition with light (ultraviolet rays) and curing the radicals by radical polymerization.
[0054]
Known photopolymerization initiators (E) can be used, and preferred photopolymerization initiators (E) include, for example, benzoins such as benzoin, benzyl, benzoin methyl ether and benzoin isopropyl ether. And benzoin alkyl ethers, acetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2- Aetophenones such as morpholino-propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, N, N-dimethylaminoacetophenone, 2-methylanthraquinone, 2-methylanthraquinone, Ethyl anthraquinone, 2-ami Anthraquinones such as anthraquinone, thioxanthones such as 2,4-dimethylthioxanthone, ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal, benzophenone, methylbenzophenone, 4,4′-dichlorobenzophenone, and 4,4′-bisdiethylamino Examples thereof include benzophenones such as benzophenone and xanthones, and these can be used alone or in combination of two or more.
[0055]
Further, such a photopolymerization initiator (E) may be a benzoic acid ester such as ethyl-4-dimethylaminobenzoate or 2- (dimethylamino) ethylbenzoate, or a tertiary amine such as triethylamine or triethanolamine. Such known photosensitizers can be used alone or in combination of two or more.
The amount of the photopolymerization initiator (E) used is a photocurable resin (A) and a photocurable resin comprising an epoxy-based saturated polycarboxylic acid compound (B) and / or an acrylic-based saturated polycarboxylic acid compound (C). It is preferably used in an amount of 0.1 to 30 parts by weight, more preferably 1 to 20 parts by weight, based on 100 parts by weight of the composition. If the amount is less than 0.1 part by weight, polymerization does not proceed by irradiation with ultraviolet rays, and the formed film becomes uncured and developability is deteriorated. On the other hand, when the amount exceeds 30 parts by weight, the heat resistance and mechanical properties of the cured film are undesirably reduced.
[0056]
Next, the diluent (F) in the resin composition of the present invention will be described in detail.
The diluent (F) used in the present invention dissolves the photocurable compound (A), the epoxy-based saturated polycarboxylic acid compound (B) and / or the acrylic-based saturated polycarboxylic acid compound (C), and forms an ink. Those having the action and reactivity of ensuring an appropriate working viscosity are taken into the network during radical polymerization, and have an effect on photocurability, improvement in heat resistance, and the like.
[0057]
Examples of such a diluent (F) include ketones such as methyl ethyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene, methyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol and propylene. Glycol ethers such as glycol monoethyl ether, dipropylene glycol diethyl ether, and triethylene glycol monoethyl ether; esters such as ethyl acetate, butyl acetate, butyl cellosolve acetate, and carbitol acetate; ethanol, propanol, ethylene glycol, propylene glycol, and the like Organic solvents such as alcohols, aliphatic hydrocarbons such as octane and decane, petroleum ethers, petroleum naphtha, hydrogenated petroleum naphtha, solvent naphtha, etc. It can be exemplified, but the invention is not limited thereto. These can be used alone or in combination of two or more.
[0058]
The diluent (F) can be used by replacing part or all of the organic solvent with (meth) acrylates having photocurability. Examples of such (meth) acrylic esters include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, i-butyl (meth) acrylate, and t-butyl. Alkyl (meth) acrylates such as (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, and stearyl (meth) acrylate; epoxy group-containing (meth) acrylates such as glycidyl (meth) acrylate; Aminoalkyl (meth) acrylates such as meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl Hydroxyalkyl (meth) acrylates such as (meth) acrylates; mono- or di (meth) acrylates of glycols such as ethylene glycol, methoxytetraethylene glycol, and polyethylene glycol; N, N-dimethyl (meth) acrylamides; Aminoalkyl (meth) acrylates such as dimethylaminoethyl (meth) acrylate, polyhydric alcohols such as hexanediol, trimethylolpropane, pentaerythritol, ditrimethylolpropane, dipentaerythritol, and tris-hydroxyethylisocyanurate; or Polyethylene (meth) acrylates of these ethylene oxide or propylene oxide adducts, phenoxyethyl (meth) acrylate, polyethoxydi of bisphenol A ( (T) (meth) acrylates of glyceryl ethers such as ethylene oxide or propylene oxide adducts of phenols such as acrylates, glycerin diglycidyl ether, trimethylolpropane triglycidyl ether, triglycidyl isocyanurate, and ε. -Caprolactone-modified [epsilon] -caprolactone-modified (meth) acrylates such as tris (acryloxyethyl) isocyanurate; melamine (meth) acrylate; and the like, but are not limited thereto. These can be used alone or in combination of two or more.
[0059]
The amount of the diluent (F) used is 100 parts by weight of a mixture of the photocurable compound (A) and the epoxy-based saturated polycarboxylic acid compound (B) and / or the acrylic-based saturated polycarboxylic acid compound (C). In the range of 1 to 300 parts by weight. In the case where (meth) acrylic acid esters are used in the diluent (F), the amount of the (meth) acrylic esters used is the above-mentioned photocurable compound (A), epoxy-based saturated polycarboxylic acid compound (B) and / or Alternatively, it is used in an amount of 3 to 50 parts by weight, preferably 5 to 15 parts by weight, based on 100 parts by weight of a photocurable resin composition comprising a mixture of an acrylic saturated polycarboxylic acid compound (C). Is preferred. When the amount is less than 3 parts by weight, the effect of imparting photocurability is not sufficient, and when the amount exceeds 50 parts by weight, the dryness of the dry film to the touch is reduced, which is not preferable.
[0060]
The resin composition of the present invention comprises a light curable compound comprising a mixture of the photocurable compound (A) in the heat curing step and an epoxy-based saturated polycarboxylic acid compound (B) and / or an acrylic-based saturated polycarboxylic acid compound (C). For the purpose of accelerating the reaction between the carboxyl group of the curable resin composition and the epoxy compound (D) having two or more epoxy groups in one molecule, a curing accelerator can be added. As the curing accelerator, for example, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- Imidazole derivatives such as (2-cyanoethyl) -2-ethyl-4-methylimidazole, guanamines such as guanamine, acetoguanamine and benzoguanamine, dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine And amine compounds such as 4-methyl-N, N-dimethylbenzylamine and melamine. These can be used alone or in combination of two or more.
[0061]
The amount of the curing accelerator used is such that the photocurable compound (A) is mixed with the epoxy saturated polycarboxylic acid compound (B) and / or the acrylic saturated polycarboxylic acid compound (C). It can be used in an amount of 0.1 to 10 parts by weight, preferably 0.5 to 2 parts by weight, based on 100 parts by weight of the conductive resin composition. When the amount is less than 0.1 part by weight, the effect of accelerating the curing reaction of the epoxy compound (D) having two or more epoxy groups in one molecule is reduced. The life of the object is shortened, and neither is preferable.
[0062]
An inorganic filler can be added to the resin composition of the present invention for the purpose of improving the adhesion to a printed wiring board. For example, inorganic fillers such as talc, silica, barium sulfate, barium titanate, silicon oxide, aluminum oxide, calcium carbonate, and aluminum hydroxide can be blended. These inorganic fillers can be added in a range of up to 150 parts by weight based on 100 parts by weight of the resin composition. If the amount exceeds 150 parts by weight, the curability is adversely affected, and the physical properties of the cured film are reduced.
[0063]
To the resin composition of the present invention, in addition to the above components, various coloring agents, leveling agents, defoaming agents, and the like, which are added to ordinary resin compositions, can be added.
[0064]
The resin composition of the present invention can be obtained by uniformly mixing the above-described components with a roll mill, a sand mill, or the like. The application of the resin composition of the present invention onto a printed wiring board is usually performed by a screen printing method, an electrostatic coating method, a roll coater method, a curtain coater method, or the like. After coating, the coating is dried at 60 to 90 ° C. for 10 to 60 minutes, and after irradiating with active energy rays such as ultraviolet rays, unexposed portions are removed with a dilute alkali aqueous solution such as a 0.1 to 5% by weight aqueous sodium carbonate solution. And develop. Finally, a heat treatment (100 to 180 ° C. for 5 to 60 minutes) using a hot-air drier or far-infrared ray to completely cure the film, the epoxy compound having two or more epoxy groups in one molecule. In addition to the curing reaction of (D), the polymerization of the (meth) acrylates of the photocurable compound (A) and the diluent (F) is promoted, and a cured film having excellent adhesion, heat resistance and mechanical properties is formed. Obtainable. Furthermore, for example, by heating to a temperature of 140 to 180 ° C. to thermally cure, if necessary, the polymerization of the (meth) acrylates of the photocurable compound (A) and the diluent (F) is further performed. Exposure with light (ultraviolet light) can also be performed for the purpose of accelerating.
As an irradiation light source for curing light (ultraviolet light), a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, a metal halide lamp, or the like can be used.
[0065]
【Example】
Hereinafter, the present invention will be described more specifically with reference to examples. The present invention is not limited to the following examples. In this example, "parts" are parts by weight unless otherwise specified.
[0066]
(1) Example of synthesizing epoxy compound as raw material for synthesizing photocurable compound (A)
[0067]
Synthesis Example 1
In a flask equipped with a gas inlet tube, a stirrer, a cooling tube, a thermometer, and a dropping device, 763 parts of a bisphenol A type epoxy compound (trade name “Araldite 2600” manufactured by Asahi Kasei Kogyo Co., Ltd.) and 237 parts of bisphenol F are charged, and Was replaced with nitrogen and heated to 100 ° C. with stirring to dissolve. Next, 0.5 part of triphenylphosphine was charged under stirring, reacted at 150 to 160 ° C. for 1 hour, and diluted with 2452 parts of epichlorohydrin. Next, the mixture was cooled and maintained at 40 ° C. with stirring, and 17 parts of 98 wt% tetrabutylammonium bromide was charged and dissolved. Thereafter, 265 parts of 48% by weight caustic soda was continuously added dropwise over 1 hour under stirring, and the mixture was reacted for 3 hours after the addition. After completion of the reaction, excess epichlorohydrin was distilled off under reduced pressure, and the reaction product containing by-product salts was diluted with 2000 parts of methyl isobutyl ketone and washed three times with 500 parts of water. Then, methyl isobutyl ketone was distilled off under reduced pressure to obtain an epoxy equivalent of 273 g / eq. (This means that one molecule has an average of 5.0 epoxy groups.) A bisphenol F-modified bisphenol A type polyfunctional epoxy compound (a) having a softening point of 59 ° C was obtained.
[0068]
Synthesis Example 2
A flask equipped with the same apparatus as in Synthesis Example 1 was charged with 714 parts of a cresol novolak compound in which the value of n in the general formula (2) is 2 to 3 and 2775 parts of epichlorohydrin, and the inside of the flask was replaced with nitrogen. The mixture was heated to 40 ° C. under stirring to dissolve. Thereafter, the temperature was raised to 68 ° C. with stirring, and the reaction was carried out for 3.5 hours while continuously dropping 450 parts by weight of 48% by weight caustic soda. After completion of the reaction, excess epichlorohydrin was distilled off under reduced pressure, the reaction product containing by-product salts was dissolved in 2000 parts of methyl isobutyl ketone, and 10% by weight of sodium hydroxide was further charged. Allowed to react for hours. After the completion of the reaction, the resultant was washed three times with 500 parts of water. Thereafter, methyl isobutyl ketone was distilled off under reduced pressure to obtain an epoxy equivalent of 208 g / eq. A cresol novolak-type epoxy compound (b) having a softening point of 87 ° C. was obtained.
[0069]
(2) Synthesis example of photocurable compound (A)
[0070]
Synthesis Example 3
346 parts of the epoxy compound (a) obtained in Synthesis Example 1 was charged into a flask equipped with a gas inlet tube, a stirrer, a cooling tube, and a thermometer, and was heated to 100 to 110 ° C and dissolved under stirring. Then, while blowing air under stirring, 91 parts of acrylic acid, 0.4 parts of monomethyl ether hydroquinone and 1.3 parts of triphenylphosphine were charged and reacted at 110 to 120 ° C. for 10 hours. Then, the mixture was diluted with 280 parts of carbitol acetate under stirring, 163 parts of tetrahydrophthalic anhydride was charged, reacted at 110 to 120 ° C. for further 8 hours, diluted with 120 parts of solvent naphtha and cooled to obtain an acid. Value (nonvolatile content) 100 mgKOH / g, nonvolatile content 60%, double bond equivalent 473 g / eq. The photocurable compound (A-1) was obtained.
[0071]
Synthesis Example 4
Using the same apparatus as in Synthesis Example 3, 436 parts of the epoxy compound (a) obtained in Synthesis Example 1, 115 parts of acrylic acid, 0.6 parts of monomethyl ether hydroquinone, 1.7 parts of triphenylphosphine, and tetrahydrofuran Except that phthalic anhydride was changed to 49 parts, the same blending and operation as in Synthesis Example 3 was performed to obtain an acid value (non-volatile content) of 30 mgKOH / g, a non-volatile content of 60%, and a double bond equivalent of 376 g / eq. The photocurable compound (A-2) was obtained.
[0072]
Synthesis Example 5
Using the same apparatus as in Synthesis Example 3, 346 parts of the epoxy compound (a) obtained in Synthesis Example 1 was charged, and heated and dissolved at 100 to 110 ° C. with stirring. Thereafter, while blowing air under stirring, 78 parts of acrylic acid, 14 parts of propionic acid, 0.4 parts of monomethyl ether hydroquinone, and 1.3 parts of triphenylphosphine were charged and reacted at 110 to 120 ° C. for 10 hours. Then, the mixture was diluted with 280 parts of carbitol acetate under stirring, 163 parts of tetrahydrophthalic anhydride was charged, reacted at 110 to 120 ° C. for further 8 hours, diluted with 120 parts of solvent naphtha and cooled to obtain an acid. Value (nonvolatile content) 100 mgKOH / g, nonvolatile content 60%, double bond equivalent 557 g / eq. The photocurable compound (A-3) was obtained.
[0073]
Synthesis Example 6
Using the same apparatus as in Synthesis Example 3, 343 parts of the epoxy compound (b) obtained in Synthesis Example 2 was charged, and heated and dissolved at 100 to 110 ° C. with stirring. Thereafter, 119 parts of acrylic acid, 0.5 part of monomethyl ether hydroquinone, and 1.4 parts of triphenylphosphine were charged and reacted at 110 to 120 ° C. for 10 hours while blowing air. Then, after diluting with 280 parts of carbitol acetate under stirring, 138 parts of tetrahydrophthalic anhydride is charged, reacted at 110 to 120 ° C. for further 8 hours, diluted with 120 parts of solvent naphtha and cooled to obtain an acid. Value (nonvolatile content) 85 mgKOH / g, nonvolatile content 60%, double bond equivalent 364 g / eq. (A-4) was obtained.
[0074]
Synthesis Example 7
In the same apparatus as in Synthesis Example 3, 330 parts of the epoxy compound (b) obtained in Synthesis Example 2 was charged, and heated and dissolved at 100 to 110 ° C. with stirring. Thereafter, while blowing air under stirring, 80 parts of acrylic acid, 51 parts of cresol, 0.5 part of monomethyl ether hydroquinone, and 1.4 parts of triphenylphosphine were charged and reacted at 110 to 120 ° C. for 10 hours. Then, after diluting with 280 parts of carbitol acetate under stirring, 138 parts of tetrahydrophthalic anhydride is charged, reacted at 110 to 120 ° C. for further 8 hours, diluted with 120 parts of solvent naphtha and cooled to obtain an acid. Value (non-volatile content) 85 mgKOH / g, non-volatile content 60%, double bond equivalent 547 g / eq. The photocurable compound (A-5) was obtained.
[0075]
(3) Synthesis example of epoxy-based saturated polycarboxylic acid compound (B)
[0076]
Synthesis Example 8
In the same apparatus as in Synthesis Example 3, 326 parts of a hydrogenated bisphenol A type epoxy compound (trade name “HBE-100” manufactured by Nippon Rika Co., Ltd.) and 63 parts of adipic acid were charged, and the inside of the flask was replaced with nitrogen. The mixture was heated to 100 ° C. with stirring to dissolve. Next, 0.2 parts of triphenylphosphine was charged under stirring and reacted at 150 to 160 ° C. for 1 hour. Thereafter, the mixture was cooled to 100 ° C, and 48 parts of propionic acid and 1.3 parts of triphenylphosphine were charged and reacted at 130 to 140 ° C for 5 hours with stirring. Then, under stirring, after diluting with 280 parts of carbitol acetate, 163 parts of tetrahydrophthalic anhydride was charged, reacted at 110 to 120 ° C. for further 8 hours, diluted with 120 parts of solvent naphtha and cooled, An epoxy-based saturated polycarboxylic acid compound (B-1) having an acid value (non-volatile content) of 100 mgKOH / g and a non-volatile content of 60% was obtained.
[0077]
Synthesis Example 9
In the same apparatus as in Synthesis Example 3, 411 parts of the same hydrogenated bisphenol A type epoxy compound as used in Synthesis Example 8, 80 parts of adipic acid, 61 parts of propionic acid, 1.7 parts of triphenylphosphine, The same blending and operation as in Synthesis Example 8 was carried out except that the phthalic anhydride was changed to 49 parts, and an epoxy-based saturated polycarboxylic acid compound (B-2) having an acid value (non-volatile content) of 30 mgKOH / g and a non-volatile content of 60% was used. ) Got.
[0078]
Synthesis Example 10
In the same apparatus as in Synthesis Example 3, 266 parts of a bisphenol F-type epoxy compound (trade name “Epiclon 830S” manufactured by Dainippon Chemical Co., Ltd.) and 98 parts of bisphenol F were charged, and the flask was replaced with nitrogen. Heated to ° C. to dissolve. Next, 0.2 parts of triphenylphosphine was charged under stirring and reacted at 150 to 160 ° C. for 1 hour. Thereafter, the mixture was cooled to 100 ° C., charged with 73 parts of benzylmethylamine, and reacted at 110 to 120 ° C. for 5 hours with stirring. Then, under stirring, after diluting with 280 parts of carbitol acetate, 163 parts of tetrahydrophthalic anhydride was charged, reacted at 110 to 120 ° C. for further 8 hours, diluted with 120 parts of solvent naphtha and cooled, An epoxy saturated polycarboxylic acid compound (B-3) having an acid value (non-volatile content) of 100 mgKOH / g and a non-volatile content of 60% was obtained.
[0079]
(4) Synthetic example of acrylic saturated polycarboxylic acid compound (C)
[0080]
Synthesis Example 11
In the same apparatus as in Synthesis Example 1, 280 parts of carbitol acetate were charged and, after purging with nitrogen, at 130 to 135 ° C., 118 parts of methyl methacrylate, 390 parts of ethyl acrylate, 92 parts of methacrylic acid, 92 parts of di-t A mixture of 3.6 parts of -butyl peroxide was continuously dropped over 3 hours to carry out a polymerization reaction, and further reacted at 130 to 135 ° C. for 3 hours. Thereafter, the mixture was diluted with 120 parts of solvent naphtha and cooled to obtain an acrylic saturated polycarboxylic acid compound (C-1) having an acid value (non-volatile content) of 100 mgKOH / g and a non-volatile content of 60%.
[0081]
Synthesis Example 12
Using the same apparatus as in Synthesis Example 1, the same blending and operation as in Synthesis Example 11 was performed except that methyl methacrylate was changed to 133 parts, ethyl acrylate to 439 parts, and methacrylic acid to 28 parts, and the acid value (nonvolatile content) was 30 mg KOH. / G, an acrylic saturated polycarboxylic acid compound (C-2) having a nonvolatile content of 60%.
[0082]
Synthesis Example 13
Using the same apparatus as in Synthesis Example 1, the same blending and operation as in Synthesis Example 11 was performed except that methyl methacrylate was changed to 97 parts, ethyl acrylate to 319 parts, and methacrylic acid to 184 parts, and the acid value (nonvolatile content) was 200 mg KOH. / G, an acrylic saturated polycarboxylic acid compound (C-3) having a nonvolatile content of 60%.
[0083]
Examples 1 to 14 and Comparative Examples 1 to 14
The photocurable compound (A) obtained in Synthesis Examples 3 to 7 and the epoxy-based saturated polycarboxylic acid compound (B) obtained in Synthesis Examples 8 to 10 and / or obtained in Synthesis Examples 11 to 13. Photocurable resin composition obtained by mixing an acrylic saturated polycarboxylic acid compound (C) A composition having the composition shown in Tables 1 and 2 using a varnish was kneaded with a three-roll mill, and the photosensitive thermosetting resin was cured. A resin composition was obtained. Tables 3 and 4 show the physical properties of each composition.
[0084]
In Tables 1 and 2,
1) "Irgacure 907" is 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinoaminopropane-1 (a photopolymerization initiator manufactured by Ciba Specialty Chemicals).
2) "YX-4000" is a xylene biphenyl type epoxy compound (manufactured by Japan Epoxy Resin Co., Ltd.).
3) "BYK-A555" is an acrylic defoamer (manufactured by BYK Big Chemie).
4) "Carboxyl group" is a carboxyl group of the photocurable resin composition.
5) “Epoxy group” is an epoxy group of the epoxy compound (D).
[0085]
[Table 1]

[0086]
[Table 2]

[0087]
The evaluation of physical properties in Tables 3 and 4 was performed by the following methods.
[0088]
(1) Dryness to the touch
The compositions of the above Examples and Comparative Examples were applied to the entire surface of a copper foil substrate (thickness: 1.6 mm) by screen printing, dried at 80 ° C. for 30 minutes in a hot-air drying furnace, and allowed to cool to room temperature. Thereafter, the dryness to the touch of the coating film was confirmed with a finger. The criteria are as follows.
：: no tack.
×: There is tack.
[0089]
(2) Alkaline developability
The compositions of the above Examples and Comparative Examples were applied to the entire surface of a copper foil substrate (thickness: 1.6 mm) by screen printing, dried at 80 ° C. for 30 minutes in a hot-air drying furnace, and allowed to cool to room temperature. Thereafter, a 1% aqueous solution of sodium carbonate at 30 ° C. was developed for 60 seconds under the condition of a spray pressure of 0.2 MPa, and the presence or absence of undeveloped portions of the coating film was visually checked. The criteria are as follows.
：: Completely developed.
Δ: Part of the coating film remains.
X: The coating film remains completely.
[0090]
(3) Sensitivity
The compositions of the above Examples and Comparative Examples were applied to the entire surface of a copper foil substrate (thickness: 1.6 mm) by screen printing, dried at 80 ° C. for 30 minutes in a hot-air drying furnace, and allowed to cool to room temperature. Thereafter, a step tablet (Kodak No. 2, total 14 steps) is placed on the coating film, and the exposure amount is 500 mJ / cm. ² The film was exposed to light under a condition of 1), developed with a 1% aqueous solution of sodium carbonate at 30 ° C. under a spray pressure of 0.2 MPa for 60 seconds, and visually evaluated for the number of steps of the remaining coating film.
[0091]
(4) Adhesion
The compositions of the above Examples and Comparative Examples were applied to the entire surface of a polyimide film (50 μm thick) by screen printing, dried in a hot-air drying oven at 80 ° C. for 30 minutes, allowed to cool to room temperature, and exposed. 500mJ / cm ² And cured in a hot air drying oven at 150 ° C. for 60 minutes, and allowed to cool to room temperature (film thickness: 20 μm). The adhesion of the cured coating film was evaluated according to the following criteria in accordance with JIS D0202.
：: The number of grids completely remains.
Δ: Less than 100 crosses, 60 or more crosses remaining.
X: Less than 60 crosscuts remained.
[0092]
(5) Folding resistance
The composition of each of the above Examples and Comparative Examples was applied to the entire surface of a polyimide film (25 μm in thickness) by screen printing, dried in a hot-air drying oven at 80 ° C. for 30 minutes, allowed to cool to room temperature, and exposed. 500mJ / cm ² And cured in a hot air drying oven at 150 ° C. for 60 minutes, and allowed to cool to room temperature (film thickness: 20 μm). The bending resistance of the cured coating film was evaluated according to the following criteria by bending the obtained cured coating film by 180 degrees.
：: No crack in the cured coating film.
Δ: The cured coating film has some cracks.
X: The cured coating film has many cracks.
[0093]
(6) Warpage
The composition of each of the above Examples and Comparative Examples was applied to the entire surface of a polyimide film (25 μm in thickness) by screen printing, dried in a hot-air drying oven at 80 ° C. for 30 minutes, allowed to cool to room temperature, and exposed. 500mJ / cm ² And cured in a hot air drying oven at 150 ° C. for 60 minutes, and allowed to cool to room temperature (film thickness: 20 μm). Thereafter, the obtained cured coating film was cut into a size of 5 cm × 5 cm to obtain a test piece. For the warpage of the cured coating film of each composition, the height at which the four corners of each test piece were warped was measured with a ruler, and the average value was evaluated according to the following criteria.
A: No warpage.
：: Warpage rising from 0 mm to less than 1 mm.
Δ: Warpage rising of 1 mm or more and less than 5 mm.
×: Warpage of 5 mm or more.
[0094]
(7) Solder heat resistance
The composition of each of the above Examples and Comparative Examples was applied on the entire surface of a copper foil substrate (1.6 mm) by screen printing, dried at 80 ° C. for 30 minutes in a hot air drying furnace, and allowed to cool to room temperature. Exposure 500mJ / cm ² And cured in a hot air drying oven at 150 ° C. for 60 minutes, and allowed to cool to room temperature (film thickness: 20 μm). A rosin flux was applied to the obtained cured coating film, immersed in a solder bath at 260 ° C. for 10 seconds (twice), and the state of the coating film was evaluated according to the following criteria.
：: The cured coating has no blistering, peeling or discoloration.
Δ: The cured coating film slightly swells, peels off, and has discoloration.
×: Most of the cured coating film has blisters, peeling, and discoloration.
[0095]
(8) PCT (pressure cooker test) resistance
The composition of each of the above Examples and Comparative Examples was applied on the entire surface of a copper foil substrate (1.6 mm) by screen printing, dried at 80 ° C. for 30 minutes in a hot air drying furnace, and allowed to cool to room temperature. Exposure 500mJ / cm ² And cured in a hot air drying oven at 150 ° C. for 60 minutes, and allowed to cool to room temperature (film thickness: 20 μm). For the PCT resistance, the obtained cured coating film was placed in an environment of 121 ° C. and 100% RH, and the state of the coating film after 50 hours was evaluated according to the following criteria.
：: The cured coating has no blistering, peeling or discoloration.
Δ: The cured coating film has some blistering, peeling, and discoloration.
×: Most of the cured coating film has blisters, peeling, and discoloration.
[0096]
[Table 3]

[0097]
[Table 4]

[0098]
As is clear from the results in Tables 3 and 4, the photosensitive thermosetting resin composition of the present invention is balanced in dryness to the touch of a coating film, alkali developability, and sensitivity, and the cured product is sufficiently cured. A cured product having excellent flexibility, no or small warpage, excellent adhesion to the polyimide film of the substrate, and excellent solder heat resistance and PCT resistance can be provided. On the other hand, the resin composition of the comparative example had poor balance in dryness to the touch, alkali developability, sensitivity, and adhesion to the substrate, and had a large warpage.
[0099]
【The invention's effect】
As described above, the photocurable resin composition of the present invention includes a photocurable compound produced from an epoxy compound having three or more epoxy groups in one molecule, and an epoxy-based saturated polycarboxylic acid compound and / or It is composed of a mixture of acrylic saturated polycarboxylic acid compounds, and the photocurable compound has an effect of maintaining photocurability and heat resistance, and further has an epoxy saturated polycarboxylic acid having only a carboxyl group as a functional group in the molecule. By mixing the compound and / or the acrylic saturated polycarboxylic acid compound, the compound has an effect of alleviating stress distortion in a coating film after thermosetting which is a cause of warpage.
[0100]
Further, the photosensitive thermosetting resin composition of the present invention containing such a photocurable resin composition as a photocurable component has excellent balance between dryness to touch, photocurability, and alkali developability, and Produces a cured product with a high level of sufficient flexibility, heat resistance, adhesion, and PCT resistance, and has no warpage after thermosetting. Therefore, manufacturing of printed wiring boards and printed wiring boards with solder resist Of IC packages such as BGA (Ball Grid Array) and CSP (Chip Scale Package) using a resin and sealing resin, especially COF (Chip-on-Film) using thin film base material such as polyimide film and And / or facilitate mounting of electronic components on flexible printed wiring boards.

Claims (8)

An epoxy compound (a) having three or more epoxy groups in one molecule represented by the following general formulas (1) and / or (2), and an unsaturated group-containing monocarboxylic acid (b) or an unsaturated group-containing A reaction product obtained by reacting a monobasic acid selected from a mixture of a monocarboxylic acid (b) and a saturated active hydrogen compound (c) is further reacted with a polybasic acid anhydride (d) to obtain a light. A curable compound (A),
A polybasic acid anhydride (d) is further reacted with a reaction product obtained by reacting an epoxy compound (e) having two or more epoxy groups in one molecule with a saturated active hydrogen compound (c). With an acrylic saturated polycarboxylic acid compound (C) obtained by polymerizing a polymerizable monomer (f) containing an epoxy-based saturated polycarboxylic acid compound (B) and / or (meth) acrylic acid as an essential component. The mixture has a double bond equivalent of 600 to 4000 g / eq. A photocurable resin composition characterized by the above range.
General formula (1)

(Where M is -H or

And at least one of M is

X and Y are the same or different divalent aromatic groups, and m represents 1 to 20. )
General formula (2)

(In the formula, R represents —H or CH ₃ , and n represents 1 to 20.) The photocurable composition according to claim 1, wherein the saturated active hydrogen compound (c) is at least one or more saturated active hydrogen compounds selected from the group consisting of monocarboxylic acids, monophenols, and secondary monoamines. Resin composition. The mixture of the photocurable compound (A) and the epoxy-based saturated polycarboxylic acid compound (B) and / or the acrylic-based saturated polycarboxylic acid compound (C) has an acid value in a range of 40 to 160 mgKOH / g. The photocurable resin composition according to claim 1, wherein: The photocurable resin composition according to claim 1, an epoxy compound (D) having two or more epoxy groups in one molecule, a photopolymerization initiator (E), and a diluent (F). A photosensitive thermosetting resin composition, comprising: The equivalent of the epoxy group of the epoxy compound (D) having two or more epoxy groups in one molecule is in the range of 0.1 to 1.5 equivalent to 1 equivalent of the carboxyl group in the photocurable resin composition. The photosensitive thermosetting resin composition according to claim 4, which is blended. The photopolymerization initiator (E) is blended in an amount of 0.1 to 30 parts by weight based on 100 parts by weight of the photocurable compound (A) in the photocurable resin composition. 6. The photosensitive thermosetting resin composition according to 4 or 5. The diluent (F) is an organic solvent and / or (meth) acrylic acid ester, and is mixed in an amount of 1 to 300 parts by weight based on 100 parts by weight of the photocurable resin composition. Item 7. The photosensitive thermosetting resin composition according to any one of Items 4 to 6. A cured product obtained by curing the photosensitive thermosetting resin composition according to any one of claims 4 to 7.